Abstract Book

Abstract Book 06/25/2007 06:28 PM
1. Self assembly and immunity of microemulsion and polymer networks

Samuel A. Safran, Weizmann Institute of Science, Rehovot, Israel
Self-assembling networks occur in diverse colloidal systems including cylindrical micelles and microemulsions,
ferrofluids, and polymer-colloid assemblies. Although the microscopic nature of these systems can be quite different, the
statistical thermodynamics and phase behavior can be quite similar. In particular, we show theoretically that such
networks generally exhibit phase coexistence between dilute and dense network phases; these transitions are driven by
the competition of the translational entropy (that dominates in the dilute phases) and the configurational entropy (that
dominates in the dense network phases). The predictions are in agreement with both structural and thermodynamic
studies. Recently, we have focused on the immunity of networks comprising (several) telechelic polymers that connect
oil in water microemulsion drops. The dense network phase of this system has higher immunity if it survives a random
degradation of polymers, that is, if the network is more likely to maintain a macroscopic connected component. We
predict that gel immunity decreases with an increase of the variance of the distribution of the number of polymers that
connect a given pair of drops. Repulsive interactions between the polymers decrease the variance, while attractive
interactions increase the variance.
*Work done in collaboration with: G. Hed, T. Tlusty, A. Zilman - theory; A. Bernheim, T. Foster, G. Porte, T. Sottmann,
R. Strey, Y. Talmon - experiment.
2. Keynote: DFT Modeling of Novel Materials

Matthew Neurock, University of Virginia, Charlottesville, VA
DFT Modeling of Novel Materials
3. Mechanisms of Metal Atom Clustering and Nanofilament Formation in Vapor Deposition

of Metal Atoms on Alkanethiolate Self-Assembled Monolayers on Au{111}
Masato Maitani, Thomas A. Daniel, Orlando M. Cabarcos and David L. Allara, The Pennsylvania State University,
University Park, PA
A fundamental understanding of the metal deposition process on organic self-assembled monolayers (SAMs) is
important in designing high quality interfaces between metal and organic materials for organic electronic device
applications. The behavior of thermally evaporated Al deposition on S(CH2 ) 15 CH3 SAMs on Au {1 1 1} is interesting,
since a previous report showed a distinct transition in the deposition process from penetration through the SAM to the
underlying substrate to cluster generation at the vacuum interface, based on in-situ XPS, IRS, and ToF-SIMS probes
[1]. We have now studied this behavior with in-situ AFM to observe the topographic features and electrical
conductance properties with increasing Al coverage. The AFM results confirm Al penetration in the initial stage, then a
transition to a uniform growth of metal nanofilaments and finally surface cluster generation. We have probed the I-V
characteristics of individual filaments which can be as small in diameter as single atoms in the limit.
[1] A. Hooper, G.L. Fisher, K. Konstadinidis, D. Jung, H. Nyugen, R. Opila, R.W. Collins, N. Winograd, and D.L. Allara,
J.Am.Chem.Soc., 121, 8052-8064 (1999).
4. Selective deposition of metals on patterned self-assembled monolayer surfaces: Towards

molecular electronic circuitry
Amy Walker, Washington University, St. Louis, MO
We have developed a robust method by which to construct complex two- and three- dimensional structures based on
controlling interfacial chemistry. This work has important applications in molecular/organic electronics, sensing, and
other technologies. Our method is extensible to many different materials, easily parallelized, affords precise nanoscale
placement and is fully compatible with photolithography. Our work to date has provided a simple method for the
construction of complex 2D molecular electronic circuitry using UV-photopatterning and the reaction of deposited metals
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with self-assembled monolayers (SAMs). To demonstrate the method we have selectively vapor-deposited Mg on a
patterned -CH3 /-COOH terminated alkanethiolate surface. The deposited metal penetrates through the -CH3 SAM to
the Au/S interface while reacting with and accumulating on top of the -COOH SAM. In a second demonstration we have
employed room temperature chemical vapor deposition (CVD) to selectively deposit on patterned -CH3 /-COOH
terminated alkanethiolate SAMs. Applying these ideas to the rational design of metal/organic structures requires a
fundamental understanding of the underlying metal-molecule interactions; we therefore shall also discuss experiments
that elucidate these.
5. Surface preparation of supported flat gold nanoparticles for use as Au{111} substrates
Daminda H. Dahanayaka, Wesley D. Tennyson, Christopher E. Allen, Preston R. Larson, Daniel J. Wasielewski,
Marshall D. McCutchen, David S. Hartnett, Matthew B. Johnson and Lloyd A. Bumm, University of Oklahoma, Norman,
OK
Flat gold nanoparticles (FGNPs) grown in aqueous solution have large Au{111} facets that are excellent substrates for
scanning probe microscopy. However adsorbed stabilizers (e.g. polyelectrolytes) must be removed or displaced before
the FGNP surfaces can be used as single crystal surfaces. We have explored the effects of plasma cleaning, UV
ozone, CO2 snow cleaning, and thermal annealing on the Au{111} terrace structure using STM. We have also applied
an addressed grid system to track and to correlate images of selected particles through the cleaning and annealing
procedures using SEM, AFM, and optical.
This work has been supported by NSF CAREER grant No. CHE- 0239803, NSF MRSEC No. DMR-0080054, and
AFOSR No. FA9550- 06-1-0365.
6. The Initial Stages of Self-Organization of Silica-Alumina Gels in Zeolite Synthesis

Joseph M. Fedeyko1 , Dustin Fickel2 , Raul F. Lobo2 and Dionisios G. Vlachos 2 , (1)Johnson Matthey Catalysts,
Wayne, PA, (2)University of Delaware, Newark, DE
Zeolites have consistently been a topic of intense research because of their tunable catalytic properties, the result of the
incorporation of different elements (aluminum, germanium, boron, etc.) in the silica crystalline framework. For many
years, alumina incorporation has been shown to result in different crystalline structures and particle morphologies;
however, the majority of studies focusing on the nucleation and growth of zeolite materials have focused solely on all-
silica syntheses. Here, we expand on our recent research of the self-assembly of silica in basic solutions of small
organic cations by studying the impact of alumina on these systems.
The effect aluminum on the initial condensation of silica in basic solutions of organic and inorganic cations is analyzed
using conductivity, pH, NMR spectroscopy and small angle scattering methods. The addition of alumina to these
solutions decreases substantially the point at which nanoparticles form. At high alumina concentrations, the particles
are smaller than those found in all-silica solutions and spherical in shape. We argue, using equilibrium thermodynamic
theory, that the composition should be rich in aluminum. In the case of sodium, larger rather than smaller particles are
observed and the data strongly suggests that sodium cations are being incorporated within the inorganic silica/alumina
core, as opposed to organic cations that appear to be excluded from such clusters. As was the case for the pure-silica
system, important insights are gained by making analogies to the behavior of mixed surfactant systems.
7. The Effect of an Embedded Mid-Chain Dipole on the Properties and Characteristics of

Ester-Functionalized Self-Assembled Monolayers on Au{111}
Orlando M. Cabarcos 1 , Andrey Shaporenko 2 , Sundar Uppili 3 , Michael Zharnikov 2 and David L. Allara 1 , (1)The
Pennsylvania State University, University Park, PA, (2)Universtät Heidelberg, Heidelberg, Germany, (3)University of
Kansas, Lawrence, KS
Over the last 20 years, self-assembled monolayers (SAMs), particularly those with alkyl chains, have been extensively
studied by modifying the terminal group present at the air/SAM interface. Less well known are the effects which
incorporation of a functional group within the middle of the chains might have on the overall monolayer structure and
properties. We have used IRS, XPS and NEXAFS to examine the structure and characteristics of mid-chain ester
functionalized alkanethiols, SH(CH2)10CO2(CH2)4CH3, SH(CH2)10CO2(CH2)9CH3, SH(CH2)15CO2(CH2)4CH3 and

SH(CH2)5CO2(CH2)9CH3 on Au{111}. The embedded functional group leads to a model “stratified layer” type system
with the chain below the functional group exhibiting different orientation and conformational order then the upper chain.
XPS measurements show that the electrical dipole moment of the ester group affects the photoemission workfunction of
the two chains differently, relevant to the phenomena arising in devices such as organic electroluminescent devices and
organic field-effect transistors.
8. Keynote: Electrical microchips in the biocolloidal domain: On-chip assembly and

detection of live cells and biological molecules
Orlin D. Velev, Shalini Gupta and Peter Kilpatrick, North Carolina State University, Raleigh, NC
Two examples of the use of biocolloidal interactions for on chip synthesis of materials and biosensing will be presented
and discussed. In the first part we will demonstrate how biocomposite materials can be fabricated by precise electric
field driven co-assembly of live cells and synthetic colloidal particles. The process is based on dielectrophoresis (DEP),
mobility and interaction of particles in AC electric fields. Live cells such as baker's yeast and mouse fibroblasts were
co-assembled with colloidal particles into freely suspended 1D chains and 2D membranes. Experimental observations of
the DEP co-assembly dynamics showed that particles smaller in size than the cells were drawn and captured into the
cell junctions by the electric field. The process was modeled by a combination of electrostatic field computation and
MD-type of particle motion simulation. Magnetic microparticles conjugated with lectins could be used to bind the cells
irreversibly via bio-specific lectin-saccharide interactions. The cell membranes and chains formed could be manipulated
by magnetic field and interfaced with on-chip electrodes. Such functional biomagnetic cell-particle assemblies may find
applications in sensors, microassays, microsurgery, or as responsive biomaterials. In the second part of the talk we will
present a simple new technique for the on-chip detection of antigen induced binding of particles coated with antibodies.
The detection of antigen-induced agglutination is performed by impedance measurement through arrays of
microelectrodes interfacing the microchamber with the particle suspension.
9. The zeta potential of freshly cleaved mica just after immersion

Paul J. Sides, James D. Hoggard and Dennis C. Prieve, Carnegie Mellon University, Pittsburgh, PA
Muscovite mica was cleaved in air and quickly submerged in aqueous solutions of alkali metal salts. The zeta potential
was measured as soon thereafter as possible with the aid of an apparatus based on detection of streaming potential in
the vicinity of a rotating disk. The time between cleaving the sample and immersion was less than one minute and the
elapsed time before the first measurement after immersion was as low as 20 seconds with subsequent measurements
being taken at intervals of similar duration. When mica was immersed in 1 mM KCl at pH 5.8, the mica adopted a zeta
potential that was essentially constant within this time frame at -80 mV. When the mica was submerged in 1 mM NaCl
at a similar pH, however, the first measured zeta potential was -120 mV and a decay to a steady value at -95 mV was
observed with a decay time of order 1000 s. When freshly cleaved mica was immersed in solutions at lower pH, a
maximum appeared in the zeta potential and the transition time was reduced. These results are discussed in the
context of a dynamic single site binding model that tracks the surface coverage of potassium, sodium, and hydrogen
ions. Appropriate choices of dissociation and association rate constants allow fitting of the dynamic response of the
mica to the model.
10. A scalable route to gold nanoshell - liposome composites for photothermal therapies
Brian G. Prevo, Shelley Esakoff and Joseph A. Zasadzinski, University of California, Santa Barbara, Santa Barbara,
CA
Near infrared (NIR) light is especially useful for in vivo applications as physiological media are relatively transparent to
these wavelengths. Nanoscopic hollow shells of gold possess a strong NIR plasmon absorption. Recently, many
researchers have demonstrated an array of different imaging and therapeutic applications taking advantage of these
phenomena. Galvanic replacement chemistry (GRC) offers a facile and scalable ‘one pot' route to metal nanoshell
synthesis, providing a distinct advantage over conventional layer by layer nanoshell fabrication techniques. Using GRC,
template metallic nanoparticles (e.g. silver) act as reductants, nucleating the desired metal nanoshell (e.g. gold) around
them provided that the template metal has a lower standard reduction potential. The resulting aqueous core/metal shell
particles are formed in minutes, and can be tunably varied from ~ 20 – 75 nm shells with varying thickness (depending
on reagent ratios). The use of pulsed NIR laser irradiation for inducing plasmonic heating effects minimizes the

temperature rise in the surrounding media due to the fast relaxation times (~ ps) of the metal particles. The kinetics of
the laser attenuation by the particles correlates well with the corresponding UV/Vis/NIR spectroscopy, TEM,
experimental calorimetry, and heat transfer calculations. We are currently exploring these particles as remote
photothermal actuators within submicron liposomes. While bilayer compartments are quite deformable, they pop like
balloons if stretched too far (in excess of approximately 5-10%). This could give both spatial and temporal control of
drug delivery from liposomes without the need for specialized liposome compositions or large scale heating of the tissue
itself.
11. Synthesis and Imaging of Plasmonic Magnetic Nanoparticles

JitKang Lim, Robert D. Tilton, Alexander Eggeman, Frederick Lanni and Sara A. Majetich, Carnegie Mellon University,
Pittsburgh, PA
We describe the development of iron oxide-core, gold-shell nanoparticle probes for eventual use in cell or single
molecule sorting technologies and as intracellular probes. These nanoparticles combine the potential for magnetic
manipulation and plasmonic sensing in a single entity. The surface plasmon resonance of gold makes it possible to
track the positions of individual nanoparticles with darkfield microscopy. In addition, the gold shell is more easily
biofunctionalized than the surface of a bare iron oxide nanoparticle. This presentation will emphasize the synthesis and
physical characterization of the hybrid nanoparticles. Eighteen nanometer magnetic cores are first synthesized in
organic solvents, then transferred into water and coated with gold nanoparticle seeds that are further grown to a
complete shell. Transmission electron microscope images obtained at various stages of the process reveal the
development of the core-shell morphology. The completion of the gold shell produces an intensification and pronounced
shift of the surface plasmon resonance peak in the optical absorbance spectrum. These particles are
superparamagnetic at room temperature. Darkfield optical imaging shows the feasibility of detecting single nanoparticles
undergoing Brownian motion. Magnetophoretic and drag force calculations will be described that indicate the potential
utility of these nanoparticles for microfluidic single molecule and cell sorting applications. The calculations are tested by
measuring magnetophoretic velocities using darkfield microscopy and a micropatterned magnetic array.
12. Squishy particles: modulating the mechanical properties of polymer vesicles

James A. Silas, Jeffery Gaspard and Karym Kinnibrugh, Texas A&M University, College Station, TX
Polymer vesicles show great promise as both a targetable delivery vehicle and a platform for cellular mimicry. In pursuit
of both these goals, it is important to exercise control over the final properties of the colloid, including surface
chemistry, surface topology and mechanical properties. Since polymer vesicles are self-assembled fluids, they respond
to all stresses imposed by the solution by changing shape and size. The self-assembly process is critical to forming
uniform and reproducible surfaces on the particles, but limits the conditions in which the particles can be utilized. To
stabilize the vesicles and introduce a structural element to the particles that can be both solution responsive and
tunable, we confined hydrophilic monomers inside the polymer vesicles and polymerize them in situ. The crosslinked
particles are the same size as the starting vesicle population, which can be tailored from several hundred nanometers to
tens of microns. Since the resulting particles have the same surface as the original vesicle population, this approach
allows the mechanical properties of the particles to be tuned independently of the surface chemistry and bilayer
properties. By varying the monomer composition and crosslink density, the deformability of the polymer vesicles may be
varied continuously from a fluid to nearly a solid particle.
13. Bio-polyelectrolyte deposition and stabilisation of mineral colloidal particles

Peter Peter Versluis, Alois Popp, Leonard Flendrig and Krassimir Velikov, Unilever Food & Health Research Institute,
Vlaardingen, Netherlands
Polymer - colloidal particle mixtures are encountered in many industrial products like paints, agricultural, home and
personal care, and pharmaceutical products. Understanding the interactions and stability of such soft mater systems,
where biopolymers are added both to alter material and particle surface properties, in many cases remains a
challenging task. Here we present results on stabilisation of colloidal particles of sparingly soluble minerals by
deposition of bio-polyeletrolytres. Because of the strong electrostatic interactions with ions, the bio-polyectrolytes can
absorb on the particles, can partially dissolve the colloidal particles, and also form insoluble complexes with free ions.
These interactions result in change of stability and material properties of the system.

14. Keynote: Some theory of colloid transport in aquatic environments

Charles R. O'Melia, The Johns Hopkins University, Baltimore, MD
The author's perspective on the current status of the aquasol transport theory in environmental systems is presented.
Gaps in knowledge and future directions are proposed.
15. Effects of surfactant and ionic strength on transport and retention of colloid particles in
partially saturated porous media
Yuniati Zevi, Annette Dathe, Bin Gao, Brian K. Richards, J-Yves Parlange and Tammo S. Steenhuis, Cornell
University, Ithaca, NY
The effect of surfactant and ionic strength concentration on colloid transport through saturated or partially saturated
media has typically been studied using breakthrough curves. In this study, we performed pore-scale observations in a
small flow chamber to quantify colloids retained on the grain, air and liquid interfaces using a confocal microscope
system and ImageJ image analysis software. Stacks of images were analyzed for colloid retention in tests in which the
ionic strength and concentration of surfactant (nonionic Surfynol 485) were varied. Colloid retention primarily occurred at
the thin film along the edge of meniscus where the air-water and water-solid (AW, WS) interfaces closely approach
each other (also called the air-water meniscus-solid (AWmS) interface). The results show that colloid retention at the
AWmS decreased with increasing concentrations of ionic strength. At the same time more colloids were attached to the
sand grains, resulting in overall increased colloid retention with increasing ionic strength. We also observed that
increasing the surfactant concentration reduced colloid retention at the AWmS interfaces due to decreased contact
angle and surface tension. The results are consistent with the theory that capillary forces are mainly responsible for
colloid retention at the AWmS interface.
16. On role of air-water interface and surface tension in colloid transport

Volha Lazouskaya and Yan Jin, University of Delaware, Newark, DE
Current environmental and health concerns associated with transport of colloids, bio-colloids, and nanoparticles in soils
and aquifers increase the demand of predictive ability in colloid transport. Although colloid transport and colloid-
facilitated transport of contaminants have received close attention in past years, gaps in knowledge remain. To improve
fundamental understanding of colloid retention and transport processes, complex natural soil media are often simplified
to model porous media. At present, the major physical mechanisms involving colloids in unsaturated porous media
include retention on solid-water interface (SWI), air-water interface (AWI), and contact line (where all three phases
meet). Additionally, physical straining of colloids in pore spaces has been discussed in the literature. However, some
uncertainties in colloid transport exist, and many are related to colloid retention on air-water interface. While some
researchers considered AWI as an important retention site others did not observe significant retention of colloids on
AWI. The capillary structure of porous media suggests the importance of surface tension, and its experimental variation
would provide valuable information about underlying retention mechanisms. In our experiments, we investigate the effect
of surface tension on colloid behavior in model static and dynamic systems. The principle experimental design includes
an open capillary channel observed with confocal microscope. Such design allows direct observation of colloid retention
on AWI with different surface tensions. In addition to primary retention mechanisms studied in static system, dynamic
experiments aid the estimation of the relative impact of colloid retention on AWI and surface tension values on the
overall colloid transport.
17. Grain Surface-Roughness Effects on Colloidal Retention in the Vadose Zone

Veronica Morales, Cornell University, Ithaca, NY
The retention and release of micron sized particles and organisms in the vadose zone greatly affect the degree of
contamination to groundwater systems. Existing models need improvement to more accurately predict the physical
conditions under which such particle transportation occur. Recent theory on capillary and friction forces acting at the
air/water meniscus/solid (AWmS) interface suggests that grain roughness is an important factor in colloid retention in
unsaturated media. The objective of this work is to further investigate the effects of grain surface roughness and size as
a primary contaminant transport variable. Unsaturated column experiments with sands of different grain roughness were

performed to determine colloidal retention at the AWmS interface. A rectangular 40 mL acrylic vertical flow chamber
was built to take advantage of collecting visual and numerical data under the effects of gravity. Colloid behavior was
visualized in situ with digital bright field microscopy and breakthrough colloid concentrations were measured with
spectrophotometry. Spherical, 5 ìm sized, synthetic colloids were chosen to emulate homogeneous bacteria in shape
and size. Two sizes of quartz sand were modified and thoroughly pre-cleaned for tests of unaltered and smoothed (by
lapidary rotation) grain surfaces. Completed experimental results demonstrate that smoother grain surfaces retain a
lesser amount of colloids than rougher grain surfaces. This effect has shown to be consistent, although in different
magnitudes, for both saturated and unsaturated conditions. Current results indicate that the effects of surface
roughness diminish with increasing grain size.
18. Adsorption of nanomaterials to air-water interfaces in porous media during primary

drainage
Lixia Chen, David A. Sabatini and Tohren C. G. Kibbey, University of Oklahoma, NORMAN, OK
Nanomaterials are being produced and used in increasingly significant amounts. Although they can enter the
environment in a number of ways, little is known about their fate or environmental implications as emerging
contaminants. To understand the transport of nanomaterials in the unsaturated zone, the dynamic adsorption of
nanomaterials to the air-water interface during primary drainage was studied in laboratory experiments using two
different sizes of glass beads. Three similarly-sized nanomaterials were selected for this work: polystyrene latex
nanospheres, and tin oxide (SnO2) and titanium dioxide (TiO2) nanopowders. Measurements involved tracking the
concentration decrease of nanomaterials in the pore solution due to adsorption to air-water interfaces created during
drainage, and simultaneous tracking of capillary pressure and saturation in the porous medium. A continuous mass
balance was used to calculate the mass of nanomaterials adsorbed at air-water interfaces. Results indicate that total
mass adsorbed to air-water interfaces increases with decreasing saturation, as more interfacial area is formed.
However, normalization to measured interfacial areas indicates that for most systems, the adsorbed nanomaterial mass
per unit area is approximately the same for both sizes of glass beads over a wide range of saturations. Experiments
with three different concentrations of SnO2 showed increased adsorption at the air-water interface with increasing
concentration. Differences between the adsorption behavior of the three nanomaterials will be discussed.
19. Colloid deposition in a radial stagnation point flow system: The role of hydrodynamic
and DLVO forces
Gexin Chen 1 , Saeed Torkzaban 1 , Scott A. Bradford2 and Sharon Walker 1 , (1)University of California, Riverside,
Riverside, CA, (2)USDA-ARS George E. Brown, Jr. Salinity Laboratory, Riverside, CA
The influence of hydrodynamic conditions on the deposition of 1.1 ìm carboxylate-modified polystyrene latex
microspheres has been investigated using a radial stagnation point flow (RSPF) system. This experimental system
utilized an optical microscope and an image-capturing device to directly observe and determine the colloidal deposition
kinetics near the stagnation point. Experiments were carried out under well-controlled solution and surface chemistry,
allowing for the sensitivity of colloidal adhesion behavior to be examined under a wide range of hydrodynamic
conditions (capillary flow velocity from 0.01 m/s to 0.1 m/s), simulating various natural and engineered environments.
Deposition kinetics was quantified at two ionic strengths (0.01 and 0.1M KCl) under electrostatically unfavorable and
favorable attachment conditions (using pure quartz and quartz that was modified to have a positive charge,
respectively). Hydrodynamic forces were implicated as an important factor on the initial colloidal deposition under both
unfavorable and favorable conditions. The colloidal attachment efficiency decreased with increasing flow rate and was
also a function of the system chemistry. To better understand and interpret these observations, numerical simulations of
the RSPF system were conducted that considered relevant hydrodynamic and DLVO forces. The results of the
experimental and theoretical studies will be presented and the implications for various water quality and industrial
applications will be discussed.
20. Keynote: Imaging the flow of colloidal glasses

Wilson C. K. Poon, University of Edinburgh, Edinburgh, United Kingdom
Using fast confocal microscopy, it is now possible to study the flow of concentrated colloidal suspension at the single
particle level. In this talk, I will briefly review this methodology, and present results obtained in two simple flow

geometries: shearing between parallel plates, and pipe flow in a square capillary. Both flows display features that
cannot be understood under a traditional rheology paradigm. Instead, the flows exhibit features reminiscent of granular
materials. Indeed, in the case of capillary flow, a stress fluctuation model borrowed from granular materials can be used
to understand our observations in considerable detail.
21. Glass-like dynamics of microgel suspensions
Giovanni Romeo 1 , Alberto Fernandez-Nieves1 , Domenico Acierno 2 and David A. Weitz 1 , (1)Harvard university,
Cambridge, MA, (2)University of Naples Federico II, Napoli, Italy
Materials consisting of concentrated soft particles closely packed in an amorphous state are found in many day-to-day
systems like pastes, tissues or emulsions. The rheological properties of these systems are usually characterized by
slow relaxations and by the existence of a yield stress, among other signatures, reflecting the existence of glassy
dynamics. A key point in soft condensed matter is to establish a link between the macroscopic properties and the
microscopic structure and dynamics of these glassy systems. We show that suspensions of microgel particles are a
flexible model system sharing some of the fundamental characteristics of molecular glasses. Here, the particle size
depends on external variables, such as temperature and pH, and on the degree of network cross-linking. Size can also
be tuned with concentration above random close packing, since microgels are then forced to shrink to fit in the given
volume. By changing any of these parameters the system shows a rich behavior. In particular, it undergoes glass-like to
liquid-like to gel-like dynamics as function of temperature; this is shown with bulk rheological measurements and with
the use of dynamic light scattering and confocal imaging to access the system local dynamics.
22. Ideal glass transitions, barrier hopping and viscoelasticity in fluids of nonspherical
colloids
Galina Yatsenko and Kenneth S. Schweizer, University of Illinois, Urbana, IL
The slow translational dynamics of glassy isotropic fluids of hard polyatomic rods and spherocylinders of aspect ratios
up to forty have been theoretically investigated. The approach is based on a preaveraging of orientational degrees of
freedom to a center-of-mass description, and a nonlinear stochastic Langevin equation of motion that includes activated
barrier hopping on a nonequilibrium free energy profile. Variable site bond length effects have also been studied for
symmetric diatomics and linear triatomics. The excluded volume driven ideal glass transition (GT) boundary is predicted
to be a nonmonotonic function of particle length-to-width ratio, and rather remarkably resembles the random close
packing volume fraction of nonspherical granular objects. The location of the rod and spherocylinder ideal GT boundary
relative to the percolation threshold, isotropic-nematic liquid crystal phase transition, and mechanical jamming volume
fraction has been determined. The ideal GT signals a crossover to noise-driven activated barrier hopping dynamics.
The consequences of shape anisotropy on the entropic barrier height, localization length, elastic modulus, yield stress
and nongaussian dynamic heterogeneity aspects have been studied. The theory has also been applied to suspensions
of rigid disks, in both the isotropic and discotic liquid crystalline state, and the results contrasted with the rod-like
systems.
23. Aging and non-Gaussian dynamics in a colloidal glass

Gianguido C. Cianci and Eric R. Weeks, Emory Universty, Atlanta, GA
As a hallmark of the glassy state of matter, aging has attracted substantial attention, yet it remains a poorly understood
phenomenon. It manifests itself by a dependence of the dynamical properties of the sample on the time elapsed since
vitrification. The glassy state is also marked by dynamics that are heterogeneous in both time and space, and that
exhibit non-Gaussian statistics over moderate to long timescales. We use a density and refractive index matched
suspension of micron sized PMMA colloids as a model glassy material. At these length scales, laser scanning confocal
microscopy allows us to follow the motion of a few thousand particles in real time and real space. We study the
interplay between the timescales at which the dynamics are non-Gaussian and the age of the sample. We also analyze
the spatial extent over which the dynamics are heterogeneous and examine the age dependence of this length scale.
24. Microscopic structure and collapse of depletion-induced gels in vesicle-polymer

mixtures

Ji Yeon Huh 1 , Eric M. Furst1 and Matthew L. Lynch2 , (1)University of Delaware, Newark, DE, (2)Procter & Gamble
Company, Cincinnati, OH
Non-adsorbing polymers are added to colloidal dispersions to tailor their rheological properties. However, this leads to a
number of undesirable phenomena including phase separation and gel collapse. Because they affect the stability of
many food and personal care products, understanding and controlling these issues remains a crucial aim. In this study,
we present the time-dependent collapse and microstructure of depletion-induced vesicle gels. The vesicle dispersion is
prepared from a commercial-grade dichain cationic surfactant through a standard milling process (d mean =256nm and
Φ=0.46). As a depletant, we add the cationic poly(diallyldimethylammoniumchloride) (MW=14.5kDa and R g =11.2nm).
To investigate the phase behavior, vesicles (Φ=0.05~0.3) are systematically mixed with polymer (Cp=0.01~2.0wt%). As
density gradients build up, an interface is developed between a vesicle-rich phase and a polymer-rich phase upto
Cp=0.2wt%. Increasing the polymer concentration further forms a gel, which subsequently collapses. Height profiles are
characterized by a slow initial rising for a finite delay time, a rapid collapse, and a slow final compaction to an
equilibrium height. The time-scale associated with the collapse rate is predicted by the poroelastic model [1]. However,
we observe a remarkably different polymer concentration dependence on the collapse rate. Unlike other colloidal gels
[2], we find the delay time decreases with increasing polymer concentration. We show this surprising behavior can be
explained by considering the permeability for solvent backflow [3], which is directly related to the characteristic pore
area of the gel obtained using confocal microscopy.
[1] Manley et al. (2005), [2] Kilfoil et al. (2003), [3] Buscall and White (1987)
25. Origin of the slow dynamics and the aging of a soft glass
Sylvain Mazoyer, Luca Cipelletti and Laurence Ramos, University of Montpellier and CNRS, Montpellier, France
We study by light microscopy a soft colloidal glass consisting of a compact arrangement of polydisperse elastic spheres.
We show that its slow and non-stationary dynamics results from the unavoidable small fluctuations of temperature,
which induce intermittent local shear deformations in the sample, because of thermal expansion and contraction.
Temperature-induced shear provokes both reversible and irreversible rearrangements whose amplitude decreases with
time, leading to an exponential slowing down of the dynamics with sample age. Moreover, we find that the motion of
the irreversible rearrangements is close to ballistic, in agreement with our previous light scattering results. Our
observations provide the first direct experimental evidence of ballistic motion associated with the slow dynamics of a
variety of soft glassy materials, as inferred from scattering techniques, and suggest a possibly general mechanism for
these dynamics.
26. Keynote: Langmuir-Blodgett films of oriented collagen films as cell culture substrates
Gerald G. Fuller, Stanford University, Stanford, CA
It is known that embryonic skin can heal without scarring prior to the first trimester. Although the reasons for this
remarkable ability to recover from a wound are not completely understood, it is known that the nature of the collagen
making up the embryonic skin becomes progressively disorganized and disoriented with age. This lecture describes a
method of distributing thin layers of soluble collagen at the air/water interface. These films can sustain high surface
pressures and can be subjected to surface flow that lead to uniform orientation of the collagen protein. This orientation
is verified directly at the air/water interface by measuring dichroism arising from sirius red dye molecules that are
intercalated within the collagen chains. Appropriate Langmuir-Blodgett deposition of the layers onto smooth substrates
results in coatings of uniaxially oriented protein. The influence of collagen orientation on the growth and proliferation of
both human fibroblast cells and adipose-derived stem cells has been studied. It is demonstrated that these substates
cause the cells to become polarized and oriented parallel to the collagen orientation. In addition, the cells proliferate to
a much greater extent on the oriented collagen in comparison with standard cell culture media.
27. Barcoded microparticles for multiplexed biomolecule analysis
Patrick S. Doyle 1 , Daniel Pregibon 1 and Mehmet Toner2 , (1)Massachusetts Institute of Technology, Cambridge, MA,
(2)Massachusetts General Hospital and Harvard Medical School, Boston, MA
High-throughput screening for genetic analysis, combinatorial chemistry, and clinical diagnostics benefits from

multiplexing, which allows for the simultaneous assay of several analytes but necessitates an encoding scheme for
molecular identification. Current approaches for multiplexed analysis involve complicated or expensive processes for
encoding, functionalizing, or decoding active substrates (particles or surfaces) and often yield a very limited number of
analyte-specific codes. We present a method based on continuous-flow lithography (Dendukuri et al. Nat. Mat. 2006)
that combines particle synthesis, encoding, and probe incorporation into a single process to generate multifunctional
particles bearing over a million unique codes. By using such particles, we demonstrate a multiplexed, single-
fluorescence detection of DNA oligomers with encoded particle libraries that can be scanned rapidly in a flow-through
microfluidic channel. Furthermore, we demonstrate with high specificity the same multiplexed detection using single,
multiprobe particles.
28. A new biosensor chip: local mapping of mechanical properties using suspended lipid
bilayers as “nano drums“
Siegfried Steltenkamp 1 , Ingo Mey 2 and Andreas Janshoff 2 , (1)University of California, Santa Barbara, CA,
(2)Johannes Gutenberg Universitaet, Mainz, Germany
Suspended bilayers, which bridge the gap between solid-supported and black lipid membranes, have been developed
to cover a of porous alumina substrates. The so called “nano drums”, help solve the problem of close membrane
surface contact and concomitant limited lateral mobility. Scanning force microscopy was employed in order to visualize
and probe the free standing membranes with regard to mechanical stability. The starting point is a planar gold-coated
alumina substrate with a chemisorbed 3-mercaptopropionic acid monolayer displaying circular pores of very well defined
and tunable size, over which N,N,-dimethyl-N,N,-dioctadecylammonium bromide or N-[1-(2,3-dioleoyloxy)propyl]-N,N,N-
trimethylammonium methyl-sulfate bilayers are spread. Indenting these “nano drums” centrally with an AFM tip yields
force-indentation curves which were quantitatively analyzed by solving the corresponding shape equations of continuum
curvature elasticity. Since the measured response depends in a predictable way on the system geometry (pore size, tip
radius) and on material parameters (bending modulus, lateral tension), this opens the possibility to monitor local elastic
properties of lipid membranes in a well-controlled setting by addressing each pore separately. Thus we have developed
a technique for forming a biosensor, utilizing suspended bilayers allows for the first time to locally determine the
mechanical properties of the bilayer such as bending modulus or surface tension.
29. Hyaluronan-based hydrogel particles and particle crosslinked networks with tunable
mechanical properties
Xinqiao Jia, University of Delaware, Newark, DE
Recent studies suggest that cells preferentially differentiate on artificial extracellular matrices that have mechanical
stiffness similar to that of their natural tissues. Therefore, hydrogels to be used for soft tissue regeneration need exhibit
viscoelasticity that approximates that of the targeted tissue. To this end, we have developed hyaluronan (HA)-based
soft hydrogel particles (microgels and nanogels) with controlled size, chemistry and structure. HA microgels were
prepared by in situ crosslinking of chemically modified HAs within an inverse microemulsion stabilized by Span 80.
Similarly, HA nanogels were synthesized by in-situ crosslinking of HA with divinyl sulfone (DVS) using the AOT reverse
micelle system. In vitro cytotoxicity studies using vocal fold fibroblasts indicate that these hydrogel particles are
essentially non-toxic. HA microgels exhibit residual functional groups that can be used to form doubly crosslinked
networks (DXN) with tunable viscoelasticity. Alternatively, free radical polymerization/crosslinking of acrylamide (AAm) in
the presence of HA nanogels resulted in semi-interpenetrating networks (IPN) that are highly elastic. Mechanical
measurements using torsional wave apparatus indicate that the HA DXN have mechanical properties similar to that of
the vocal fold mucosa; whereas the HA/PAAm IPN exhibit viscoelastic responses close to that of the vocal ligament.
Controlled release of model drugs was achieved through their anchorage at predetermined locales of the particulate
hydrogel system. These materials are promising candidates for vocal fold tissue regeneration.
30. Multilayer drug delivery films studied by sum frequency generation spectroscopy and
attenuated total reflection fourier transform infrared spectroscopy
Michael E. Pedley, Michael T. L. Casford and Paul B. Davies, University of Cambridge, Cambridge, United Kingdom
Hydroxypropylmethylcellulose (HPMC) matrices are commonly used as drug delivery media providing controlled release

of pharmaceuticals. HPMC films also find application as tablet coatings, rapid release carrying media and buccal
delivery systems. Combining thick films of water soluble, swellable and edible polymers with a substrate material, for
example polyethylene terephthalate (PET) film, to reinforce the polymer media presents the potential to create a
disposable topical or buccal drug delivery system.
While films of HPMC and PEG on their own have been extensively studied, the use of multilayer films as drug carrying
substrates has not been widely considered. In particular the structure of cast films of HPMC has not received much
attention using vibrational spectroscopy. For example, the techniques of attenuated total reflection fourier transform
infrared spectroscopy (ATR-FTIR) and sum frequency generation spectroscopy (SFG) have not been extensively used
for this purpose.
This work reports studies on mixed films of HPMC or PEG cast upon a PET film, using both ATR-FTIR and SFG
techniques. Whilst the former provides information about many different functional groups and about how water is
incorporated in or near the film, the SFG technique provides information in the C-H stretching region only but which
nevertheless is interface specific. Results will be presented on the stability of the films in aqueous environments under
both static and flowing conditions. These results will precede experiments designed for controlled release of
pharmaceutical or taste additives enclosed in composite films of two or more layers.
31. Polycation-Clay Composites as a Basis for Controlled Release Herbicide Formulations

Yael G. Mishael and Adi Radian, Hebrew University of Jerusalem, Rehovot, Israel
Herbicide controlled release formulations (CRFs) are designed to reduce undesired herbicide leaching and increase the
herbicide concentration at the top of the soil for reduced soil and water contamination and improved herbicidal activity.
In the current study we developed novel CRFs for the anionic herbicide imazapyr (IMP) based on its binding to poly
dimethyldiallylammonium chloride (PDADMAC)-montmorillonite composites. Polycation adsorption on the clay was rapid
and reached a high loading of 0.9 g/g which results in charge reversal of the surface. Fourier transform infrared and X-
ray diffraction of the composites indicated electrostatic interaction between the polycation and the surface, intercalation
of the polycation in the clay and formation of loops and tails on the surface at high polycation loadings. Such a
configuration, in comparison to a train configuration, creates available positive binding sites resulting in high IMP
binding. However, IMP binding to the composites was found to be affected not only by polycation configuration but also
by composite flocculation. Upon adding high concentrations of IMP to a PDADMAC-montmorillonite composite (0.16 g
polymer/g clay) a high herbicide loadings was reached (66% active ingredient). Testing IMP release from formulations
applied on a thin layer of soil demonstrated that its release from PDADMAC-montmorillonite formulations was
substantially slower than its release from the commercial formulation. The ability of the newly designed formulations to
decrease leaching while maintaining good herbicidal activity was demonstrated by applying a soil column bioassay.
32. Keynote: Self-assembly of colloids: The shapes of things to come

Sharon Glotzer, University of Michagan, Ann Arbor, MI
Recent breakthroughs in particle synthesis leading to nanocolloidal particles of unusual shape and patterning have
paved the way for a revolution in materials formed from the self-assembly of these building blocks. The unprecedented
anisotropy of today's new nanoparticle and colloidal building blocks starkly contrasts with the isotropic, spherical colloids
that have been the focus of particle assembly for more than a generation. No general theory exists to predict the range
of structures possible for these new building blocks as a function of thermodynamic conditions, and the complementary
problem of inverse design of a particular building block that can self-assemble into a desired target structure is difficult
with as yet no standard design algorithm. In this talk, we present a conceptual framework with which to consider the
key factors controlling the assembly of these new building blocks. We present results of computer simulations of patchy
particle nanoparticle design and assembly, and show how various measures of anisotropy, including particle shape,
patterning, functionalization and interaction selectivity, can be combined and exploited to achieve complex mesoscale
one-, two- and three-dimensional structures such as wires, sheets, virus-like shells and colloidal “molecules”, diamond,
icosahedral, gyroid, and other complex structures through self-assembly.
. DNA directed assembly of non-close-packed colloidal crystals

Paul V. Braun, Margaret Shyr, Daryl Wernette, Yi Lu and Pierre Wiltzius, University of Illinois at Urbana-Champaign,

Urbana, IL
DNA directed assembly of non-close-packed colloidal crystals
34. An investigation of the assembly conditions of dielectric particles in polymers using the
electrorheological effect
Jacques Persello 1 , Aladin Kossi1 , Bernard Cabane 2 and Georges Bossis 3 , (1)University of Franche-Comte,
Besancon, France, (2)Ecole superieur de physique et de chimie industrielles, Paris, France, (3)University of Nice Sofia
Antipolis, Nice, France
Some fluids can respond to an applied electric fluid, switching from a disordered structure with a fluid-like response to
an ordered structure with a solid-like response. These fluids are called electrorheological fluids. These fluids are made
of polymeric materials into which colloidal particles are dispersed. When an electrical field is applied, the particles are
polarized and become small electrical dipoles. If the field exceeds a certain threshold, these dipoles attract each other
and assemble into chains that are aligned along the field direction.
We show that electric field induced ordering of dielectric nanoparticles in a polymeric liquid is a potential fabrication
means to assemble nanoparticles-polymer composites. The resulting composite material consists of a quasi 1–3
connectivity pattern due to the formation of chains by the nanoparticles. The degree to which these rows form is
strongly dependent on both the magnitude and frequency of the applied field.
A critical feature in the performance of such fluids is the control of interparticle interactions. We report a real-time,
Small Angles Neutrons Scattering and dynamic rheological measurements study of the evolution of structure in a
electrorheological fluid during the particles ordering. When an electrical field was applied, a two-dimensional set of
diffraction spots was obtained, located in the direction of chain alignment. The spacing of these diffraction spots yields
the average interparticle distance, which is found to vary with the electrical field, the field frequency and the surface
chemistry of the nanoparticles.
35. Disappearance of the gas-liquid phase transition for highly charged colloids
Antti-Pekka Hynninen and Athanassios Z. Panagiotopoulos, Princeton University, Princeton, NJ
We calculate the full phase diagram of spherical charged colloids using Monte Carlo free energy calculations. The
system is described using the primitive model, consisting of explicit colloids and counterions in a uniform dielectric
continuum. We show that the gas-liquid critical point becomes metastable with respect to a gas-solid phase separation
at colloid charges Q>=20e. Figure shows the phase diagram for colloid charge Q=20e in the colloid packing fraction,
reduced temperature representation. The phase diagram consists of a broad gas-solid phase coexistence at low
temperatures, a narrow fluid-solid coexistence at high temperatures, and a metastable gas-liquid coexistence (whose
critical point marked by the star). Employing approximate free energy calculations, we are able to determine the critical
temperature Tc below which a broad gas-solid phase separation occurs for highly charged colloids up to Q=2000e and
propose a scaling law Tc = Q^0.5. We therefore extend the knowledge of like-charge attraction from modestly charged
micellar systems with charge Q < 100e to highly charged colloidal suspensions with Q=2000e.

36. Patchy Particles and their Assembly Properties

Ilona Kretzschmar, The City College of City University of New York, New York, NY
Our work is concerned with fabricating particles with reactive patches and testing the assembly and interactions of
these particles. Specific spatial modification of spherical particles with patchy anchor points presents an exciting new
area of directed particle assembly. The position of the patches, the patch material and possibly linker molecules
assembled onto these patches as well as the patch roughness result in a variety of new parameters important for the
assembly, which may allow predicting of structures and directing of particles into desired structures.
We have developed methods for the synthesis of silver- and gold-capped 2.4 µm polystyrene particles using both
template-assisted electroless deposition 1 and physical vapor deposition. We find that electroless deposition results in
patches with rough surfaces, while vapor deposition gives much smoother patch surfaces. We have begun to study the
assembly of these patchy particles into two-dimensional monolayer films. In addition, we have employed a lattice
density functional method to model parameters important for patchy particle assembly such as temperature,
concentration and binding strength. 2
We will report our results from the two- and three-dimensional assembly of the patchy particles. For example,
preliminary data show a striking difference in the assembly of particles with rough and smooth patches.
1) Cui, J.; Kretzschmar, I. Langmuir 2006, 22, 8281-8284.
2) A. B. Pawar, I. Kretzschmar, G. Aranovich, M. D. Donohue J. Phys. Chem., 2006, in press.
37. Dielectrophoretic assembly and electrohydrodynamic mobility of "Janus" particles in AC

electric fields
Sumit Gangwal 1 , Olivier J. Cayre1 , Martin Z. Bazant 2 and Orlin D. Velev 1 , (1)North Carolina State University, Raleigh,
NC, (2)Massachusetts Institute of Technology, Cambridge, MA
The synthesis of “Janus” particles (whose hemispheres are physically or chemically different) is of growing importance
for the development of novel materials, but the behavior of such particles in external fields has not been studied in
depth. We investigated the effect of external AC electric fields on Janus particles consisting of a dielectric hemisphere
and a conductive hemisphere. The operational diagram of particle response and structure assembled as a function of
frequency and field intensity will be presented. At low frequencies (< 10 kHz) of the applied AC fields, the tangential
component of the electric field on the polarized double layer at the metal-dielectric interface leads to directional ionic
flow along the surface. This AC electrohydrodynamic (EHD) flow forces the particles to move normal to the electric field
with their dielectric hemispheres facing forward. We present the first experimental verification of this EHD effect, which
has been recently predicted theoretically. The EHD effect is suppressed in AC electric field of higher frequency (> 15
kHz). In this case the particles self-assemble by dielectrophoresis into new types of metallodielectric colloidal crystals,
where the metallized halves of neighboring particles align into conductive lanes through the crystals (see Figure). The
propelling metallodielectric particles could be used as microscopic mixers, "shuttles" and self-propelling on-chip
sensors. Their self-assembly at high frequency could be used in the fabrication of photonic crystals of new symmetries,
massively parallel waveguides, and materials with directional electrical and heat transfer.

38. Keynote: Controlling the packing of block copolymer micelles: interfacial tension,
depletion, and superlattices
Timothy P. Lodge and Sayeed Abbas, University of Minnesota, Minneapolis, MN
Solutions of block copolymers in selective solvents exhibit a rich variety of structures, both intramicellar (spheres, disks,
worms, vesicles…) and intermicellar (fcc, hcp, bcc, A15, AB13,…). The choice of structure may be dictated by a host of
variables, including block molecular weights, concentration, choice of solvent, temperature, blending, and addition of
homopolymers. In this talk we will describe three illustrative examples, involving (i) the control of micelle morphology by
temperature, (ii) the disruption of ordered phases by addition of homopolymer, and (iii) the formation of superlattices by
mixing two different micelle populations. Scattering techniques (X-ray, neutron, and light) play the crucial role in
quantifying these phenomena.
39. Morphological Transitions in dilute region of CTAB/SDS/Water system: a SAXS study

A.S. Abdul Rasheed and Jayesh R. Bellare, Indian Institue of Technology,Bombay, Mumbai, India
Mixtures of oppositely charged surfactant in aqueous system self assemble to form to a variety of microstructures such
as micelles, vesicles, lamellar sheets and nano discs. In this study, various microstructures arising in the water rich
corner of CTAB/SDS/Water system with excess anionic surfactant is evaluated with Small Angle X-ray Scattering
(SAXS) and the partial phase diagram is obtained. Unique microstructural transformation in the presence of excess
anionic surfactant at the dilute region led to prolate micelles first transforming to spherical micelles and then to rod-like
micelles. The strong electrostatic interaction between ions in these mixed surfactant aqueous solutions leads to phase
separation with multitude of microstructures. The size and shape of a self–assembled aggregate is the product of a
balance between different free energy contributions. In order to minimize the electrostatic repulsions between the polar
head groups pure SDS self-assemble to form prolate micelles. Upon addition of the cationic surfactant CTAB to SDS,
electrostatic attraction circumvents repulsion between like charges of the surfactant, and elongated microstructures
evolve by counteracting the initially formed anisotropic structure. The growth and transition of micelles from prolate to
rod-like is evident from SAXS scattering curves. Also, spontaneous formation of vesicles is observed at a locus of
concentrations depending on mole fractions of the surfactant mixture and the overall concentration. Light scattering
confirms that vesicles are poly disperse with average size of 200 nm. Transition from micelle to vesicle seems to be first
order from the study.
40. Fast Dynamics of Wormlike Micelles

Florian Nettesheim and Norman J. Wagner, University of Delaware, Newark, DE
We present first measurements of the segmental diffusion of cationic wormlike micelles using neutron spin echo (NSE).
The measured scaling of the relaxation rate with wavevector is observed to follow the predictions of Zilman and
Graneck ( Phys. Rev. Lett., 1996) for semi-flexible chains. The rate of segmental diffusion does not depend strongly on
either surfactant or salt concentration, in agreement with expectations. NSE has been proposed as a method to
determine the bending constant kappa and thus persistence length (lp=kappa/kT) of wormlike micelles; however
previous measurements on nonionic WLMs by (Seto et al. J. Phys. Chem. Solids, 1999) showed large discrepancies

with light scattering measurements. Here, we resolve these discrepancies by identifying the lower cut-off length for the
bending modes a, which is a parameter in the theory. Therefore, NSE is demonstrated to be a quantitative tool to
determine the bending modulus and persistence length of wormlike micelles.
41. Scattering form-factors for self assembled Y-junctions
Tobias Foster1 , Samuel A. Safran 2 , Thomas Sottmann1 and Reinhard Strey 1 , (1)University of Cologne, Cologne,
Germany, (2)Weizmann Institute of Science, Rehovot, Israel
Networks of branched cylinders are found as microstructures in many different self-assembled systems such as
microemulsions, dipolar fluids or tubulin- and actin-filaments. In order to structurally characterise these cylinder
networks, we have calculated the scattering functions that can be used to analyse small angle neutron scattering data
obtained from such microstructures. We first focused on microstructures with high densities of network junctions
connecting the cylindrical elements. In this limit, the network microstructure can be regarded as an assembly of
randomly oriented, closed packed network junctions (i.e. we neglect the cylinder scattering contributions). In this case,
the scattering spectrum of the network microstructure can be calculated as the product of the junction number density,
the junction form-factor, that describes the scattering from a single junction, and a structure factor, that describes the
local correlations of different junctions due to junction interactions (including excluded volume type interactions). In a
second approach, we included the cylinder scattering contribution in the junction form-factor. The theoretical predictions
are compared with results of scattering measurements of several microemulsion systems.
42. Analysis of Microemulsions Containing a pH-Degradable Alkyl Ethoxylate Surfactant by

Small-Angle Neutron Scattering
Douglas G. Hayes 1 , Javier A. Gomez del Rio 1 , Mayson H. Alkhatib 2 , Volker S. Urban 3 , J. S. Lin 3 and Guangming
Luo3 , (1)University of Tennessee, Knoxville, TN, (2)University of Alabama in Huntsville, Huntsville, AL, (3)Oak Ridge
National Laboratory, Oak Ridge, TN
A 1,3-dioxolane alkyl ethoxylate surfactant (CK) that undergoes hydrolysis in acidic pH has been successfully combined
to form binary surfactant systems with Aerosol-OT (AOT), employed to form 3-phase microemulsion systems with water
and heptane which effectively isolate proteins (within the middle, bicontinuous microemulsion phase), and temperature-
insensitive phases that may be useful for drug delivery. Small-Angle Neutron Scattering (SANS) experiments have been
useful in further understanding the systems' nanostructures. SANS analysis of water-in-oil microemulsions
demonstrates that the substitution of AOT with CK (20%) has no effect on geometrical parameters, but greatly
increases the level of attractive interactions. At 20-25% surfactant (equimolar amounts of AOT and CK) and sub-
ambient temperature, highly anisotropic phases form, with a reversible transition to a less-ordered, slightly anisotropic
system occurring upon the increase of temperature and salinity. Analysis by polarized light microscopy suggests their
identity as reverse hexagonal phases. SANS analysis using three different contrasts is consistent with a cylinder form
factor, in agreement with the H2 assignment, but inconsistent with H2's structure factor. SANS analysis of protein-
containing middle (bicontinuous) phases of 3-phase systems suggest that proteins with amphiphilic structure, such as
cytochrome c, alter the nanostructure, and that oil-in-water microemulsions form in the bottom, aqueous, phase.
43. Interplay between surface and solution behaviour in di-alkyl chain cationic / nonionic
surfactant mixtures
Jeffrey Penfold, ISIS , CLRC, Didcot, United Kingdom, I. Tucker, Unilever Research and Development Laboratory, Port
Sunlight, United Kingdom and R. K. Thomas, Oxford University, Oxford, United Kingdom
Understanding the complex surface and solution behaviour of di-alkyl chain cationic and nonionic surfactant mixtures is
important for a wide range of applications including detergents, shampoos, and conditioners. Furthermore, by analogy,
it has wider implications for membrane solubilisation, a key technique in biochemistry, and for the manipulation of
membrane properties.
Neutron reflectivity, small angle neutron scattering, light scattering, and surface tension have been used to characterize
surface and solution behaviours of the cationic surfactant, di-hexedecyl dimethyl ammonium bromide, DHDAB, with a
range of different nonionic surfactants, from C 12 E3 to C 12 E12 .

Solution phase behaviour for the different cationic / nonionic mixtures has been determined in some detail. For the
nonionic surfactants C 12 E6 and C 12 E12 the nonionic rich region of the phase diagram is comprised of mixed globular
micelles. For the cationic rich composition the predominant microstructures are bi-lamellar to multi-lamellar vesicles and
L β lamellar phase. At intermediate compositions there is a coexistence region comprised of micellar and planar
structures in coexistence. For C 12 E3 the phase behaviour is different and shows an evolution of different planar
structures with composition.
The surface behaviour is characterized by a much more marked departure form ideal mixing than is normally
encountered in surfactant mixtures. For solutions rich in cationic the surface adsorption is dominated by the cationic
surfactant, and the nonionic only competes for the surface for solutions rich in the nonionic surfactant. It is shown how
this surface behaviour is correlated with the solution phase behaviour which is determining the relative monomer
composition and concentrations.
44. Keynote: Self-Assembly: Connecting academia with industrial perspectives

Alex Lips, Unilever, Trumbull, CT
TBA
45. Self-assembly in anhydrous sugar glasses

Hiteshkumar Dave, Chia-Chi Ho and Carlos Co, University of Cincinnati, Cincinnati, OH
In aqueous systems, the hydrophobic effect drives the self-assembly of amphiphiles into a broad range of micellar, rod-
like, bicontinuous, and liquid-crystalline complex fluids, which have myriad biological, materials, and product
applications. Amphiphilic self-assembly is not limited to aqueous systems, however. Replacement of water with
supercritical carbon dioxide, for example, results in complex fluids that combine the best properties of gases and
liquids. Along this vein, we explored the self-assembly of surfactants in anhydrous sugars, where the low-cost, water-
solubility, low toxicity, and stabilizing properties of glassy sugars make them ideal water-replacements for many
pharmaceutical, food, and materials synthesis applications.
A recent letter to Nature Materials reported how anhydrous powders of sugars and surfactants suspended in oil can
spontaneously form molten glasses with nanometer size domains of sugar and liquid oil without mixing. In this
presentation, we will discuss the latest findings on the liquid-crystalline phase behavior and microstructure of
glucamide- and lactobionamide-based surfactants in sucrose/trehalose glasses.
46. Surfactants for carbon dioxide

Julian Eastoe, University of Bristol, Bristol, United Kingdom
For some 15 years the attainment of efficient, non-fluorinated CO2-active surfactants has been a “Holy Grail” for
researchers spanning pure and applied chemical sciences. This talk outlines the history of small molecule CO2-active
surfactants, from the first tentative observations with fluorinated compounds in 1991, up to recently discovered fluorine-
free oxygenated amphiphiles.
Reference Surfactants for CO2 Julian Eastoe, Sarah Gold, David C Steytler, Langmuir 2006, 22, 9823-9842.
47. Characterization of nanostructures of mixed surfactant aggregation using Analytical

Ultracentrifugation
Shaohua Lu and Ponisseril Somasundaran, Columbia University, New York, NY
Nanostructures of aggregation determine the behavior and performance of surfactant systems, especially surfactant
mixtures. However, the characterization of nanostructures remains a challenge due to the lack of techniques. Analytical
ultracentrifuge (AUC) was first successfully used to study surfactant micellar systems to obtain quantitative data on
micelles including size, shape, aggregation number and diffusion coefficients. Various mixed surfactant systems and
individual surfactants involved have been studied using AUC in this work, including both nonionic/nonionic and

nonionic/ionic combinations. The aggregation numbers obtained for sugar based n-dodecyl-â-D-maltoside (DM) and
noneyl phenol ethoxylated ester (NPn) are in accordance with literature values. In contrast, those for anionic sodium
dodecyl sulfate (SDS), cationic dodecyltrimethylammonium chloride(DTAC) and the cationic gemini surfactant are
smaller than the literature values, because the electrostatic repulsion reduce the sedimentation velocity. Spherical
micelles were identified in mixed DM/SDS and DM/DTAC systems, while cylindrical micelles were observed in mixed
nonionic DM/NPn and NPn/NPm system,. It was found that the decrease of the average number of ethoxylated groups
in NPn surfactants increases the size and aggregation number of the system and also causes a shape transition from
spherical to cylindrical. Interesting to note that the coexistence of two different types of micelles was identified in the
mixed nonionic systems, depending on the mixing ratio. The information obtained will help quantitatively understand the
packing of surfactant molecules in micelles, which leads to a relationship between the nanostructure of aggregates and
the chemistry of the molecules.
48. Characterization of alkyl polyglucoside microstructure and phase behavior

Christina M. Russo and Eric W. Kaler, University of Delaware, Newark, DE
Due to rising environmental concerns, nonionic alkyl polyglucosides, such as decyl-b-glucoside (C10 bG 1 ) and
dodecyl-b-glucoside (C12 bG 1 ), have been seen as an alternative to conventional surfactants. Unfortunately, these
nonionic surfactants phase separate at the concentrations and temperatures of interest. A common solution to this
problem is the use of hydrophilic co-surfactants, in this case the maltosides, to close the miscibility gap. Our interest is
to link the thermodynamics of the phase behavior with changes in micellar microstructure. The model of Zilman et al.
(Langmuir, 2004) provides a way to do this by connecting the formation of a saturated network to phase separation.
This model has been fitted to cloud point data of aqueous solutions of C 10 bG 1 /C10 bG 2 and C 12 bG 1 /C12 bG 2 . The
transition in micellar shape from spheres to cylinders was characterized using quasi-elastic light scattering (QLS), and
the micellar network region was probed using small angle neutron scattering (SANS), pulsed-gradient spin-echo
neutron magnetic resonance (PGSE NMR), and direct imaging cryogenic transmission electron microscopy (cryo-TEM).
49. In-situ polymerization and self-assembly of cationic surfactants

Kathryn A. White, Edinburgh University, Edinburgh, United Kingdom and Gregory G. Warr, The University of Sydney,
Sydney, Australia
Polymerization of self-assembled amphiphiles with preservation of nanostructure is a goal that is not commonly
achieved. Often the properties of the monomer and the oligomers produced as reaction proceeds differ so dramatically
that the polymerized structure is unrecognizable from its starting point. Successful control over self-assembly as the
structure evolves from dynamic equilibrium into a permanently-rendered polymerized state offers a novel route to the
preparation of hierarchically structured, functional and novel composite materials.
In this work we will describe a base-catalysed ionic polymerization of derivatives of cationic, N-alkylpyridinium
surfactants that may be carried out in polar or aqueous solutions. The reaction may be started and stopped at will by
addition of base or acid, allowing oligomer distributions to be isolated and characterized. Characterization of the micelles
and lyotropic phases formed by the monomer and oligomer mixtures by optical microscopy and small-angle x-ray
scattering will be described.
We will also report on the in-situ polymerization and controlled reorganization of an aqueous micellar solution of
monomer into a dispersion of polymerized hexosomes. Using real-time kinetic small-angle neutron scattering together
with SAXS and electron microscopy characterization of the nanostructured dispersion, we will demonstrate how the size
of the hexosomes can be controlled by acid quenching.
50. Keynote: Surfactant Effects at Alkane-Water Interfaces: Freezing and Deformation

Colin D. Bain, Durham University, Durham, United Kingdom
Surfactants have dramatic effects on the properties of oil-water interfaces. This talk will describe two avenues of
research conducted in our group in recent years. The first concerns surface freezing. Pure alkanes are almost unique in
showing surface freezing at the air-liquid interface. Interfacial freezing is not observed at the alkane-water interface, but

can be induced by the presence of surfactants. One consequence of interfacial freezing is that the interfacial tension
can vanish. The second area of research concerns the deformation of emulsion droplets with optical fields. Optical
tweezers do not normally deform oil droplets since the force constant of optical traps is much weaker than the
interfacial tension. Near microemulsion phase boundaries, the interfacial tension drops to ultralow values and optical
fields can then be used to sculpt the shape of droplets. One unexpected observation is the formation of stable
nanothreads of oil.
51. Lateral Adhesion Balance (LAB) -- a Novel Surface Characterization Technique

Rafael Tadmor, Lamar University, Beaumont, TX
Drop lateral adhesion to a surface and the condition for drop sliding along a surface are key issues in many disciplines
including biophysics, environmental science, fluid dynamics and agriculture. Yet, to date, except for the tilt stage
method, which is extremely limited in range of forces, there is no systematic experimental instrumentation to measure
the forces required for drop sliding. We present a new instrument that uses centrifugal forces to slide any drop along a
surface. Beyond extending the range of measurable drop-surface interaction, the instrument enables decoupling of
some parameters that are bound to be coupled with the simple tilt stage method. Specifically the tilt stage method has
two variables varying at the same time: the lateral and normal forces. This violates a fundamental principle of
experimental science which leads to obscured understanding of surface characteristics. The LAB avoids this problem.
52. Classification of Nano-Friction Characteristics of Silica Surfaces in Electrolyte Solutions

Investigated by AFM
E. Taran, D.C. Donose, I.U. Vakarelski, H. Shinto, Y. Kanda and Ko Higashitani, Kyoto University, Kyoto, Japan
We conducted very carefully a series of friction measurements between completely-hydrophilic silica surfaces in various
electrolyte solutions of normal and high pH's, and found that the friction behaviours are classified into 4 Cases.
In the case of normal pH, the lubrication was observed for solutions of mono-valent cations, which was classified as
Case A, although the degree of lubrication depends on the kind and concentration of cations. As for the divalent
cations, the transition from Case A to Case B was found with increasing hydration enthalpy of cations. In the case of
trivalent cations, the behaviour was classified as Case, where the anions play an important role.
In the case of high pH, the surfaces were hairy-like and elastic. It was found that (1) the relation of the friction FL vs.
the loading force L is non-linear, (2) whether the friction behaviour was classified as Case C or D depends on the
adhesive property of adsorbed layers of cations on the hairy-like surfaces. The interesting relation of FL vs. v shown in
Case B and D was explained theoretically. The details will be given in the talk.
53. Surfactant Adsorption at the Air-Liquid and Hydrophobic Solid-Liquid Interfaces:

Unraveling the Mechanism for Superspreading
Makonnen M. Payne 1 , Alexander Couzis2 and Charles Maldarelli2 , (1)Graduate School of CUNY (City College of New
York), New York, NY, (2)The City College of New York, New York, NY
In this paper we report our findings with regard to the synergistic interactions between polyethylene oxide surfactants of
the general structure CiEj and compare the behavior to a known super wetting surfactant. Pendant drop tensiometry
experiments and sessile drop contact angle measurements on hydrophobic surfaces were conducted on combinations of
CiEj surfactants with 1-dodecanol. We found that a number of combinations were capable of reducing significantly the
air-liquid tension, however only systems that exhibited the propensity to form extended liquid crystalline phases, as
shown by the combination of cross-polarized microscopy, cryo-TEM, and light scattering experiments, were able to
improve on the wetting performance of the these systems. We have also conducted the parallel experiment focused on
the surfactant adsorption at the hydrophobic solid-liquid interface. Using in-situ infrared internal reflection spectroscopy
and complimentary sum-frequency generation spectroscopy, we are able to dynamically interrogate the surfactant
adsorption kinetics and interfacial water structure evolution at the hydrophobic solid-liquid interface. We will relate these
findings to gain insight into the molecular requirements for superspreading.
54. Adsorption of highly extended polymers using Optical Reflectometry

Shaun C. Howard1 , Vincent SJ Craig 1 , Erica Wanless2 and Paul Fitzgerald 2 , (1)the Australian National University,
Canberra, ACT, Australia, (2)The University of Newcastle, Callaghan, NSW, Australia
Optical Reflectometry (OR) is a form of ellipsometry that is used to measure adsorption of surfactants, polymers and
particles at the solid-liquid interface and is ideal for following the kinetics of adsorption. Certain polymer systems have
been shown to produce unphysical results when observed using the standard OR setup including some adsorbed
polymeric layers measuring up to several hundred nanometres in thickness. These systems yield an apparent negative
adsorption at the interface when measured by OR. Investigation of this phenomenon has revealed that this occurs in
part due to the minimal difference in the refractive indices of highly solvated adsorbed polymer and solvent. Further
analysis has resulted in a more robust model for the OR technique which greatly broadens its applicability to the
measurement of polymers and particles which were previously impractical.
Recent developments in the technique of Optical Reflectometry will also be presented. These include improved
versatility in substrate selection and the effect of external forces on adsorption.
55. Ion-specific bubble coalescence inhibition in single and mixed electrolytes

Christine L. Henry and Vincent S.J. Craig, Australian National University, Canberra, Australia
Ion specificity is at the heart of many biological processes and is important in all soft matter systems at high electrolyte
concentrations, under which conditions the double layer interaction is screened and short-range forces determine
colloidal behavior. Consequently interactions become considerably more complex and the precise character (charge,
size, polarisability etc.) and pairing of ions are important. It remains a great challenge for colloid scientists to develop a
detailed understanding of ion-specificity.
A simple system that reveals such complex behavior is that of gas bubbles in salty water. For one hundred years it has
been recognized that some electrolytes at sufficiently high concentrations can inhibit bubble coalescence relative to the
pure liquid. Electrolytes inhibit coalescence or have no effect as predicted by ion combining rules based on empirical
cation and anion assignments. The mechanism behind electrolyte inhibition, as well as the salt differentiation, is not
understood.
I here report a considerable volume of work on measurements of surface tension and bubble coalescence in aqueous
solutions of both single electrolytes and electrolyte mixtures. This has enabled us to rule out surface tension effects as
the mechanism of bubble coalescence inhibition. Mixed electrolyte results are consistent with the hypothesis recently
put forward by Marcelja, that electrolyte effects depend upon ion separation within the interfacial region. I explore
mechanisms by which the organization of molecules at the interface can control film rupture at separations of tens of
nanometers. We have further extended our investigation to electrolyte effects on bubble coalescence in non-aqueous
solvents.
56. Keynote: Alcohol Reforming over Pd/ZnO Catalysts

John Vohs, University of Pennsylvania, Philadelphia, PA
Alcohol Reforming over Pd/ZnO Catalysts

57. Reforming of Oxygenates for H2 Production on Bimetallic Surfaces

Orest Skoplyak, Mark A. Barteau and Jingguang G. Chen, University of Delaware, Newark, DE
Production of hydrogen for use in fuel cells can be achieved by selective reforming of oxygenates. The oxygenates may
be derived from renewable biomass and offer advantages such as low toxicity, low reactivity and compatibility with the
current infrastructure for transportation and storage. In this study, the reactions of oxygenates, such as methanol,
ethanol and ethylene glycol, were investigated on 3d-Pt(111) bimetallic surfaces using temperature-programmed
desorption (TPD), high-resolution electron energy loss spectroscopy (HREELS), and Density Functional Theory
calculations (DFT). The bimetallic surfaces were prepared by physical vapor deposition (PVD) of the desired second
metal onto Pt(111), using Auger electron spectroscopy (AES) to monitor surface compositions. Oxygenates reacted on
3d-Pt(111) to primarily form H 2 and CO. Surfaces prepared by deposition of a monolayer of Ni on Pt(111) at 300 K,
designated as Ni-Pt-Pt(111), displayed increased reforming activity compared to Pt(111), subsurface monolayer Pt-Ni-
Pt(111), and thick Ni/Pt(111). The experimentally measured reforming yield displayed a linear trend with the surface d-
band center for both ethylene glycol and ethanol. The reforming activity increased as the surface d-band center moved
closer to the Fermi level, opposite to the trend previously observed for hydrogenation reactions. DFT results indicated
that the binding energy of methanol and ethanol increased as the d-band center of the bimetallic surface shifted closer
to the Fermi level, which could be achieved by choosing 3d metals from the left side of the periodic table as the
surface monolayer. Further studies are underway to investigate oxygenate reforming on other 3d-Pt-Pt(111) bimetallic
surfaces.
58. Photocatalytic properties of ETS-10 & ETVS-10s toward the reduction of VOCs
Michael J. Nash, Anne Marie Shough, Doug Doren and Raul Lobo, Univesity of Delaware, Newak, DE
We have investigated ETS-10 and vanadium-incorporated ETS-10 as photocatalysts for the reduction of volatile
organic components (VOCs) since their unique structure may help elucidate the material and surface properties needed
to overcome some of the disadvantages of traditional semiconductors like anatase. ETS-10 is a microporous
titanosilicate composed of octahedral chains of TiO6 embedded in a tetrahedral SiO4 framework. These chains stack
perpendicular to each other to form a 7.5 Å, three-dimensional channel structure with an ideal stoichiometry of (Na,
K)2TiSi5O13. Vanadium has been shown to substitute for the titanium along the chain forming (V/(V+Ti))ETVS-10s and
can completely replace titanium forming an analogous structure to ETS-10, called AM-6. This incorporation of vanadium
has also shown visible photocatalytic activity that has been explained experimentally and theoretically. These chains of
TiO2 behave as 1D semi-conducting wires which are insulated by the SiO2 framework. Therefore chain termination
sites on the surface of the crystal or at defects along the chain play a crucial role in the electron-hole transfer from the
chain to adsorbed organic molecules. Previous work has shown that ion exchange leads to an increase in chain
termination for ETS-10 samples along with different photocatalytic properties. In this research we will determine the
effects of acid site formation through NH4 ion exchange in an attempt to maximize the photocatalytic reactivity of the
ETVS-10 samples for VOCs decomposition.
59. Wet oxidation of phenol over transition metal oxide catalysts supported on
Ce 0.65 Zr0.35 O 2 prepared by continuous hydrothermal synthesis in supercritical water
Kyoung-Hun Kim, Jeong-Rang Kim and Son-Ki Ihm, KAIST, Daejeon, South Korea
Continuous hydrothermal synthesis in supercritical water (supercritical synthesis) is a method to prepare highly
crystalline nanoparticles of homogeneous complex metal oxides as well as single metal oxides rapidly and continuously
using supercritical water as antisolvent. Ceria-zirconia mixed oxide has widely been used as catalytic promoter due to
its oxygen storage capacity (OSC). Ceria-zirconia mixed oxide with high surface area could be prepared by the
supercritical synthesis, so that it also has the potential application as catalyst support due to its high surface area. In
this study, ceria-zirconia mixed oxide with high surface area prepared by the supercritical synthesis was used as a
support of transition metal (Mn, Fe, Co, Ni, Cu) oxide catalysts for wet oxidation of phenol. Intermediate selectivity and
mineralization selectivity were investigated together with catalytic activity. Copper oxide catalyst showed the highest
catalytic activity which could be explained with the surface reducibility of the catalysts. Also, copper oxide catalyst
showed the highest mineralization selectivity indicating that it remarkably enhanced the deep oxidation of phenol. Ceria-
zirconia mixed oxide prepared by superciritical synthesis is a promising catalyst support for wastewater treatment. Its

oxygen storage capacity can assist the active element in removing organic pollutant such as phenol.
60. Characterization of K-promoted Ru catalysts for ammonia decomposition discovered

using high-throughput experimentation
William D. Pyrz, Rohit Vijay, Raul F. Lobo, Dionisios G. Vlachos, Jochen Lauterbach and Douglas J. Buttrey, University
of Delaware, Newark, DE
The necessity for alternative energy solutions is motivated from increasing fuel prices, stringent emission regulations,
and depleting fuel resources. The most attractive option is H 2 , as it has high-energy efficiency and H 2 O is the only
byproduct of its combustion. Ammonia has emerged as an attractive source for H 2 because of its high hydrogen
storage capacity (17.7 %), energy density (3000 Wh/kg), and the catalytic decomposition of NH3 is free of CO x
emissions. Ru catalysts have been successful for this reaction and we have chosen to examine this system further.
Using incipient wetness impregnation, we have investigated the effect of several promoters (K, Cs, Ba, Na, Rb, Li, Sr)
and solvents (H2 O, DMSO, ACN, THF, MEK, 2-propanol) on the low-temperature ammonia decomposition over Ru
catalysts supported on Al 2 O 3 . Using the high-throughput screening, we have determined that K promotion provides
dramatic enhancement (up to 30%) in the conversion of NH3 at a reduced temperature of 350°C (Figure 1). Using TEM
and SEM, it was discovered that the addition of K to Ru induces the formation of potassium ruthenium oxide
“nanowhiskers” as opposed to Ru agglomerates (Figure 1) that appear to be responsible for the enhanced
performance. Furthermore, it was discovered that changing the preparation solvent from H 2 O to an alcohol for an
identical Ru/K ratio provides an additional boost in the NH3 conversion (up to 30%) at even lower temperatures (T=300°
C).
61. Preparation of MgO (111) Nanosheets and their Catalytic Behavior

Ryan M. Richards, Juncheng Hu and Kake Zhu, International University Bremen, Bremen, Germany
Information about the elementary processes involved in heterogeneous catalysis is often obtained from studies with
well-defined crystal surfaces. However, current techniques are not efficient in preparing the desired well-defined crystal
surfaces. In particular, preparation of MgO (111) has remained illusive to date although theoretical studies have
predicted its' stability in the form of a hydroxide. Recently, we reported a simple, efficient and cheap wet chemical route
for preparation of MgO (111) nanosheets. We have discovered that MgO nanosheets possessing the exposed (111)
plane as a main surface can grow preferentially from magnesium methoxide-benzyl alcohol via self-assembly through
slow hydrolysis. The MgO (111) nanosheets have a thickness of less than 10 nm, typically between 3 and 5 nm. The
(111) surface is particularly interesting; because it possesses alternating polar monolayers of negatively charged oxygen
anions and positively charged magnesium cations. Thus, a strong electrostatic field perpendicular to the (111) surface is
created. Such a surface has provided a prototype for the study of surface structure and surface reactions of oxides,
which drew great attention for both experimental and theoretical studies. The MgO (111) nanosheets have been studied
by in-situ DRIFT spectroscopy and TPD revealing insights into the surface chemistry. Additionally, the catalytic
properties of the nanosheets for the Claisen-Schmidt reaction and low temperature decomposition of methanol have
been studied and mechanistic insights have been elucidated spectroscopically.
62. Keynote: Self-assembly of static and dynamic nanostructured materials

Bartosz A. Grzybowski, Northwestern University, Evanston, IL

Self-assembly of nanoscopic components into higher-order architectures defines the forefront of fundamental
nanoscience research and is important for the development of new materials with potential applications in
optoelectronics, high-density data storage, catalysis, and biological sensing. In my talk, I will discuss how the peculiar
nature of electrostatic and photoinduced dipole-dipole forces acting between nanoscale components can mediate their
self-assembly into various superstructures and materials. I will show how the interactions underlying self-assembly can
be studied and understood in quantitative detail, and how they can be tailored to synthesize unusual higher-order
architectures: ionic-like crystals of nanoparticles, crystalline aggregates that can be assembled and disassembled by
light, as well as extremely durable and yet very flexible metallic structures. Since these materials display a range of
novel optical, electrical and mechanical properties, the discussion of experimental results will be accompanied by
theoretical analyses combining elements of thermodynamics, statistical mechanics, electrodynamics and elasticity.
63. Light induced property changes

Ana Vesperinas and Julian Eastoe, University of Bristol, Bristol, United Kingdom
Recent advances address the capability to exert externally-triggered photo-control over interfacial and aggregation
properties. If a surfactant molecule contains a suitable chromophore, illumination can be used to achieve different
physical photo-induced responses. The advantage of this approach is it eliminates the need for composition or
temperature changes. Photodestructible surfactant sodium 4-hexylphenylazosulfonate (C6PAS) has been used to drive
interesting and dramatic changes in properties of different systems by UV light. Light-induced macroscopic phase
separation of micelles and emulsions systems occurs when C6PAS is mixed with an inert noninoic surfactant in the
presence of salting-out electrolyte. The initial mixed micelle systems can disperse an insoluble additive marker dye that
may be recovered and spatially segregated from the starting heterogeneous aqueous environment by UV light. Other
samples, employing photodestructible surfactants in gelatin-based aqueous gels present a novel approach to control
rheological and aggregation gel properties with possible applications in systems requiring rheological switches. Light-
triggered breakdown of the gelatin-bound photosurfactant aggregates causes dramatic changes in viscosity and
aggregation.
64. Partition of a Cleavable, 1,3-Dioxolane, Nonionic Surfactants, sodium bis (2-ethylhexyl)

sulfosuccinate and n-octyl-beta-D-glucopyranoside in 2- and 3-Phase Water-Isooctane
Microemulsion Systems
Javier A. Gomez del Rio and Douglas G. Hayes, University of Tennessee, Knoxville, TN
The equilibrium partitioning of a 1,3-dioxolane (pH-degradable) alkyl ethoxylate surfactant in 2- and 3-phase
microemulsion systems formed from equal volumes of water and isooctane was determined as a function of
temperature (20-50oC) and surfactant concentration (5-10 wt. %), in single and binary surfactant systems, the latter
with Aerosol-OT and octyl-beta-D-glucoside. The head group of the surfactant molecules consist of poly(ethylene
glycol) monomethyl ether (or MPEG) with degree of polymerization distributed around the average value of 7.2 as a
Poisson function. Semilog plots of partition coefficient (surfactant concentration ratio of isooctane to water-rich phases)
versus MPEG degree of polymerization correlate well to straight-line models, consistent with theory and previously
published results for alkyl ethoxylate surfactants. The slope and the y-intercepts of the linear models are strong
functions of temperature. The addition of a second surfactant had only a minor effect on the equilibrium partitioning of
the 1,3-dioxolane surfactant.
65. A journey towards novel template materials for nanoparticle synthesis

Regina Schwering, Thomas Sottmann and Reinhard Strey, University of Cologne, Colgone, Germany
Dynamic self-assembled structures found in complex fluids containing surfactant, water, and oil, range from spherical
and cylindrical swollen micelles to bicontinuous microemulsions and ordered liquid crystalline phases [1]. These
structures are extensively used as templates for the synthesis of nanomaterials [2,3]. However, up to date, it is not
possible to copy the microemulsion-structure to the microstructure of polymer particles on a one-to-one scale. Recently
Co et al. [4,5] used a new class of highly viscous microemulsions that comprise surfactant, polymerizable oil, and
concentrated water/(sucrose/trehalose) solutions to maintain the microstructure. The addition of sugar enables the
kinetic of the phase behaviour to be slowed down compared to the changing monomer/polymer ratio during
polymerization. In this study we systematically investigated the phase behaviour of highly viscous sucrose-

microemulsions. Starting from the sugar-free nonionic system H 2 O – n-octane – C 10 E6 the amount of sucrose within
the water phase was increased up to 75%. It is found that the addition of sucrose shifts the phase behaviour to low
temperatures. By replacing the surfactant C 10 E6 by a more hydrophilic surfactant the temperature drop can be
compensated. The system H 2 O/(sucrose/trehalose) – C 6 MA – Agnique PG 264-G which is a highly viscous,
polymerizable microemulsion was further polymerized with varying amounts of cross-linker in the oil phase and the
structures were investigated by SEM and TEM. Additionally, the kinetics of the phase behaviour of systems containing
various amounts of sugar in the water phase was investigated by temperature jump experiments.
66. Controlling Demixed Micelle Architectures in Silica Particles Templated with Combined
Fluorinated and Hydrogented Cationic Surfactants
Stephen E. Rankin 1 , Rong Xing 1 , Barbara L. Knutson1 and Hans-Joachim Lehmler2 , (1)University of Kentucky,
Lexington, KY, (2)University of Iowa, Iowa City, IA
When incompatible surfactants are combined to serve as micellar templates for porous metal oxides, a large variety of
organizations of the surfactants can be imagined. These include (1) a single type of particle with a mesophase
determined by the majority surfactant and a morphology determined by the minority surfactant, (2) completely demixed
particles, each containing different surfactants and different mesophases, (3) a single type of particle composed of a
mixture of separate phases formed by the two surfactants, (4) a single type of particle in which separate micelles
composed of the two types of surfactants mix into a single disordered phase, and (5) a single type of particle in which
the two demixed surfactants organize into a novel mesophase. We will show that silica particles with any of the first
four structures can be prepared by the hydrolysis of tetraethoxysilane in aqueous ammonia in the presence of mixtures
of 2-perfluorooctylethylpyridinium chloride and cetyltrimethylammonium chloride. The first type of particles is formed
under mildly alkaline conditions, without added salts or alcohol. The second is favored by a moderate amount of
ethanol, although excess ethanol leads to surfactant mixing. The third type of particle is formed by increasing the
ammonia concentration. The fourth structure is formed by adding salts. These results are discussed in terms of the
effects of additives on micelle mixing, precipitation rate, and partitioning between the bulk solution and the precipitated
phase. The third and fourth structures are of particular interest for their controlled bimodal mesopore size distributions.
67. Carbon Dioxide Processing of Surfactant Templated Nano-Structured Silica Probed by

In-Situ Spectroscopy
Barbara L. Knutson1 , Kaustav Ghosh 1 , Stephen E. Rankin 1 and Hans-Joachim Lehmler2 , (1)University of Kentucky,
Lexington, KY, (2)University of Iowa, Iowa City, IA
Synthesis of nanoporous ceramic materials by surfactant templating provides opportunities to control pore size, shape,
and functionalization for advanced materials applications. Ordered silica material is synthesized through a co-assembly
process, in which the hydrophobicity of the surfactant tail group drives the formation of the mesophase, while the
hydrolyzed silica precursor associates with the surfactant head group. Polymerization of the precursor and subsequent
surfactant removal results in pore structures that mimic the surfactant mesophase. We have demonstrated the ability to
tune pore size of fluorocarbon surfactant templated nanoporous silica thin films and precipitated particles using
compressed and supercritical CO 2 . Compressed CO 2 results in a significant increase in pore diameter for cationic
fluorinated surfactant templated materials due its favorable interactions with the ‘CO 2 -philic' fluorinated tail. In-situ
fluorescence spectroscopy is used to monitor the dynamic changes in the film structure in the presence of CO 2 and to
interpret the difference in pore size increase observed for hydrocarbon and fluorocarbon templates. The structures of
the fluorescent probes are tuned to preferentially localize them in either the hydrophobic interior of the micelles or at the
ionic silicate-tail interface and their responsiveness to CO 2 pressure is demonstrated. A significant increase in the time
period of modulable steady state (MSS), indicating delayed condensation of silica structure, is observed in the presence
of CO 2 . The results suggest time scales and approaches to further refine the nano-structured materials (i.e., infuse
pores with reactive agents, functionalize pores, and reorient functional groups within the pores) using CO 2 processing.
68. Kinetics of Coupled Primary- and Secondary-Minimum Deposition of Colloids Under

Unfavorable Chemical Conditions

Yan Jin1 , Chongyang Shen 1 and Yuanfang Huang 2 , (1)University of Delaware, Newark, DE, (2)China Agricultural
University, Beijing, China
This study examines the deposition/release mechanisms involved in colloid retention under unfavorable conditions
through theoretical analysis and laboratory column experiments. A Maxwell approach was utilized to estimate the
coupled effects of both primary- and secondary-minimum deposition. Theoretical analysis indicates that the secondary
energy minimum plays a dominant role in colloid deposition even for nano-sized particles (e.g., 20 nm) and primary-
minimum deposition rarely happens for large colloids (e.g. 1000 nm) under unfavorable conditions. Polystyrene latex
particles (30 nm and 1156 nm) and clean sand were used to conduct three-step column experiments at different ionic
strengths and a constant pH of 10. The results confirm that small colloids can also be deposited in the secondary
minimum. Additional column experiments involving flow interruption further indicates that the deposited colloids can be
spontaneously released to bulk solution when the secondary energy minimum is comparable to the average Brownian
kinetic energy. Experimental collision efficiencies are in good agreement with Maxwell model predictions but largely
different from the theoretical calculations by the interfacial force boundary layer approximation. Our study proposes a
priori approach to estimate collision efficiencies accounting for both primary- and secondary-minimum deposition and
suggests that the reversibility of colloid (e.g. viruses and bacteria) deposition must be considered in transport models
for accurate predictions of their travel time in the subsurface environments.
69. Transport Behavior of Adhesion-Deficient Bacterial Strain in a Radial Stagnation-Point

Flow System
Vishal Gupta 1 , William P. Johnson 2 and Jan D. Miller 1 , (1)Department of Metallurgical Engineering, University of Utah,
Salt Lake City, UT, (2)Department of Geology & Geophysics, University of Utah, Salt Lake City, UT
The fate, transport and adhesion characteristics of microbes are of significant interest in restoration and maintenance of
drinking water supplies, and as infectious agents from which drinking water supplies must be protected. This
investigation examines the origins of observed differences in transport behavior of two different adhesion-deficient,
gram-negative bacterial strains – DA001 & OY107 in a radial stagnation-point flow system. Measured surface
characteristics (e.g. surface potential, electrostatic interaction chromatography, and hydrophobic interaction
chromatography) indicate equivalent surface properties for these two strains. However, field scale and benchtop
transport experiments demonstrate strongly contrasting transport behaviors for these two strains in porous media.
Observation of these strains in the radial stagnation-point flow system provides directly-observed differences in their
attachment detachment behaviors that may lead to better understanding of their contrasting transport behaviors despite
their equivalent surface characteristics.
70. Activity, growth, and transport of Dehalcoccoides sp. in saturated soil

Charles E. Schaefer, Charles W. Condee and Robert Steffan, Shaw Environmental, Inc., Lawrenceville, NJ
Chlorinated ethene contamination in groundwater is a major environmental concern at several sites. Bioaugmentation,
which involves in situ delivery of electron donor, nutrients, and microorganisms to degrade the chlorinated ethenes, has
been shown to be a cost-effective approach for addressing such sites. Dehalococcoides sp. (DHC) is the only microbial
species known to completely dechlorinate PCE and TCE, and have been used extensively for bioaugmentation
treatment of chlorinated ethenes. Despite their widespread application, a fundamental understanding of DHC activity,
growth, and transport in situ is lacking.
A series of laboratory batch and column experiments were performed to evaluate the activity (with respect to chlorinated
ethene biodegradation), growth, and transport of a commercially available DHC consortia. The specific objective of the
study was to determine the mechanisms controlling DHC migration through the column while the bacteria were actively
growing and degrading the contaminants.
Results of the column experiments showed that only a small fraction (<1%) of the injected DHC eluted through the
column. No spatial gradient in aqueous phase DHC concentrations were observed, but measured aqueous phase DHC
concentrations increased with time at a rate that was well-predicted by the Monod model coupled with a microbial
transport model. VOC concentrations were also well-predicted by the coupled model. Overall results of the column
experiments suggest that observed DHC distribution and VOC degradation during bioaugmentation is dependent upon a
relatively small fraction of mobile and active DHC that grow and detach from retained biomass.

71. Escherichia coli deposition and transport in porous media: the coupled role of
temperature and solution chemistry
Hyun J. Kim and Sharon L. Walker, University of California, Riverside, Riverside, CA
The influence of temperature and solution chemistry on cell deposition in porous media has been investigated in a well-
controlled packed-bed system using Escherichia coli D21g. Three different temperatures (4, 10, and 25 o C) and two
different electrolytes (KCl and CaCl2 ) were employed for the experiments. To compliment the transport experiments,
the bacterial viability, cell size, hydrophobicity, elecrophoretic mobility, and extracellular polymeric substances (EPS)
composition were characterized. These analyses indicated the cell surface chemistry's sensitivity to solution chemistry
and temperature. Additionally, transport experiments using 1 μm carboxyl modified latex (CML) particles were
conducted to compare with E. coli D21g deposition trends. The experimental results showed that the deposition rate of
CML particles increased with temperature in the presence of both electrolyte, suggesting that enhanced Brownian
motion and decreasing viscosity results in greater transfer of particles to the collector surface. On the other hand, the
E. coli D21g experimental results indicated the deposition rate and attachment efficiency (α) of the cell were greatest at
10 o C in the presence of KCl; however, the impact of temperature was negligible in the presence of CaCl2 . Based upon
these results, it has been observed that an additional biological phenomenon, which has not been involved in classical
filtration theory (CFT), contributes to the deposition kinetics of E. coli D21g in addition to physicochemical mechanisms.
72. Impact of bacterial surface exopolysaccharide (EPS) composition on cell deposition in

porous media
Yang Liu and Jin Li, University of Wisconsin, Milwaukee, Milwaukee, WI
The attachment of three genetically well-defined isogenic Pseudomonas aeruginosa strains (PAO1, PAO1 psl pel and
PDO300) with different EPS secretion capability and EPS composition were studied over a range of solution chemistry
in glass beads packed columns, to examine the removal of P. aeruginosa from the bulk fluid due to their attachment to
the solid surfaces. The deviation of experimental data from classic colloid filtration theory (CFT) was investigated by
comparing the distribution of bacterial as a function of column depth with CFT model. The results show that the
presence of EPS on nonmucoid strain PAO1 and mucoid strain PDO300 significantly increased bacterial adhesion over
the EPS deficient PAO1 psl pel, despite their similar surface charges as indicated by the zeta potential measurement.
EPS deficient strain exhibited the log-linear deposition pattern under high ionic strength conditions, consistent with
trends predicted from the filtration theory. In contrast, non-monotonic deviations in the form of down-gradient movement
of the maximum retained cell concentration from the column inlet were observed when the EPS secretion strains were
examined. The retained polysaccharides (carbohydrates and uronic acids) and protein profiles inversed bacterial
deposition profiles, indicating that bacterial re-entrainment and re-entrapment may have contributed to the non-
monotonic retained profiles. The detachment of bacteria leaves behind various constituents of EPS as their “footprints,”
which can interfere with cell deposition.
73. Bacterial interactions with natural organic matter, proteins, and peptides
Terri A. Camesano, Laila I. Abu-Lail, Arzu Atabek and Joshua Strauss, Worcester Polytechnic Institute, Worcester, MA
The interactions of bacteria with organic matter affects applications ranging from natural processes such as bacterial
transport in the subsurface and in situ bioremediation, to engineered processes such as bioaugmentation and bacterial
inactivation with antimicrobial peptides. In the environment, natural organic matter (NOM) is a complex mixture that
includes identifiable compounds such as proteins and polysaccharides, but is generally defined operationally into groups
such as humic and fulvic acids. This work describes how atomic force microscopy (AFM) can be used to characterize
and quantify the interfacial forces between microbes and organic matter-coated surfaces. A model polymer,
poly(methacrylic) acid, was chosen as a simple model for NOM, due to its highly charged nature and presence of
carboxylic groups. The way that the model NOM interacted with bacteria was compared with the behavior of Suwanee
River Humic Acid and a Soil Humic Acid. Based on AFM measurements of adhesion forces between bacteria and an
NOM-coated probe, PMA was not a good model for the way bacteria interacted with the humic acids. To try and
develop a more fundamental understanding of bacterial interactions with organic molecules, we also quantified the
adhesion forces between bacteria and model proteins (BSA, con A), and determined that these interactions are

dependent on bacterial LPS structure. Finally, new results are presented on the binding between bacterial LPS and
peptides having antimicrobial properties.
74. Nanofiltration of complex fluids containing colloid materials and dissolved

macromolecules: the combined fouling effect
Alison E. Harris, Jack S. Hale, Brent C. Houchens and Qilin Li, Rice University, Houston, TX
Natural waters and wastewater contain both colloidal materials and dissolved organic matter. Although extensive
research has been done on colloidal fouling and organic fouling processes separately and their mechanisms are
relatively well understood, little is known about the combined fouling process during filtration of a complex suspension
containing both types of foulants. Using a combination of experimental measurement and computational modeling, this
research explores the physicochemical mechanisms involved in the combined fouling process. In particular, the two
major mechanisms investigated were hindered back diffusion due to the high concentration of each foulant near the
membrane surface and changes in colloid deposition behavior due to adsorption of macromolecules onto the colloid
surface. The impact on the characteristics of the membrane due to macromolecule adsorption is also considered. The
model incorporates the hindered back diffusion mechanism by calculating the local fluid viscosity in the concentration
polarization layer and modifying the diffusion and flow accordingly. Fouling experiments in a cross-flow filtration system
using nanofiltration membranes were conducted with colloidal silica and two model organic foulants: a non-interacting
macromolecule, Dextran, and an interacting macromolecule, bovine serum albumin (BSA). The model organic foulants
were chosen for their respective adsorptive properties in order to isolate the effects of hindered back diffusion from the
effects of macromolecule-mediated colloid deposition. Model predictions are compared to experimental results as well
as existing concentration polarization/fouling models.
75. Polyelectrolyte-surfactant Complexes as Nanoscale Zerovalent Iron (NZVI) Surface

Modifiers for In Situ NAPL Targeting
Tanapon Phenrat, Hye-Jin Kim, Navid B. Saleh, Kevin Sirk, Robert D. Tilton and Gregory V. Lowry, Carnegie Mellon
University, Pittsburgh, PA
For in situ Non-Aqueous Phase Liquid (NAPL) source zone remediation, NZVI must be mobile in porous media and it
should have an affinity for the NAPL source zone. There are two methods to promote NAPL targeting, including
interfacial targeting where the particles adhere and become immobilized at the NAPL/water interface, and
destabilization targeting where a surface coating is desorbed in the presence of NAPL saturation or near-saturation,
leaving behind a bare, immobile particle. In this study, we assess the potential of mixtures of an anionic polyelectrolyte,
poly(styrene sulfonate) (PSS), and a cationic surfactant, cetyltrimethylammonium bromide (CTAB), as NZVI surface
modifiers to enhance NAPL targetability via interfacial targeting or destabilization targeting. Two methods of NZVI
surface modification were evaluated; 1) sequential adsorption of CTAB followed by PSS to provide a layered CTAB-
seq-PSS structure, and 2) adsorption of a premixed PSS-co-CTAB complex .CTAB-seq-PSS and PSS-co-CTAB
modified NZVI dispersions were mixed with excess NAPL (dodecane, TCE, or PCE) in water, or with NAPL-saturated
water to evaluate their affinity for the NAPL-water interface (interfacial targeting) and the desorption of PSS and CTAB
from NZVI due to the change of solvent quality for the complex (destabilization targeting). Complex desorption and
NZVI destabilization in the presence of NAPL was more extensive for the layered CTAB-seq-PSS than for the PSS-co-
CTAB complex . Transport of both types of modified NZVI dispersions are through a column of sand partially saturated
with NAPL will be discussed to evaluate the potential for in situ NAPL targeting.
76. Phase diagram and dynamics of patchy colloidal systems

Emanuela Zaccarelli, CNR-INFM-SOFT and Universita' La Sapienza, Rome, Italy
We study patchy models for colloidal systems to investigate the suppression of phase separation at low packing fraction
Φ. We find that, on reducing the number of patches, the critical point moves towards zero packing fraction, providing
the possibility to generate "empty liquids"[1]. Moreover, we find a new topology for the interplay of dynamical arrest with
the phase separation region, that appears universal for various models of patchy systems[2]. Differently from spherically
symmetric attraction where the glass line merges into the spinodal at large Φ allowing only for dynamic arrest as an
arrested spinodal decomposition, for patchy interactions a whole region of optimal network formation opens up, where
arrested states (gels) can be approached in equilibrium. We also discuss the deep analogy between patchy colloids and

network-forming liquids (e.g. water, silica)[3].
[1] E. Bianchi et al., Phys. Rev. Lett. 97, 168301 (2006)
[2] E. Zaccarelli et al, J. Chem. Phys. 124, 124908 (2006)
[3] C. De Michele et al, J. Phys. Chem. B 110, 8064 (2006); J. Chem. Phys. 125, 204710 (2006).
77. Gels, glasses and attractive glasses in the Laponite system

Daniel Bonn, University of Amsterdam and Ecole Normale Superieure, Amsterdam, Netherlands
The study of colloids allowed for a significant contribution to elucidating the basic physics of glass transition. In colloidal
systems, as the particle volume fraction is increased, the particles become increasingly slower and for even higher
volume fractions the glass transition is encountered. On the other hand, colloidal gels are known to form at extremely
low volume fractions in the presence of strong attractions. Gelation and the glass transition have important similarities.
Both are ergodic to non-ergodic transitions that are kinetic, rather than thermodynamic in origin, and distinguishing
between these two types of non-ergodic states experimentally is a longstanding controversy We report experiments that
allow for distinguishing gels from glasses in the Laponite system. This allows us to show that for a range of
concentrations, two distinctly different non-ergodic states can result at late times: either the glass or the gel forms at
late times with roughly equal probability. There is no way to tell beforehand which of the two options will be taken by
the sample, suggesting that there are at least two metastable minima in the system. We also report that a third state:
an attractive glass may be found in the same system.
78. Gel Transition in Silica Nanoparticle/Kaolinite Suspensions

John Y. Walz, Virginia Tech, Blacksburg, VA and Jason C. Baird, Yale University, New Haven, CT
Addition of silica nanoparticles and salt to an aqueous suspension of kaolinite particles can cause a rapid transition to a
gel. SEM micrographs indicate that the structure of the gel consists of the disk-like kaolinite particles arranged in edge-
to-face contacts, forming a porous honeycomb structure. The gel also shows a remarkable ability to rejuvenate after
breakage by shear. Although the exact mechanism responsible for this gellation is not known, it is hypothesised that
the nanoparticles first completely cover surfaces of the clay particles. Upon addition of sufficient amounts of electrolyte,
the electrostatic repulsion between silica particles on opposing kaolinite surfaces is screened enough that a van der
Waals bond can form. Random Brownian motion of the clay particles would create the edge-to-face arrangement. In
addition, because of the relatively large size of the clay platelets (several microns), this structure could be easily broken
by shear. This ability to rejuvenate is completely different from the behavior of gels formed from silica nanoparticles
only.
79. Direct Imaging of Biphasic Colloidal Mixtures

Summer K. Rhodes, Robert H. Lambeth, Jeffrey S. Moore and Jennifer A. Lewis, University of Illinois, Urbana-
Champaign, Urbana, IL
Concentrated colloidal gels have been utilized as inks for the direct-write assembly of complex 3D architectures.
However, such inks undergo a “jamming transition” when deposited through cylindrical nozzles with diameters on the
order of 100 mm or less. To overcome such difficulties, we are exploring a new ink design based on mixtures of
attractive and repulsive colloidal particles. Specifically, these biphasic inks are composed of silica microspheres coated
with either a cationic polyelectrolyte or a comb polymer consisting of a cationic backbone and charge neutral
polyethylene oxide teeth. Upon adding salt to this system, the cationic polyelectrolyte-coated silica microspheres
spontaneously flocculate while the comb polymer-coated colloids remain fully stabilized. Using confocal microcsopy, we
have directly imaged the 3D structural evolution of such mixtures as a function of total microsphere volume fraction,
ratio of attractive-to-repulsive microspheres, and salt concentration. Experiments are now underway to characterize the
structural evolution of ink filaments patterned by direct ink writing.
80. Gelation of Carbon Nanotube Networks

Daniel T.N. Chen 1 , Larry A. Hough 2 , Mohammad F. Islam 3 and Arjun G. Yodh 1 , (1)University of Pennsylvania,

Philadelphia, PA, (2)Rhodia Inc., Bristol, PA, (3)Carnegie Mellon University, Pittsburgh, PA
We investigate the gelation of a rigid rod network comprised of an aqueous suspension of surfactant stabilized Single-
Wall Carbon Nanotubes (SWNT). Using particle tracking microrheology, we follow the gelation of the SWNT suspension
from an initial sol of contacting, but unbonded, tubes to a fully cured gel of contacting tubes bonded by van der Waals
interactions. The SWNT network exhibits many features found in critical sol-gel transitions, including divergence of the
viscosity as the gel point is approached from below, emergence of a finite elastic modulus above the gel point, and
power law scaling of the viscosity and shear modulus below and above the gel point, respectively. The viscoelastic
moduli obtained at different times above the gel point can be collapsed onto a master curve using time-cure
superposition. Additionally, we present a scheme based on two-point statistics to characterize rheological
inhomogeneities in the network during gelation.
81. Slow dynamics and ageing in soft colloids

Dimitris Vlassopoulos, Christina Christopoulou, Emmanuel Stiakakis and George Petekidis, FORTH and Univ. of
Crete, Heraklion, Crete, Greece
Using light scattering (multispeckle DLS) and rheological (dynamic frequency sweep, creep and start-up in shear)
techniques, we investigate the slow dynamics of concentrated suspensions of star polymers, a model soft colloidal
system with tunable interactions. We focus on the transition to the glassy regime which, depending on the suspending
medium used, can be reached by increasing the number concentration or the temperature. We observe a rich dynamics
associated with this reversible liquid to solid transition. The rheology changes from viscoelastic to viscoplastic rather
gradually, and very long stress transients are detected. At the same time, the appearance of slow relaxation process in
the intermediate scattering function is evidenced, which appears to be responsible for the macroscopic immobilization of
the system. This relaxation process exhibits a logarithmic decay over 3 decades in time with extremely slow kinetics
(ageing); the latter is also manifested in a second ultraslow process in start-up experiments. The above relaxation
process decays gradually from stretched to logarithmic manner at high temperatures. We attempt at comparing this
systematic information with the analogue experimental evidence from hard sphere suspensions, attributing the
similarities to universality in behavior, the differences to the nature of the interactions, and leaving several open
questions for further research.
82. Flow of attractive colloidal suspensions in microchannels

Jacinta C. Conrad and Jennifer A. Lewis, University of Illinois, Urbana-Champaign, Urbana, IL
We use confocal microscopy to investigate the behavior of suspensions of attractive colloids at a constriction. We flow
suspensions of attractive silica colloids through microchannels and directly image both their structure and dynamics
during flow. Specifically, we investigate the flow properties as a function of applied pressure, microchannel geometry,
and the colloid volume fraction. When the applied pressure or displacement is relatively small, the particle velocity is
nearly constant across the channel, yet small rearrangements can still occur in the gel structure. When the applied
pressure or displacement is large, the gel structure is disrupted and the flow velocity changes across the channel width.
In addition, we also explore the non-equilibrium clogging that occurs when the system experiences jamming within
these microchannels.
83. Anomalous behavior in aqueous thin liquid films between hydrocarbons and fluorinated
hydrocarbons
Raymond R. Dagastine, Ivan U. Vakarelski, Lucy Y. Clasohm, Geoffery W. Stevens, Derek Y.C. Chan and Franz
Grieser, The University of Melbourne, Melbourne, Australia
Recent advances in the atomic force microscopy (AFM) force measurement techniques have allowed the direct
measurement and theoretical interpretation of the interaction between a liquid droplet and a solid surface or two liquid
droplets.1 Here we investigate the interaction across an aqueous thin film between fluorocarbon oil droplets,
hydrocarbon droplets or a droplet and a flat solid in the absence of stabilizers. The initial interest of the study was to
measure the short ranged van der Waals interaction forces operating in these systems. The van der Waals interaction
is usually attractive, but it can become repulsive when two dissimilar phases interact through a third phase of
intermediate optical properties. 2 Preliminary results between fluorocarbon droplets and solid surfaces did show

repulsion, but forces between symmetric oil droplets also show repulsion, even at high electrolyte concentrations.
These repulsive interactions also exhibited a pH dependence. Theoretical analysis of the magnitude and the range of
these forces suggest that DLVO forces can not explain the observed behaviour. The force behaviour will be discussed
in the context of ion adsorption and charging effects at bare oil water interfaces.
1. Dagastine, R.R, Manica, R., Carnie, S.L., Chan, D.Y.C., Stevens, G.W., Grieser, F. Science, 2006, 313, 210.
2. Milling, A., Mulvaney, P., and Larson, I., J. Colloid and Interface Sci., 1996, 180, 460.
84. Stability of foams and single foam films in the presence of n-alkyl polyoxyethylene
homologues
Ruijia Wang and Roe-Hoan Yoon, Virginia Tech, Blacksburg, VA
It was shown previously that at low concentrations of sodium dodecylsulfate (SDS) and methylisobutylcarbinol (MIBC),
hydrophobic force plays an important role in the stability of foam films (Wang and Yoon, 2005, 2006). In the present
work, effects of nonionic surfactants (n-alkyl polyoxyethy1ene homologues) on the stability of foam films have been
studied, with particular emphasis on the role of hydrophobic force. The magnitudes of the hydrophobic forces in foam
films were determined from the equilibrium film thicknesses and the film thinning kinetics measured using the thin film
pressure balance (TFPB) technique. The results show that single foam films thin much faster than predicted by the
DLVO theory due to the presence of hydrophobic force. In general, hydrophobic force decreases with increasing
concentration of a non-ionic surfactant. It was found also that hydrophobic force decreases with increasing chain length
of the n-alkyl group and with decreasing chain length of the EO groups.
85. Unexpected non-ideal mixing in homologous surfactants
Laura K. Hudson 1 , Julian Eastoe 1 and Peter J. Dowding 2 , (1)University of Bristol, Bristol, United Kingdom, (2)Infineum
UK Ltd, Abingdon, United Kingdom
Air-water interfacial studies with mixtures of linear and branched analogue give rise to surprising and unexpected
behavior: apparently a strong interfacial partitioning of branched chain surfactant at the expense of the linear chain
relative (non-idealities). This behavior is not predicted by the established theories, where it is believed that surfactants
bearing the same headgroup type and similar chains (hydrocarbons) mix ideally: i.e. it is straightforward to predict
physico-chemcial properties based on those of the individual compounds, and the known mixture composition. These
trends are also seen in water-in-oil (w/o) microemulsion phase stabilities and aqueous solubility measurements.
Neutron reflectivity (NR), small angle neutron scattering (SANS), surface tension (ST), phase behavior and aqueous
solubilities have been used to interrogate these mixed surfactant systems (comprising a homologous series of di-alkyl
anionic surfactants based on Aerosol-OT (AOT, sodium bis(2-ethyl-1-hexyl)sulfosuccinate - linear and branched alkyl
chains).
The understanding of complex surface chemistry and bulk behavior of mixtures of surfactants from a homologous series
is important for a wide range of applications such as detergents, drug delivery systems and tertiary oil recovery. This is
because mixtures provide synergistic enhancement of properties, or because commercial surfactants are naturally a
distribution of molecular masses.
86. Micellization of charged, water-soluble triblock copolymers with polyethylene oxide end
groups
Richey Davis, Beth Caba and Judy Riffle, Virginia Tech University, Blacksburg, VA
Novel triblock copolymers consisting of end blocks of polyethylene oxide (PEO) and a center block consisting of
urethane and carboxylic acid groups constitute an interesting class of polymers that can self-associate to form micelles
in water. Micelles of hydrophilic block copolymers are of interest due to their use in the controlled delivery of drugs and
other bioactive molecules. Micellization of these block copolymers results from a balance between hydrogen bonding
and hydrophobic attraction in the core and repulsion between PEO chains in the corona. The size and mass of these
micelles can be tuned by controlling pH and temperature, with ionic strength playing a lesser role. At pH 7 and 25 C,

the copolymers are fully soluble unimers with hydrodynamic radius RH ~2 nm whereas at pH 2-3, protonation of the
carboxylic acid groups in the core drives assembly of micelles with RH ~10-15 nm over a range of temperatures (25-65
C). These micelles were characterized by static and dynamic light scattering and small angle neutron scattering. The
micelle size can be predicted with reasonable accuracy from aggregation number measurements using the Density
Distribution model by Vagberg, et.al., that was based on the blob model for star polymers. The second virial coefficients
can be predicted semi-quantitatively using a model by Likos, et al., also based on star polymers.
87. Thermoreversible micellization and gelation for a blend of PEO-PPO-PEO and PPO-PEO-
PPO copolymers
Lin Li, Qiqiang Wang and Lee Hoon Lim, Nanyang Technological University, Singapore, Singapore
Aqueous solutions of a blend consisting of a PEO-PPO-PEO triblock copolymer and a PPO-PEO-PPO triblock
copolymer were prepared. Thermoreversible micellization and gelation properties of the blend were studied as a
function of temperature and molar ratio of two copolymers by means of micro-DSC and rheology. The completely
thermoreversible behaviors of micellization and gelation were observed for all solutions with various molar ratios. At a
given concentration of the PEO-PPO-PEO copolymer, three effects of the PPO-PEO-PPO copolymer were found: (a)
micellization shifted to a lower temperature with increasing the concentration of the PPO-PEO-PPO copolymer,
implying a “salt-out” like effect; (b) there appeared a secondary peak due to the interaction between two copolymers,
which increased in height with increasing the PPO-PEO-PPO copolymer; and (c) also the significant changes in
enthalpy and entropy were shown. The rheological studies allowed the determination of the sol-gel transition, the gel
strength, and the polymer-polymer interaction-induced unique features of rheology. The possible mechanism for the
PPO-PEO-PPO copolymer induced micellization and gelation will be proposed and discussed.
88. Dependency of calcium carbonate inhibition on structural characteristics of carboxylic-

acid containing polymeric antiscalants
Matthew R. Dubay1 , Steven J. Severtson 1 and Brian N., Brogdon 2 , (1)University of Minnesota, Saint Paul, MN,
(2)Kemira Chemicals, Inc., Marietta, GA
Formation of inorganic deposits or scale is a serious issue for industries that process large quantities of water. These
deposits increase energy consumption by heat transfer units, hinder separation and transport processes, and mandate
regular shutdowns for cleaning. One approach for mitigating this problem is the use of chemical additives that slow
crystal growth processes leading to deposit formation. These additives work primarily by adsorbing to developing nuclei
and growing crystal faces to slow the further incorporation of mass. These interactions are poorly understood and
information to guide the selection of an effective treatment chemical is not readily available. In this presentation,
research aimed at identifying the optimal structure for polymeric additives used to inhibit scale formation will be
reviewed. Discussed will be the use of polymeric additives to inhibit calcium carbonate scale formation in kraft pulping
liquors, which are processed at high temperatures and supersaturations. The focus will be on carboxylic acid containing
polymers, whose performance appears to be strongly dependent on its structural characteristics. Naturally occurring
polymers such as lignin along with synthetic co- and terpolymers produced from maleic and acrylic acid monomers will
be of particular interest. The most effective molecular weight distributions will be identified and possible explanations for
this dependency will be discussed. Also reviewed will be the role of other structural characteristics such as the
concentration of carboxylic acid functional groups and their distribution throughout the polymer backbone and the role of
chain flexibility.
89. Morphology evolution through viscous oil emulsification by catastrophic phase

inversion in semi-batch process
Johanna M. Galindo 1 , Veronique Sadtler 1 , Lionel Choplin 1 and Jean-Louis Salager2 , (1)Laboratoire GEMICO, ENSIC
- INPL, Nancy, France, (2)Laboratorio FIRP, Universidad de los Andes, Merida, Venezuela
Viscous oil emulsification by catastrophic phase inversion allows to obtain fine and homogeneous drop size without an
excessive energy addition. During the inversion process, a competition between composition (water/oil ratio) and
formulation induces the formation of unstable multiple emulsions.

We studied aqueous phase addition rate and stirring speed effects on emulsion characteristics, particularly on water
mass fraction value (Fw) at the inversion point. The studied system is composed of silicone oils (viscosities between 1
and 12 Pa.s), aqueous phase (1 % NaCl) and a mixture of nonylphenol polyethoxylate as surfactant. The emulsification
process is followed-up, in situ, by simultaneous viscosity and conductivity measurements. The aqueous phase is added
to the oily one, under continuous agitation until the inversion point, detected by an abrupt change in viscosity and
conductivity measurements, is reached.
Water mass fraction (at the inversion point) depends on multiple emulsion formation, and is also affected by the oil
phase viscosity. There is a total or partial inversion depending on the viscosity phase ratio. According to microscopic
observations of local morphologies obtained during the inversion process, for systems with low viscosity phase ratio,
the inversion is triggered through the following morphology evolution: W/O → w/o/W/O → w/O/W → O/W. For more
viscous oils, no morphology formation of type w/o/W/O has been observed before inversion point. Final emulsions are
highly concentrated emulsions either because Fw is about 5 to 9% in high oil viscosity systems, or because of the
persistence of multiple emulsions (w/O/W) in low oil viscosity systems.
90. Shear deformation in polymer networks

Qi Wen, Anindita Basu, Arjun G. Yodh and Paul A. Janmey, University of Pennsylvania, Philadelphia, PA
We explore the effects of macroscopic shear stress applied to a filamentous polymer network. In particular, we aim to
understand whether the network transforms affinely on microscopic length scales. Network deformations in response to
external stress were measured by tracking fluorescent beads embedded in the networks, using the 3D imaging
techniques. Networks of both flexible and semi-flexible polymers, for example, polyacrylamide and fibrin gels, are
studied at strain values ranging from linear to nonlinear regime. (This work is supported by the MRSEC grant DMR-
0520020, NSF grant DMR-0505048, and NSF MRSEC grant DMR00-79909.)
91. Critical stresses and cracking in thin films of colloidal dispersions

Weining Man Man, William B. Russel and Ning Wu, Princeton University, Princeton, NJ
Colloidal dispersions are often coated on a substrate to allow the solvent to evaporate and leave a uniform thin film.
However, cracks can form in the latter stages of drying. A negative capillary pressure develops as the air-water
interface is pulled down into the interstices between particles, putting the drying film in tension. The film responds by
collapsing normal to the surface but is constrained from shrinking laterally unless cracks open. Only through
understanding of the mechanism can colloidal dispersions be formulated to produce crack-free films.
In this study, we use a high-pressure ultra-filtration device to measure directly the pressure responsible for cracking in
uniform films of latex or silica dispersions containing particles of varying radii. The results confirm that cracking is
controlled by the recovery of elastic energy with the critical pressure increasing with the modulus of the particle,
decreasing with increasing film thickness, and independent of particle size. The Griffith¹s criterion for equilibrium crack
propagation along with the nonlinear stress-strain relation for drying films provides a necessary, but not sufficient,
condition for crack formation. As the pressure is increased beyond the critical value, additional cracks open in
qualitative agreement with our elastic energy recovery model. Films that lack of defects crack at a higher pressure than
predicted, while introducing flaws at the edges promotes cracking at the critical pressure. These observations suggest
an important role for defects in nucleating cracks.
92. Cracking in Drying Colloidal Films

Karnail B. Singh and Mahesh S. Tirumkudulu, Indian Institute of Technology-Bombay, Mumbai, India
When a thin film of wet paint or coating is dried on a substrate, evaporation of the solvent concentrates the particles
into a closed packed array. Further evaporation generates a compressive capillary force on the particle network. The
film generally binds to the substrate and resists deformation in the transverse direction giving rise to transverse tensile
stresses. If the particles are soft, they deform to close the pores but in case of hard particles the film cracks to release
the stresses. Though cracking has been investigated on various systems such as wet clays, ceramic films, latex and
model colloidal dispersions, it is only recently that a fundamental understanding of the cracking mechanism is beginning
to emerge. In the present investigation, we identify two distinct regimes for obtaining crack free films. The first
corresponds to soft particles that completely deform to give impermeable crack free films. The second regime is

applicable for films containing hard particles where the existence of a maximum attainable capillary pressure limits the
deformation and leads to porous crack free films. The measured critical heights for the latter regime over four orders in
shear modulus and an order in particle size are in remarkable agreement with the theoretical predictions. We anticipate
our results to not only form the basis for design of coating formulations for the paints, coatings and ceramics industry
but also assist in the production of crack free photonic band gap crystals.
93. Novel Dispersion and Self-Assembly of Single Wall Carbon Nanotubes

Mohammad F. Islam, Carnegie Mellon University, Pittsburgh, PA
I will describe our explorations of carbon nanotube science and technology from a soft materials perspective. We first
created stable dispersions of purified single wall carbon nanotubes (SWNTs) using an anionic surfactant, sodium
dodecyl benzene sulfonate (NaDDBS), and then studied their structure and rheology in suspension, demonstrating
interconnected networks of stiff filaments. Our attempts to induce nematic liquid crystalline alignment of SWNTs in
suspension did not succeed, but eventually led us to create a new class of nanocomposite: nematic nanotube gels.
These gels exhibit rich physical properties due to a coupling between the nematic alignment and the polymer network
elasticity.
94. Structure and phase behavior of melts and dense solutions of polymer tethered
nanoparticles and colloids
Arthi Jayaraman and Kenneth S. Schweizer, University of Illinois Urbana-Champaign, Urbana, IL
The microscopic Polymer Reference Interaction Site Model (PRISM) theory has been generalized and applied to study
dense solutions and melts of polymer tethered spherical particles. Intermolecular pair correlation functions, collective
structure factors, and bulk moduli are calculated to understand the equilibrium organization and tendency to microphase
separate. The complex interplay of entropy (translational, conformational and packing) and enthalpy (monomer-particle
attraction) leads to different spatial arrangements with distinctive scattering signatures, and a rich phase behavior. For
melts of these tethered particles, at low monomer-particle cohesive strengths the particles experience depletion
attraction. As the monomer-particle attraction is increased strong polymer mediated bridging of particle cores is
observed. The location of the peaks in the structure factors suggest that these tethered particles prefer to organize
themselves in a specific geometry that is dictated by the subtle competition of depletion attraction, osmotic repulsion,
monomer adsorption and grafting constraints. The effect of the length of tethered chains, number of tethered polymers
per particle, core radius, total fluid packing fraction, and monomer-particle interfacial attraction strength on the statistical
structure, properties and phase behavior will be discussed.
95. Modelling colloidal suspensions: Gelation, network formation and phase separation
Emanuela Del Gado, ETH Zurich, Zurich, Switzerland
In attractive colloidal suspensions at low volume fractions the underlying thermodynamics may significantly interplay
and/or compete with gel formation via phase separation processes. In particular I will consider the case of a colloidal
suspension with competing attraction and repulsion, where gelation results to be directly coupled to microphase
separation[1]. Then I will discuss a model in which directional interactions are able to produce a persistent gel network
at relatively high temperatures, where phase separation does not occur, without imposing a local functionality of the
meso-particle[2]. The numerical study shows in this case that the formation of the gel network does induce a non-trivial
length scale dependence of the dynamics in a simple model for colloidal gels: In the incipient gel, the relaxation at high
wave vectors is due to the fast cooperative motion of pieces of the gel structure, whereas at low wave vectors the
overall rearrangements of the heterogeneous gel make the system relax via a stretched exponential decay of the time
correlators. The coexistence of such diverse relaxation mechanisms is determined by the formation of the gel network
(i.e. the onset of the elastic response of the system) and it is characterized by a typical crossover length which is of the
order of the network mesh size. [1] A. de Candia, E. Del Gado, A. Fierro, N. Sator, M. Tarzia and A. Coniglio, Phys.
Rev. E 74, 010403(R) (2006). [2] E. Del Gado and W. Kob, Europhys. Lett. 72,(2005) 1032; Phys. Rev. Lett. 98,
028303 (2007).
96. Depletion-driven Colloidal Packing in Emulsions

Liang-jie Lai 1 , Chih-Chung Chang 1 , Yun-ting Chen 1 , Hui Chen 1 and Keng-hui Lin 2 , (1)National Central University,
Jhongli City, Taiwan, (2)Academia Sinica, Taipei, Taiwan
Here we observe new types of colloidal clusters produced from oil-in-water emulsions with microspheres and polymer
dispersed in oil droplets. We follow the cluster formation process as Manoharan's work [1]. The polymer induces
depletion interaction between microspheres. When the number of particles N inside the droplet is larger than 4 and not
equal to 6, we observe new configurations of final packing besides besides what Manoharan observed. Extra
configurations of packing are due to depletion interaction which gives rise to different initial packing of microspheres on
the surface of oil droplets. [1] V.N. Manoharan, M.T. Elsesser, D.J. Pine. Science 301, 483 (2003)
97. SANS studies of magnetically chained ferrofluid emulsions

Gregory G. Warr, Nirmesh J. Jain and Brian S. Hawkett, The University of Sydney, Sydney, Australia
Forces between aqueous ferrofluid droplets dispersed in tetradecane have been determined by small angle neutron
scattering (SANS) and optical interferometry using the magnetic chaining technique in an external magentic field. Force
versus separation curves obtained from both techniques are in excellent agreement for droplets stabilised by sorbitan
monooleate and polymeric emulsifiers. The anisotropic SANS pattern from magnetically-chained droplets can be
accurately described analytically as a one-dimensional string of regularly spaced spheres. In contrast with the
interferometric approach, SANS enables the droplet dimensions, separation and any deformation to be monitored in situ
as a function of applied field. SANS also thus provides a direct measure of the absolute droplet separation.
98. Small Angle Neutron Scattering Studies of the Counterion Effects on the Molecular
Conformation and Structure of Charged G4 PAMAM Dendrimers in Aqueous Solutions
Wei-Ren Chen 1 , Lionel Porcar 2 , Yun Liu 1 , Paul. D. Butler1 and Linda J. Magid 3 , (1)Oak Ridge National Laboratory,
Oak Ridge, TN, (2)National Institute of Standards and Technology, Gaithersburg, MD, (3)the University of Tennessee,
Knoxville, TN
The structural properties of generation 4 (G4) poly(amidoamine) starburst dendrimers (PAMAM) with an
ethylenediamine (EDA) central core in D2O solutions have been studied by small angle neutron scattering (SANS).
Upon the addition of DCl, SANS patterns show pronounced inter-particle correlation peaks due to the strong repulsion
introduced by the protonation of the amino groups of the dendrimers. By solving the Ornstein-Zernike integral equation
(OZ) with hypernetted chain closure (HNC), the dendrimer-dendrimer structure factor S(Q) is determined and used to fit
the experimental data, where Q is the magnitude of the scattering wave vector. Quantitative information such as the
effective charge per dendrimer and its conformational change at different pD values is obtained. The results show clear
evidence that significant counterion association occurs, strongly mediating the inter-dendrimer interaction. The influence
of interplay between counterions and molecular protonation of dendrimers imposes a strong effect on the dendrimer
conformation and effective interaction. Careful analyses of the high Q data indicate a possible development of a
secondary structure in a dendrimer evidenced by the appearance of a small high Q feature after the tertiary amino
groups begin to be charged.
99. Characterization of magnetic nanoparticles used for cancer thermotherapy

Robert Ivkov 1 , Julie Borchers 2 , Allan R Foreman 1 , Cindi Dennis 2 , P. J. Hoopes3 and Cordula Gruettner4 , (1)Triton
Biosystems Inc., Chelmsford, MA, (2)NIST, Gaithersburg, MD, (3)Dartmouth College, Hanover, NH, (4)Micromod
Partikeltechnologie, GmbH, Rostock-Warnemuende, Germany
Magnetic nanoparticles heat when exposed to an alternating magnetic field through hysteresis losses. These materials
offer the potential to selectively treat cancer by heating cancer tissue from within at the cellular level. This can be
successful provided a sufficient concentration of particles is achieved in the tumor possessing a sufficiently high
specific absorption rate (SAR) to deposit heat quickly while minimizing thermal damage to surrounding tissue. High SAR
magnetic nanoparticles have been developed comprised of iron oxide magnetic cores that have been used in mouse
models of cancer. Colloidal stability of these particles, mean diameter of 80 nm, is maintained by the incorporating a
polymer layer to form a "core-shell" construct. Structural, heating, and magnetic properties of these suspensions have
been characterized using a variety of techniques including light and neutroon scattering. These data will be presented,
as will the results of in vitro cell culture and in vivo mouse trials.

100. Slippery diffusion-limited aggregation of attractive nanodroplets measured by time-

resolved small angle neutron scattering
Thomas G. Mason, UCLA, Los Angeles, CA
The nature of the bonding between highly attractive colloids can lead to a profound difference in the structures of
aggregates, as revealed through scattering. In particular, colloidal bonds can either be 'shear-rigid', as is the case in
classic diffusion limited aggregation (DLA) experiments on solid gold particles, or they can be 'slippery', as we show for
attractive dispersions of uniform nanoscale droplets, or 'nanoemulsions', comprised of silicone oil in water. Despite the
strong attraction between the oil droplets, which has been induced by adding salt, a thin layer of the continuous phase
remains between droplets, precluding coalescence. Slippery attractions occur when the well depth of the secondary
minimum is much greater than thermal energy and the range is much smaller than the droplet radius. We use time-
resolved small angle neutron scattering (TR-SANS) to study the kinetics of the appearance of peaks related to
correlations between nearest neighbor droplets at high wavenumber, q, after abruptly creating an attractive interaction.
We show that small dense clusters of droplets are first formed, and these, in turn, aggregate into tenuous fractal
networks and gels. Simulations of slippery diffusion-limited aggregation (S-DLA) confirm an earlier hypothesis that
attractively jammed tetrahedra of spheres can be considered as the basic building block of space-filling clusters and
networks of slippery attractive spheres. The similarity between the computed structure factor, S(q), of S-DLA
aggregates and the measured S(q) indicates that slippery DLA is a useful concept for understanding scattering
signatures of attractively jammed networks of spheres.
101. Static and Dynamic X-ray Scattering from Nanoparticle Stabilized Liposome
Suspensions
Laurence B. Lurio 1 , Mrinmay Mukhopadhyay 2 , Yan Yu3 , Liangfang Zhang3 and Steve Granick3 , (1)Northern Illinois
University, DeKalb, IL, (2)University of California at San Diego, La Jolla, CA, (3)University of Illinois at Urbana
Champaign, Urbana, IL
Small angle x-ray scattering and dynamic x-ray scattering (XPCS) has been measured from nanoparticle stabilized
aqueous suspensions of approximately 200 nm diameter liposomes. Small angle x-ray scattering was used to extract
the overall liposome size, the surface distribution of the nanoparticles on the liposomes and the liposome-liposome
structure factor. Dynamic x-ray scattering was used to measure the translational motion of the liposomes in both dilute
and concentrated suspensions.
102. Small angle neutron scattering under shear flow: a new 1-2 plane flow-SANS
experiment with results for shearing colloids and surfactants
Norman J. Wagner1 , Florian Nettesheim1 , Dennis P Kalman 1 , Matthew E. Helgeson1 , Matthew W. Liberatore 2 and
Lionel Porcar 3 , (1)University of Delaware, Newark, DE, (2)Colorado School of Mines, Golden, CO, (3)National Institute
of Standards and Technology, Gaithersburg, MD
“Rheology without morphology...,” as the saying goes, becomes more unsatisfactory as complex fluids with increasingly
complex rheological behavior are investigated. However, developing structure-property relationships for flowing colloidal
dispersions, self-assembled surfactant solutions, polymer solutions and other complex fluids requires measurements of
the microstructure under flow. Small angle scattering, and in particular, neutron scattering with the advantages of
contrast matching techniques, provides one of the most complete methods for interrogating microstructure on the
submicron length scale. The most relevant microstructure for a system in simple shear is in the flow-flow gradient plane
(1-2 plane), which is the hardest to access in a scattering experiment. To address this need for direct measurements
under flow, we have developed instruments for flow-SANS in the 1-2 plane based on a short-gap Couette cell. Further,
as some systems can exhibit flow instabilities, such as shear banding, we have collimated the beam into slits as thin as
100 microns to enable exploring structure in different regions of the flow field. The instrument, its calibration, and
examples of results are presented. Case studies include a shear thinning and shear thickening near hard-sphere
colloidal dispersion, a prototypical wormlike micelle system, and a shear banding wormlike micellar system that also
exhibits shear-induced phase separation. In each case, 1-2 plane flow-SANS data provides critical information about
the mechanisms underlying the highly nonlinear rheological behavior.

103. Light scattering studies of the aging of Laponite glasses and gels
In the free energy landscape picture of glassy systems, the slow dynamics characteristic of these systems is believed to
be due to the existence of a complicated free-energy landscape with many local minima. We show here using light
scattering that for a colloidal glassy material multiple paths can be taken through the free energy landscape, that can
even lead to different 'final' non-ergodic states at the late stages of aging. We provide clear experimental evidence for
the distinction of gel and glassy states in the system and show that for a range of colloid concentrations, the transition
to non-ergodicity can occur in either direction (gel or glass), and may be accompanied by 'hesitations' between the two
directions. This shows that colloidal gels and glasses are merely global free-energy minima in the same free energy
landscape, and that the paths leading to these minima can indeed be complicated.
104. Characterization of micellar interfaces by Fluorescence Quenching and Electron Spin

Resonance: Mixed micelles of lipids and detergents
Jasmeet Singh, Justin Miller and Radha Ranganathan, California State University Northridge, Northridge, CA
The purpose of this contribution is two-fold: (1) to show the complementary application of the techniques of time
resolved fluorescence quenching (TRFQ) and electron spin resonance (ESR) in the investigation of the physicochemical
properties of micellar interfaces and (2) present results of such a study on mixed micelles of phospholipids and
detergents. We have characterized mixed micelles of the phospholipid, dimyristoyl phosphatidyl choline (DMPC) and (i)
the bile salt sodium deoxycholate (NaDC); and (ii) the zwitterionic dodecyl dimethyl ammonio propanesulfonate (DPS).
These mixed micelles are model substrates for studying phospholipase activity. Results of characterization of enzyme
activity are also presented.
Aggregation numbers of DPS/DMPC and NaDC/DMPC micelles and micellar quenching reaction rate constants are
determined by TRFQ. The hydration and microviscosity of the micelle/water interface are measured by ESR of spin-
probes inserted into the micelles. These properties vary with composition and total concentration. The ESR and TRFQ
data are interpreted together within the framework of a polar shell model of the micelle to derive its features. In the
case of NaDC/DMPC, small globular micelles are formed at low NaDC to DMPC ratios (<5), whereas DPS/DMPC forms
stable globular micelles for a wide range of compositions. These properties are found to contribute to the observed rate
enhancement of micellar lipid hydrolysis by lipolytic enzymes.
105. Micellar networks and dilute lamellar phase: transitions observed by cryogenic
transmission electron microscopy
Travis K. Hodgdon 1 , Hidehiro Nagasawa 2 and Eric W. Kaler 1 , (1)University of Delaware, Newark, DE, (2)Kao
Corporation, Tokyo, Japan
Sugar based surfactants like n-dodecyl-β-D-glucoside (C12 G 1 ) are made from renewable resources and are non-toxic
and environmentally benign; unfortunately, their use is often restricted by limited solubility in water due to Krafft
boundaries and miscibility gaps. Introducing a small amount of the ionic surfactant sodium dodecyl sulfate (SDS)
reduces the miscibility gap for C 12 G 1 , and SDS concentration is an excellent control parameter for tuning a wide
variety of available microstructure and macroscopic physical properties.
The phase behavior and resulting microstructure in the dilute region of C 12 G 1 / SDS mixtures has been established.
The microstructure was studied with light and neutron scattering techniques and by direct observation using cryogenic
transmission electron microscopy (cryo-TEM). The presence of a lamellar phase between the miscibility gap and the
micelle phase results in a wide range of microstructure. Of special interest is the evolution of microstructure between
the lamellar and micelle phases.
The elongated micelles and networks that are present near the miscibility gap are often associated with strong
increases in the viscosity of solutions. Peaks in viscosity of several orders of magnitude have been found when the
control parameter is either surfactant ratio or the addition of a simple salt (NaCl). An initial increase in viscosity as a
control parameter is increased is directly related to the axial growth of micelles. The decrease in viscosity that follows a

further increase of the control parameter is the result of branch point formation, and eventually the creation of a
saturated micelle network.
106. Myelin Formation during the Dissolution of Lamellar Phase
Louisa Reissig 1 , David Fairhurst 2 , Andrew Mount 1 , Michael E. Cates1 and Stefan U. Egelhaaf 3 , (1)University of
Edinburgh, Edinburgh, United Kingdom, (2)Nottingham Trent University, Nottingham, United Kingdom, (3)Heinrich-Heine
University, Duesseldorf, Germany
After contact with water, lamellar phases can show spectacular instabilities: multi-bilayer tubules, so-called myelins,
grow from the Lalpha/water interface into the water. We study Myelin formation in aqueous solution of the non-ionic
surfactant C12E3. We quantitatively investigate the growth of these myelins as well as changes in the lamellar phase
using confocal and optical microscopy as well as direct obsevation. This provides detailed quantitative information on
the dynamics of the myelin growth, the myelin size as well as the swelling and textural changes of the lamellar phase.
The dependence of these parameters on surfactant concentration and sample size is investigated. Based on these
observations a semi-quantitative model for myelin growth is proposed.
107. Helical tubule self-assembly using a single-tailed surfactant

Heeyoung Lee 1 , Jae-Ho Lee2 and Srinivasa R. Raghavan 1 , (1)University of Maryland, College Park, MD, (2)National
Institutes of Health, Bethesda, MD
Hollow micro or nanotubules are a remarkable type of self-assembled structure formed in aqueous solution. Self-
assembled tubules may find applications in controlled release, drug delivery, and in electroactive composites. However,
these structures are typically formed only by certain specific lipids (i.e., two-tailed amphiphiles), gluconamides or certain
peptides. While the utility of tubules has been clearly shown, at the moment, their high cost limits their accessibility and
applicability. Here we present an easy and inexpensive method for forming stable tubules in water by using a single-
tailed diacetylenic acid surfactant in conjunction with an alcohol. We will describe the formation of tubules as a function
of solution composition and temperature by using the techniques of optical and electron microscopy. Interestingly, the
tubules show helical markings, which is unusual considering that the precursor molecules are achiral. This suggests that
molecular chirality is not essential to form tubules, and this is in agreement with recent theoretical studies. The
formation of tubules from achiral molecules is believed to proceed via a chiral symmetry-breaking process.
108. Structure and rheology of self-assembled wormlike micellar networks with

incorporated nanoparticles
Matthew E. Helgeson, Florian Nettesheim, Norman J. Wagner and Eric W. Kaler, University of Delaware, Newark, DE
We study the rheology and microstructure of self-assembled wormlike micellar solutions (WLMs) in the presence of
nanoparticles smaller than the mesh size of the micelle network. The addition of cationically modified silica
nanoparticles (d = 30 nm) to WLMs of cetyltrimethylammonium bromide (CTAB) significantly modifies the linear and

non-linear rheology of the micellar network. Combining rheology, flow-birefringence, light and neutron scattering and
cryo-electron microscopy measurements provides a microstructural basis for the effects of the nanoparticles on the
WLM network. The results indicate densification of the micellar mesh near the particles, suggesting that the particles
actively participate in the micellar network due to specific micelle-particle interactions. Measurements of the energetics
of these interactions have been carried out using isothermal titration calorimetry, suggesting that the micelles associate
with an adsorbed surfactant layer on the surface of the particle. This leads to increases in elasticity of the network as
well as hindered micellar alignment under flow, resulting in macroscopic increases in viscosity and suppression of the
shear banding instability for concentrated CTAB solutions. The distribution of particles in the WLM network is consistent
with an effective interparticle attraction mediated by the adsorbed surfactants, which leads to phase separation at
higher nanoparticle loading.
109. Composition effects on lipid domain size in model membranes

Angela C. Brown and Steven P. Wrenn, Drexel University, Philadelphia, PA
The lipid raft hypothesis describes ordered domains of cell membranes, enriched in cholesterol, sphingolipids, and
saturated phospholipids, that are responsible for a number of cellular processes such as lipid sorting, protein signaling,
and signal transduction. These lipid rafts are highly mobile, and it is believed that their coalescence and separation is
what drives these cellular processes. For this reason, cellular function depends not only on the presence of lipid rafts
but also on raft size. This work uses steady-state fluorescent techniques, specifically Förster Resonance Energy
Transfer (FRET) along with a mathematical model to detect and estimate the size of lipid domains in membrane
systems modeling natural cell membranes. The fluorescence study was initially performed on a simple two-component
phospholipid and cholesterol system in order to characterize the behavior of the fluorescent probes using an
established phase diagram and was then extended to more complex, three-component systems. In these ternary
systems, the effect of phospholipid type, sterol type, and sterol composition on domain size was determined. It was
found that very slight changes in the composition of the membrane (i.e., both type and amount of “line-actant”) have
significant effects on domain formation and size by changing the amount of line tension present in the membrane.
110. Interaction of Surfactin with Phospholipids Bilayer:Neutron Reflection and Small Angle
Neutron Scattering Studies
Hsin-Hui Shen and R. K. Thomas, University of Oxford, Oxford, United Kingdom
Surfactin is a lipopetide produced by Bacillus substilis strains which contains a cyclic heptapetide and a beta-fatty acid
chain. It has biological properties such as antiviral, antibacterial and hemolytic. Although the biological properties are
suggested to be the consequence of its interaction the membrane of the target cell, the detailed molecular mechanism
of action is not clearly understood. There is a substantial interest in understanding the molecular organization and
nanomechanical properties of mixed surfactin/lipid bilayers system. Neutron reflection and small angle neutron scattering
(SANS) are able to give a direct view of how surfactin interact with phospholipid bilayers.
The results obtained on different contrasts of DPPC bilayers built on the silicon-D2O interface verify the idea of
surfactin penetrating into bilayers below the critical micelle concentration (CMC). Two mechanisms may be predicted,
(a). at low concentrations, surfactin penetrates into the phospholipid membrane by interacting via its fatty acid chain,
(b). near the CMC, surfactin self-associates to form micelles involving membrane phospholipids and leading to
membrane rupture.
Although experimental results have proved strong haemolytic activity of surfactin with blood cells, the mechanism is not
known. By using SANS technique for a series of DPPC/surfactin ratios, strong evidence of its haemolytic activity has
been found. There is insertion of surfactin into the lipid bilayer and self-aggregation of surfactin within the membrane
which results in pore formation. The results show a large surfactin aggregation number about 150 (diameter: 25 Å) and
with a d-spacing of about 200 Å between the aggregates in the membrane.
111. Binary Mixtures of β-Dodecylmaltoside (β-C12 G 2 ) with Cationic and Non-Ionic

Surfactants: Surface and Micellar Compositions
Sandeep Patil 1 , Natalie Buchavzov 2 , Enda Carey1 , Marion Lescanne 1 and Cosima Stubenrauch1 , (1)University
College Dublin, Dublin, Ireland, (2)Universität zu Köln, Köln, Germany

Surfactants used for practical applications are usually surfactant mixtures because they often exhibit superior
performance than the individual surfactants. In the present study binary mixtures of the sugar based n-dodecyl-β-D-
maltoside (β-C 12 G 2 ) with cationic dodecyltrimethyl-ammonium bromide (C12 TAB) and nonionic hexaethyleneglycol
dodecyl ether (C12 E6 ), respectively, have been investigated at different mole fractions. Surface tension measurements
were used to determine the critical micelle concentration and the surfactant composition at the surface. Interaction
parameters and the mole fractions of the individual surfactants in the mixed air/water monolayer as well as in the mixed
micelles were calculated using regular solution theory. It was found that n-dodecyl-β-D-maltoside interacts weakly with
the cationic surfactant (C12 TAB) and it dominates in both the mixed monolayer and the mixed micelles. On the other
hand, β-C 12 G 2 and C 12 E6 mix ideally in solution. For both surfactant mixtures the surfactant composition at the
surface determined by surface tension measurements and by the regular solution theory, respectively, has been
compared and discussed in detail.
112. Adsorption of Polymer/Surfactant Mixtures at the Air-Water Interface
X. L. Zhang1 , J. Penfold 2 , D. J. Taylor 1 , J. Zhang1 , R. K. Thomas1 and I. Tucker3 , (1)Oxford University, Oxford,
United Kingdom, (2)ISIS, Rutherford Appleton Laboratory, CCLRC, Chilton, Didcot, Oxon, United Kingdom, (3)Unilever
Research and Development Laboratory, Port Sunlight, United Kingdom
The interactions between oppositely charged polymer/surfactant mixtures at the air-water interface have been studied
using neutron reflectivity techniques with supplementary surface tension measurements. The cationic polyelectrolyte
poly(ethyleneimine)(PEI)/anionic surfactant sodium dodecyl sulfate(SDS) system is compared with a series of systems
containing cationic ethoxylated poly(ethyleneimine)(PEI-EOn) with different degrees of ethoxylation of the PEI/anionic
sodium dodecyl sulfate(SDS). The surface tension behavior and adsorption patterns for these systems show a strong
dependence upon the solution pH. However, the SDS adsorption for PEI/SDS and PEI-EO1/SDS at the interface is
unexpectedly most pronounced when pH is high (when polymer is essentially a neutral polymer). An obvious surfactant
multilayer adsorption can be observed especially at intermediate concentrations at higher pHs 7 and 10 (area per SDS
molecular ~20Å2 ). Based on fits to the neutron reflectivity data from different isotopic compositions the multilayer
structure is consistent with a sandwich structure with an outer surfactant layer and a submerged micellar layer or
defective bilayer. In contrast, for PEI-EO3/SDS and PEI-EO7/SDS, only monolayer adsorption is seen (area per SDS
molecular ~50Å2 ). Furthermore, the pattern of SDS, PEI-EO3 and PEI-EO7 adsorption is indicative of a strong
polymer/surfactant interaction at low pH, which decreases with increasing pH. Hence, the ethoxylation of the PEI indeed
imposes a degree of surface activity on the polymer and modifies the nature of the surface adsorption.
113. Adsorption of Lennard-Jones Surfactant Mixtures at the Liquid/Vapor Interface Studied

by Monte Carlo Simulation
C. J. Radke, University of California, Berkeley, Berkeley, CA
Based on our previous work on single surfactants, we study mixed adsorption of nonionic surfactants consisting of an
amphiphilic block-copolymer chain of Lennard-Jones solvophobic and solvophilic interaction centers, designated as
H4Tm in a monotonic LJ solvent. Single-surfactant adsorption follows the Langmuir isotherm. Larger tail lengths lead to
larger maximum coverages because the surfactant penetrates further into the vapor allowing closer packing.
Increasingly attractive tail-tail interactions produce the same effect, again because the surfactant penetrates further into
the vapor. Even small attractive tail interactions lead to drastically lower critical aggregation concentrations.
Binary mixtures of H4Tm surfactants display adsorption and tension isotherms intermediate between those of the two
single surfactants. Langmuir-based mixture theories do not obey thermodynamic consistency for unequal size species.
We successfully apply ideal adsorbed solution theory for all mixtures studied with and without lateral tail interaction. LJ
surfactants prove very useful for understanding real surfactant behavior without excessive computation time.
114. Time-Chain Length Equivalence in the Tribology of the Organic Ultrathin Films
Kenji Hisada, Akiko Hino, Daisuke Sanaka, Toshiyuki Baba and Teruo Hori, University of Fukui, Fukui, Japan
In this study, Langmuir-Blodgett (LB) films were prepared with the compounds having long alkyl tails, and their

tribological behaviors were investigated. The frictional forces were measured with lateral-force microscope (LFM), and
they were discussed as a function of chain length, scanning rate and loading force. . The LB films gave maximum
friction at a specific scan rate. For example, the LB film of poly(tetradecyl acrylate) showed maximum friction force
when it deformed with probe tip at 8–12 µm/s. The LB film having longer alkyl tails, e.g. poly(octadecyl acrylate),
showed maximum friction at slower scan rate. Deceleration of the scan rate showed an equivalent effect with shortening
the chain length. In the phase transition of the Langmuir monolayer, equivalence was reported between temperature
and the number of carbon in the alkyl tail. The phase transition temperature increased with the elongation of alkyl
chain. These results show that there is some equivalence between shear deformation rate and chain length on the
friction of the organic ultrathin films, which was similar to the time-temperature equivalence in the viscoelastic
deformation of polymers. The scanning rate at frictional maximum, νSR,max, was expressed as follows,
log(nSR,max(n))=log(nSR,max(n+m)×aCLm) where n and m are number of carbon atoms in alkyl chain, aCL is a shift
factor. The equation supports that the energy dissipation at the phase transition causes the frictional shift with chain
length for the ultrathin films.
115. Understanding chitosan enhancement of interfacial lung surfactant adsorption

Patrick C. Stenger, Omer M. Palazoglu and Joseph A. Zasadzinski, University of California, Santa Barbara, CA
The adsorption of lung surfactant to an air-water interface is strongly inhibited by the competitive adsorption of albumin
and other surface active serum proteins, and is likely the explanation of surfactant inactivation in Acute Respiratory
Distress Syndrome (ARDS). In vitro, lung surfactant adsorption to the interface is restored by the addition of hydrophilic
non-adsorbing polymers and increased mono and divalent salts, suggesting a promising therapy for ARDS. The
different approaches can be explained and quantified using classic colloidal science such as the Smolukowski analysis
of colloid stability. This paper will primarily address the mechanism by which chitosan, a highly cationic biopolymer,
enhances lung surfactant adsorption to the air-water interface. Chitsoan reverses albumin induced surfactant inhibition
at significantly lower concentrations (0.01 mg/mL) than non-ionic polymers (10 mg/mL) though its effect is surprisingly
muted by increasing the concentration greater than tenfold. Fluorescence and confocal microscopy images of the
interface show distinct changes in morphology between albumin and surfactant-covered regions offering a visual
confirmation of surfactant adsorption to the interface. We will compare these results to the depletion attraction
generated by non-ionic polymers and the electrostatic effects generated by mono and divalent salts which have both
been shown previously to enhance surfactant adsorption.
116. Limiting Extremes of Adhesion Dynamics between Polymeric Vesicles

Jin Nam and Maria Santore, University of Massachusetts, Amherst, MA
This work examines the adhesion dynamics between copolymer vesicles of poly(dimethylsiloxane)-poly(ethylene
oxide)[PDMS-PEO], where one membrane spreads over the second to partially engulf it. The project considers limiting
extremes with respect to the translational diffusion of ligands and receptors in the membrane: In one extreme, dense
membrane functionalization facilitates adhesion without requiring translational diffusion of receptors while in the other
extreme, translation diffusion of ligands and receptors within the plane of the membrane surely dominates kinetics. The
PDMS-PEO was functionalized with biotin to enable ligand-receptor binding to avidin-functionalized membranes. Using
micropipettes, an avidin-coated vesicle was brought into contact with biotinylated one and the contact area and angle
monitored in time. Densely functionalized vesicles, where diffusion was unimportant, showed strong and irreversible
adhesion dynamics which could be described in three steps: pre-adhesive latency period, rapid adhesion which was
initiated suddenly, and finally gradual relaxation. With 50 or more mol% functionalization, all three phases proceeded
relatively quickly and independent of membrane functionality. At lower functionalities, the process was slower, as a
result of diffusion, and roughly in proportion to the density of ligands and receptors. At the lowest functional densities,
adhesion proceeded without membrane deformation, giving the appearance of a latency period, but still with irreversible
adhesion. The maximum adhesion contact angles were almost same regardless of the initial membrane tensions, their
functional density, or the tension ratio between substrate and adherent one. This suggests the ultimate state is
dominated by the irreversibly binding ligands and receptors, though membrane mechanics affects adhesion dynamics.
117. Drop Retention Force as a Function of Waited Time

Preeti S. Yadav, Prashant Bahadur, Kumud Chaurasia, Aisha Leh and Rafael Tadmor, Lamar University, Beaumont,
TX

The force required to slide a drop past a surface is shown to be a growing function of the time the drop waited on the
surface prior to the commencement of sliding along it. In this first report on the “waited time” effect we explore a
number of systems and show that this phenomenon is general and takes several minutes before reaching a plateau.
Then we use one system to study the phenomenon in greater detail. We provide some semi-quantitative explanation to
the experiments.
118. The Balanced Nucleation and Growth Model for Controlled Crystal Nucleation and Size
Distribution – II. Experimental Support
Ingo Leubner, Crystallization Consulting, Penfield, NY
Based on the Balanced Nucleation and Growth (BNB) model, experiments are presented that quantitatively relate the
number and size of crystals formed in controlled batch processes to reaction variables. The experimental results are
summarized for variations of the reaction addition rate, crystal solubility, and reaction temperature, and the effect of
Ostwald ripening agents and crystal growth restrainers.
The models were initially developed and applied to the precision precipitation of silver halides in research, product
development, and manufacturing. They have since been successfully applied to the precision precipitation of boro-
fluoride salts, calcium carbonate, silicates, superheavy metal compounds, and polyacetylenes. Knowledge of the model
is essential for the control of crystallization of organic and inorganic materials from the lab to manufacturing.
119. Hydrogen reduction of perchlorate in dilute aqueous solutions

Demin Wang, H. Y. Lin, S. Ismat Shah, J. G. Chen and C. P. Huang, University of Delaware, Newark, DE
Perchlorate ion is the current candidate contaminant in drinking water under regulatory consideration by U. S. EPA. It is
of current urgency to remove perchlorate ion at low concentrations (ppb to ppm) from contaminated groundwater or
surface water to safeguard the public safety. Reduction of perchlorate by hydrogen (molecular or atomic) in the
presence of catalyst has undisputed advantages in cost, operation, and public-acceptance. In the present study, the
removal of perchlorate ions from dilute solutions was attempted in the presence of catalytic surface by either molecular
hydrogen or electrically-generated atomic hydrogen. All experiments were performed at ambient conditions, i.e., room
temperature and neutral pH. For molecular hydrogen, results indicated that perchlorate ions could be reduced to
chloride at slow but significant reaction rate. The maximum removal efficiency was less than 20% at an initial
perchlorate concentration of 10 ppm. In order to enhance the adsorption of perchlorate at catalytic membrane, positive
(anodic) potential was applied onto Ti-TiO2 surface. Significant removal efficiency of higher than 90% was achieved at
an initial perchlorate concentration of ppm level. For atomic hydrogen, reduction of perchlorate at catalytic membrane
was also found by applying constant current. Higher reaction rate was achieved with a 40% removal in 8 hours at an
initial concentration of 10 ppm. Perchlorate was reduced to chloride at catalytic membranes coated with Pt, Sn, or Cr.
However, the end product was chlorite rather than expected chloride at catalytic membrane coated with Co catalyst.
Keywords: perchlorate removal, hydrogen reduction, catalyst, catalytic membrane
120. Novel capsule formation based on stimulus responsive block copolymer films
Timothy W. Addison and Simon Biggs, University of Leeds, Leeds, United Kingdom
In recent years the layer-by-layer (LbL) technique has been demonstrated as a versatile method to provide routes to
encapsulation, surface coatings and functional capsule formation. Driven by the affinity of a charged species in solution
to that of an oppositely charged surface it provides a pathway to create multilayer films with unique properties. Many
substrates have been successfully coated using the LbL method ranging from flat surfaces to colloidal particles and
biological cells/enzymes, likewise composite films have been created with many different species including
nanoparticles, polyelectrolytes and micelle structures. Working with two diblock copolymers that undergo micellization
above a critical concentration and pH when in aqueous solution, multilayer films have been deposited on to ideal
colloidal particles. After the charged micelles are adsorbed from solution it can be demonstrated that they retain much of
their ordered nature once present within the film. It is found that these adsorbed micelles, much like when in solution
undergo a reversible change in structure when the pH of their environment is cycled between pH 4 and pH 9. Prior to
adsorption, the cores of such micelles can be pre-loaded with hydrophobic molecules. Once adsorbed, the resulting film

has the ability to be used as a nano-sized delivery system with material being released from within the micelles with a
specific trigger, in this case pH. Such delivery systems are of great interest in the development of agrochemical
formulations, personal care products and drug release systems.
121. Low Temperature Mixed Lipid Phase: Understanding Bicelle Formation

Lionel Porcar 1 , Divya Singh 2 , Gina Polimeni3 , Paul D. Butler 1 , William Hamilton 4 , Ursula Perez-Salas 5 and Gary
Lynn 6 , (1)National Institute of Standards and Technology, Gaithersburg, MD, (2)John's Hopkins University,
Gaithersburg, MD, (3)Georgia Tech, (4)ANSTO, Sydney, Australia, (5)Argonne National Laboratory, Argonne, IL, (6)Oak
Ridge National Laboratory, Oak Ridge, TN
Systems consisting of mixtures of a long and a short-tail lipid have recently shown promise in membrane protein
crystallization and have been used for some time as an alignable media for use in NMR protein structure determination.
However, the phase diagram of these lipid mixtures remains poorly understood. In particular, much of the literature
posits the existence of bicelles, or discotic micelles, as the agents of the useful properties. Recent work however
suggests that such structure only exist below the melting transition temperature of the long tail lipid (T m ), with a
transition to a lamellar phase at higher temperature. A detailed understanding of the phase behavior is essential to
adapting these systems for more general applications. We report on a systematic study at the lowest temperature
isotropic fluid like phase. Small angle neutron scattering (SANS) experiments with hydrogenated and deuterated lipids
give direct evidence of the segregated discoidal morphology, while use of standard mixed surfactant theories account to
first order for the size of the discs. SANS at higher temperatures along with phase studies and SANS measurements
on systems with different Tm and chain lengths are discussed in terms of the influence of Tm on the general phase
behavior and observed structures.
122. Time-resolved Dynamincs of Stereocomplexation of Polylactide Enantiomers on the

Water Subphase using a Planar Array Infrared (PA-IR) Spectrograph
Young Shin Kim 1 , Christopher M. Snively1 , D. Bruce Chase 2 and John F. Rabolt 1 , (1)University of Delaware, Newark,
DE, (2)DuPont Experimental Station, Wilmington, DE
Although the previously developed technique of planar array infrared (PA-IR) spectroscopy offers a number of
advantages over Fourier transform infrared (FT-IR) methods such as ultrafast speed (<100 µsec) and excellent
sensitivity, obtaining a spectrum of films in the range of 1800-1000 cm -1 on a water subphase of a Langmuir trough
remains difficult. This is due to the poor IR reflectivity of water, the extremely low concentration of the thin film on the
surface, and the interference of water bands. In this study, we report a new planar array infrared reflection spectrograph
(PA-IRRS), which has several advantages over conventional approaches. By splitting the incident infrared beam into
two sections on a plane mirror or a water trough, instead of at the front of the globar source, the performance of this
instrument is shown to be comparable to that of the dual-beam instrument although this instrumental setup is the same
with that of the single-beam instrument. Due to this design, the instrument accommodated large infrared accessories,
such as the water trough, without a loss of infrared beam intensity. Using this instrument water vapor could be
subtracted out and was obtained a high quality spectrum for a poly(L-lactic acid) Langmuir film on the water subphase,
with a resolution of about 8 cm -1 , in 10.8 sec. Hence, this PA-IRRS system has great potential for investigating the
time-resolved dynamics of a broad range of Langmuir films, such as cellular membranes or biopolymers, on the water
subphase.
123. Next generation neutron scattering analysis Tools
Jing Zhou1 , Divya Singh 2 , Matthieu Doucet 1 and Paul D. Butler3 , (1)The University of Tennessee, Gaithersburg, MD,
(2)John's Hopkins University, Gaithersburg, MD, (3)National Institute of Standards and Technology, Gaithersburg, MD
Small Angle Neutron Scattering (SANS) is a unique scattering tool used by a broad and diverse set of users and of
particular interest for colloidal and complex fluid systems. Complex fluids scientists have traditionally written their own

analysis code, used simple analytical model fitting provided by various sources, or remained at a very qualitative level
of data interpretation. A strongly integrated, easy to use, and well documented and extensible suite of tools would not
only lower the barrier for the casual user to employ SANS without having to rely on an expert (or become one
themselves), but significantly increase the amount of information extracted from the data. Over the next five years we
plan on developing SANS data analysis libraries within the DANSE framework being constructed at Caltech, that will
allow integration of various analysis and modeling methods with GUI front ends for general users, while also providing
an extensible platform for scientific programmers who want to extend the functionality beyond the existing tools without
writing everything from scratch. A first prototype/demo version of a package which will allow comparison of scattering
data to the scattering from arbitrarily complex shapes will be demonstrated along with a vision for where the
development is headed.
124. The Synthesis of meso/macroporous SBA-15 through dual-templating method

(combination of liquid crystal and colloidal crystal templating method)
Ji Sun Yun and Son-Ki Ihm, KAIST, Daejeon, South Korea
Since the existence of hierarchical pores can provide multiple advantages derived from each pore-size regime,
hierarchical porous materials have been synthesized by many researchers. SBA-15 has obvious advantages such as
good hydrothermal stability induced from thicker wall than that of MCM-41, and high surface area generated from
mesoporous structures. Furthermore, when macropores are introduced in to the mesostructure of SBA-15, the material
has additive advantages like ease access to active sites derived from macroporous structures. In this regard,
meso/macroporous SBA-15 should be very attractive for their application in the area of adsorption, catalysis and
separation. The meso/macroporous SBA-15 were prepared by a new and simple dual-templating method, which is the
combination of replicating the closed packed array of colloidal crystal and liquid crystal mesophase of surfactant. The
meso/macroporous silicate can be successfully synthesized without losing unique properties of each pore size regime.
With the PS:Si ratio, not only was the volume of macroporous space increasing, but also the macrostructures was
better ordered. The adsorption dynamics were also improved with the increase in the volume of macroporous space.
This result seems to confirm that the macropores in mesoporous silicates really provide an easy access to active sites.
125. Correlating Electronic and Catalytic Properties of Bimetallic Surfaces

Amit Goda, Mark Barteau and Jingguang Chen, University of Delaware, Newark, DE
The formation of bimetallic surfaces leads to a change in the electronic properties of the parent metal surface, which
results in changes in chemical reactivity. In this work we illustrate the correlation of electronic properties of bimetallic
surfaces with the reaction pathways of C2 hydrocarbons and of the selective reduction of acetic acid to acetaldehyde.
For the study on C2 hydrocarbons, Density Functional Theory (DFT) was used to study the binding of hydrogen,
ethylene, acetylene, ethyl and vinyl on monometallic and bimetallic transition metal surfaces. The binding energies
(B.E.) of these species were found to correlate with the d-band centers of the surfaces. DFT-calculated B.E. and BOC-
calculated activation barrier values were used to calculate the selectivity for acetylene hydrogenation vs. ethylene
hydrogenation. The results showed that for monometallic fcc(111) surfaces, the selectivity for acetylene hydrogenation
followed the trend Ni > Pt > Pd.
In the case of selective reduction of acetic acid, DFT calculations were used to study the modes and energies of
adsorption of the involved intermediates along with the overall reaction energies for the elementary steps. It was
observed that ethanol binds more strongly than acetaldehyde on Pt(111) as well as the subsurface Ni on Pt surface,
but the trend reverses for monolayer Ni on Pt. This change in B.E. affects the overall heat of reaction for ethoxy going
to ethanol. These changes in the thermodynamics of reactions should affect the overall selectivity toward acetaldehyde,
which would be determined be calculating the activation barriers for the elementary steps.
126. General trends in hydrogen binding energy and hydrogenation activity on Pt-3d
bimetallic surfaces
Michael P. Humbert, Luis E. Murillo and Jingguang G. Chen, University of Delaware, Newark, DE
Bimetallic surfaces often show novel properties that are not present on either of the parent metal surfaces. Our group

has recently investigated the electronic and chemical properties of model bimetallic surface structures, using a
combination of experimental and theoretical modeling to gain insights into these factors. Density functional theory (DFT)
can provide insight into the interaction between molecules and model surfaces. In this study we attempt to correlate
DFT findings to experimental results. Specifically, temperature programmed desorption (TPD) is performed on model
surfaces with various probe molecules to determine if reactivity can be determined from first-principles. Extensive
characterization has been performed on Ni-Pt bimetallic surfaces. The findings of this study are that Ni deposited at 300
K on Pt(111) results in a surface configuration of Ni, while Ni deposited at 600 K diffuses into the bulk resulting in a
subsurface Ni configuration. This has also been found to be the case for Co-Pt surfaces, and this idea is extended to
other 3d metals based on DFT results.
127. Gas Phase Perchlorate Reduction by Mono- and Bimetallic Catalysts Supported on
Activated Carbon
C. P. Huang 1 , Jingguang Chen 1 , Yuying Shu 2 , Sergey Rykov 1 and Rovshan H. Mahmudov1 , (1)University of
Delaware, Newark, DE, (2)Virginia Polytechnic Institute & State University, Blacksburg, VA
Catalytic reduction of perchlorate has challenged chemical and environmental communities for decades. In this work we
report the results of gas phase reduction of perchlorate by hydrogen gas in the presence of Pd- and Pt- based mono
and bimetallic catalysts supported on activated carbon. Five types of Pd and Pt based bimetallic catalysts supported on
activated carbon (AC) were tested: Pd (5% W:W), Pt (5% W:W), Pt/Ni (Pt 5% W:W, Pt:Ni = 1:1), Pt/Co (Pt 5% W:W,
Pt:Co = 1:1), and Pt/W (Pt 5% W:W, Pt:W = 1:1). First perchlorate was preadsorbed on the activated carbon
impregnated with the appropriate catalysts. The activated carbon was then separated and placed in the oven under
10% H2 + 90% N2. Results showed that bimetallic catalysts supported on activated carbon had better hydrogen
adsorption capacity and perchlorate reduction efficiency than monometallic catalysts with Pt/Co being the best.
Reaction temperature was crucial for perchlorate reduction. More than 95 % of adsorbed perchlorate was reduced in 5
hrs at temperatures > 50 oC when the Pt/Co catalyst was used. Such fast reduction of perchlorate at moderate
temperatures has not been reported in the aqueous phase. Major drawback, as showed in the XPS and EDX analysis,
was the dissolution of the second metal in the aqueous phase. Upon submerging in water relative surface
concentrations of Co and Ni dropped by factor of 2 whereas Pt was stable. Further research is needed to develop the
catalysts combination that will have better stability and efficiency.
128. Surface science studies of tungsten carbides as alternative electrocatalysts for direct
methanol fuel cells
Alan Lee Stottlemyer and Jingguang G. Chen, University of Delaware, Newark, DE
The motivation of this research is to assess the feasibility of tungsten carbides as alternative electrocatalysts in direct
methanol fuel cells (DMFC). DMFC are one possible source of energy which can be used to directly convert chemical
energy into electrical energy by the electro-oxidation of methanol. Current fuel cells require the use of Pt/Ru bimetallic
anode catalysts which suffer from CO poisoning and high cost. The commercialization of such technologies requires
less expensive and more CO tolerant materials. Transition metal carbides often show catalytic properties similar to the
Pt-group metals and recent research suggests that tungsten carbides may be an appropriate substitute.
Temperature programmed desorption (TPD) was used to draw both qualitative and quantitative conclusions about the
reactions of CO, H2, CH4 and CH3OH on polycrystalline platinum, tungsten carbide and platinum modified tungsten
carbide foils. Results from TPD studies show that all tested surfaces are capable of methanol decomposition and the
propensities for each decomposition pathway were calculated. A qualitative assessment of TPD data coupled with
Gaussian deconvolution of peaks suggests that methanol decomposition chemistry occurs predominately on the Pt(100)
face. This conclusion is supported by past Pt(111) single crystal work that suggests that the Pt(111) face is inert to
methanol decomposition. Ultimately, such studies suggest that platinum modified transition metal carbides may be
reasonable alternative electrocatalysts for direct methanol fuel cells.
129. Study of Ag and Re promoted Ag catalysts for ethylene epoxidation using traditional
and high-throughput experimentation
Joseph C. Dellamorte, Jochen Lauterbach and Mark A Barteau, University of Delaware, Newark, DE

Current global production of ethylene oxide (EO) exceeds 14 million tons per year. The current industrial process, direct
gas phase production of EO, is expensive with 20-25% of the main reactant, ethylene, being combusted in an
unselective reaction on the base catalyst, Ag. Several patents claim that promoters on Ag catalysts, such as Re, Cs,
and co-fed organic chlorides, yield EO selectivities over 80%. However, only the effects of Cs and organic chlorides
have been studied in detail. In order to establish a more fundamental understanding of the Ag and Re-Ag catalysts,
traditional and high-throughput reactor studies were executed. As Fig. 1 shows, the Ag catalyst activity was
dramatically affected by the calcination conditions, without change to the selectivity. Based on this result, it is thought
that catalyst sintering decreases the activity with larger calcination times. Results from studies with Re-Ag indicate that
Re increases the EO selectivity at the expense of catalyst activity. The optimum performance of 45% EO selectivity for
the Re-Ag, compared to 30% for Ag, was found for catalysts with 25 ppm Re. Characterization, using SEM, shows that
the addition of Re also causes an increase in the Ag particle size from 15-35 mm. An analysis of the oxygen reaction
orders showed that the Re-Ag catalyst presents a more uniform distribution of sites for oxygen adsorption than
unpromoted catalysts. Thus, it is hypothesized that Re is blocking/destroying Ag step sites, increasing the EO
selectivity.
Fig. 1. Performance of Ag catalysts calcined at 400o C for 1-21 hours
130. Photocatalytic Performance of Pulsed Laser Deposited TiO2 Thin Film – Effects of
Oxygen Vacancy, Phase Composition, and Energy Band Configuration
Hong-Ying Lin 1 , Abdul Rumaiz 2 , Demin Wang1 , Meghan Sculz1 , S. Ismat Shah 1 and C. P. Huang 1 , (1)University of
Delaware, Newark, DE, (2)University of Delaware, Newark
Nanoscale TiO2 thin films were prepared by pulsed laser deposition (PLD) technique on Indium Tin Oxide (ITO)
surfaces. TiO2 thin films were deposited as a function of oxygen pressure and substrate temperature. Results from X-
ray photoelectron spectroscopy (XPS) show a 0.6 eV shift in binding energy of Ti 2p3/2 with variation on oxygen partial
pressure. Based on linear scan voltammetry (LSV), we found that the onset potential of TiOx thin films increased in
absolute energy scale by a magnitude of 0.2 to 0.8 eV when deposition temperature decreased from 873 to 298 K. This
implies that the flatband potential as well as the Fermi energy of the TiO2 thin film vary with the concentration of
oxygen vacancies. Rutile weight fraction ranged from unity to near zero was observed, depending on experimental
condition. In photoelectrochemical study, the best incident photon conversion efficiency (IPCE) was observed at
deposition temperature of 873K which yielded 2.5 to 5 % of IPCE(l=320nm). The differences were attributed to the
variation in degree of crystallization and phase composition of TiO2. Our results suggest that the photocatalytic

reactivity of TiO2 thin film can be optimized depending on the desired redox reaction and this can be achieved by
moderately manipulating oxygen pressure and substrate temperature since these two parameters greatly impact the
oxygen vacancy concentration in the TiOx thin film deposited in PLD. This, in turn, affects the position of the flatband
potential and its photocatalytic reactivity.
131. Line energy and Line Force

Rafael Tadmor, Lamar University, Beaumont, TX
What is the physical meaning of line tension? Is it the same as line energy? How does it relate to the forces retaining a
drop to a surface? These are fundamental questions in surface science and we address them. We show that line
energy derived from energy minimization and retention force derived from fluid dynamics consideration not only have
the same dimensions (“Energy/Length” and “Force”) but also relate by their physical interpretation and one can be
derived from the other. We provide some experimental evidence for the physical picture that we present.
132. DYNAMIC arrest and activated transport in molecular colloidal glasses and gels
Mukta Tripathy, University of Illinois, Urbana-Champaign, Urbana, IL and Kenneth S. Schweizer, University of Illinois,
Urbana, IL
Molecular integral equation, simplified mode coupling, and activated barrier hopping theories have been combined to
systematically investigate the structure, slow translational dynamics, vitrification and gelation of suspensions composed
of nonspherical colloids. One (rod), two (planar) and three (e.g. cube, octahedron) dimensional shapes have been
studied. For purely excluded volume interactions, the effective dimensionality of the rigid object is the primary variable
controlling the ideal glass volume fraction and entropic barrier height. Subtle effects occur within a fixed dimensional
class (e.g., triangles versus hexagons). In the presence of strong, short range inter-site attractions, glass formation
competes with gelation, and re-entrant glass-fluid-gel behavior is predicted at high volume fractions, the quantitative
aspects of which depend on colloidal shape. Correlations of the slow dynamics with the packing, and number of sticky
contacts between the nonspherical objects, has been investigated. All the results for molecular colloids are contrasted
with their spherical particle analogs to establish the consequences of shape anisotropy. Finally, a new unified
understanding of how barriers in colloidal gels composed of sticky spheres depend on local structure, attraction
strength, and volume fraction has been achieved. The emergent physical picture suggests analogies with glasses and
mechanically jammed systems.
133. CO oxidation over Ag/TiO2 and Au/TiO2 supported nanoparticles prepared by

photodeposition
Sze Chi Chan and Mark A. Barteau, University of Delaware, Newark, DE
It has been shown that gold nanoparticles supported on metal oxides with sizes below 5 nm exhibit unique catalytic
properties for CO oxidation, water-gas shift, and epoxidation of propylene. In particular, Au/TiO 2 exhibits CO oxidation
activity at temperature as low as 90K. By far, deposition-precipitation is the most extensively used method for the
preparation of Au/TiO 2 catalysts. The main disadvantage of this method is that the weight loading of Au is very low.
Our previous study demonstrated that metal photodeposition on TiO2 nanoparticles gives rise to high highly uniform
metal nanoparticles in the 1-2 nm size range and provides new route to generate supported nanoparticles with highly
uniform sites on nanoscale. In our present work, we have scaled-up the Ag and Au photodeposition on TiO2
nanoparticles. Ag/TiO 2 and Au/TiO 2 nanoparticles obtained from the scaled-up process were characterized by atomic
absorption spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV-visible absorption, and high-angle
annual dark-field scanning transmission electron microscopy. In addition, Ag/TiO 2 and Au/TiO 2 nanoparticles were also
prepared using traditional deposition precipitation method. The catalytic activity for CO oxidation of Ag/TiO 2 and
Au/TiO 2 nanoparticles prepared by both methods were investigated using a high-throughput reactor.
134. Spin-Leakage in Nanoparticles of Paramagnetic Endometallofullerenes

Vitaly K. Koltover, Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow
Region, Russia

Endohedral fullerenes (M@C2n ) are carbon clusters that contain atoms trapped within the fullerene cage. This “atomic
park” of the 21st century counts approximately 30 elements, mainly of 2nd group (Ca, Ba, Sr) and 3rd group (Sc, Y,
Ln). Some of them, like La@C 2n , have unpaired electrons. For La@C 2n embedded in the polycarbonate film, we
discovered an intense 1 H-ENDOR (electron-nuclear double resonance) signal. Since there are no protons in La@C 2n ,
this was a matrix 1 H-ENDOR that testifies permeability of the fullerene shell for the electron spin density. For liquid
solutions of La@C 2n in hexamethylphosphoramide (HMPA), molecules of which contain NMR active phosphorus-31,
the paramagnetic shift of 31 P NMR of bulk HMPA molecules in the presence of La@C 2n was revealed. Thus, ENDOR
and NMR testify that the area of localization of unpaired electrons is not restricted by the fullerene shell but a partial
runoff of the electron spin density outside the fullerene cage (“spin-leakage”) takes place. Furthermore, M@C 2n form
nanoparticles, the mean size of which ranges up to 100 nm in polar solvents. The “spin-leakage” leads to the partial
loss of molecular paramagnetism of M@C 2n at forming the nanoparticles. The magic angle spinning (MAS) NMR of
solid complexes of La@C 82 and Y@C 82 with HMPA revealed the enormous shifts for 139 La lines along with the vast
range of the shifts for 31 P of the bound HMPA. Being unchanged with temperature, such shifts suggest their Knight
nature caused by the density of conduction electrons at the positions of the NMR observed nuclei.
135. Effect of contact time and pushing force on adhesion force between glass particle and
mica plate in electrolyte solution
Yasushige Mori and Keisuke Shimamura, Doshisha University, Kyotanabe, Japan
It is well known that the adhesion force between surfaces in an aqueous solution depends on ionic species and
concentration, and increases with contact time, when two surfaces are pressed each other. This phenomenon could be
explained that the adsorbed layer of water or cation was destroyed, and then the adhesion force mainly due to the van
der Waals attraction force increased because two surfaces could be approached each other. However, the dependence
of pushing force is not clear. In this study, an atomic force microscope was used to determine the adhesion force
between a glass particle and a mica plate in lithium chloride, cesium chloride, or calcium chloride solution for
understanding of the effects of the contact time and the pushing force. The adhesion force in these aqueous solutions
increased with the impulse, that is the product of pushing force and contact time. As the adhesion force in electrolyte
solution mainly depends on the van der Waals force, the distance between a glass particle and a mica plate could be
estimated by the calculation of van der Waals force. At the high impulse, the distance between a glass particle and a
mica plate decreased up to the diameter of a water molecule in lithium chloride and calcium chloride solution. In cesium
chloride solution, however, the distance only decreased to twice length of the diameter of cesium ion, because cesium
ions would strongly absorb on the surface.
136. Non-Surface Active Amphiphilic Diblock Copolymers. --- The Effect of Chain Length
and Hydrophobicity ---
Hideki Matsuoka, Ploysai Kaewsaiha, Shuji Kage and Hao Chen, Kyoto University, Kyoto, Japan
The "Non-Surface Active Amphiphilic Diblock Copolymer" is a novel class of molecules which is contradict with the
"common sense" of the surface and interface science. They are certainly amphiphilic so they form micelles in aqueous
media when dissolved. However, they do not adsorb onto the air/water interface. Hence, the surface tension of the
solution does not decrease with polymer concentration and the solutions show very less foam formation activity. This
curious molecule is in principle ionic amphiphilic diblock copolymers, which consist of polyelectrolyte and hydrophobic
chains. The origin of this "curious phenomenon" is thought be the balance of image charge repulsion at the air/water
interface and hydrophobic adsorption force. In addition, the "polymerity" was found to be an important factor: the block
copolymer m:n=64:53 (poly(stynrene)-b-poly(styrene sulfonate)) showed non-surface activity but that with m:n=18:18
showed very high surface activity, although the block ratio is almost 1:1 for both of these polymers. The
(poly(fluorinated styrene)-b-poly(styrene sulfonate)) with m:n=30:64 showed non-surface activity but that with m:n=11:64
showed surface activity. Hence, it can be concluded that the minimum length exists for appearance of non-surface
activity, which might be around m=30 for hydrophobic chain and n=50 for ionic chain. The effect of hydrophobicity of the
hydrophobic chains on the non-surface active nature was also investigated. Unexpectedly, the non-surface activity was
in the order of poly(n-butylacrylate) < poly(styrene) < poly(fluorinated styrene) as the hydrophobic chain with same ionic

block, although the hydrophobicity is higher in this order. Ref. P.Kaewsaiha, et al., Langmuir, 21(22), 9938 (2005).
137. Shear Ordering of Concentrated Particle Suspensions

Jason M. McMullan and Norman J. Wagner, University of Delaware, Newark, DE
Highly ordered particle crystals trapped in an exterior matrix can be used in applications that require regular structures
with uniform material properties. Creating ordered structures with particles in the ~10-100 μm range is a challenge.
This study examines oscillatory shear as a method to provide particle mobility and drive ordering. Structures are formed
with monodisperse particles in this size range above a particle loading of 54 volume percent then arrested within a
polymer matrix. This study explores the degree of order by varying particle loading and other rheometric parameters
such as shear amplitude and frequency. The bulk properties are examined as a function of the order of the particles,
particle materials and matrix materials. The extent of ordering is compared with colloidal systems under similar
conditions. Shear ordering occurs under multiple sets of conditions but is reproducible and scalable for industrial
production.
138. Quantitative parameters for surfactant-dye interaction

Syed Waqar Hussain Shah, OPF Boys College, Islamabad, Pakistan
Quantitative parameters for behavior of homologous hemicyanine dyes in micellar media were determined using
ultraviolet and visible differential spectroscopic technique. The impact of varying dye hydrophobicity on aggregation of
surfactant was related to the extent of depression in critical micelle concentration of sodium docecyl sulfate caused by
the addition of each dye. Spectral shifts were translated in terms of binding constants to highlight the involvement of
dye molecules in the formation of surfactant-dye aggregates. Both spectroscopic and conductometric data were used to
show the thermodynamic feasibility of the phenomenon.
139. Large Scale Synthesis of Magnetite Powders

Brett M. Silverman, Headwaters Technology Innovations, Lawrenceville, NJ
This research focuses on a low-cost, large-scale synthesis of magnetite nanoparticles using two different techniques.
This material will be uniform in shape, and have the characteristic magnetic properties relative to its particles size.The
first experimental detail is the formation of a colloid made from the dissolution of Fe metal in an aqueous acid solution.
Once the base colloid is prepared, there are two distinct routes to synthesizing magnetite powders. One method
involves the evaporation of the colloid followed by reduction in hydrogen. The second method involves direct reduction
of the colloid followed by centrifugation. The resulting material can be made in batches up to 0.5 kg, and have been
identified as 95-99% magnetite.
140. Deactivation of Bacteria by Blockcopolymer Micelles Loaded with Biocide

Renata Vyhnalkova, Adi Eisenberg and Theo G.M. van de Ven, McGill University, Montreal, QC, Canada
We studied micelles of PS197-b-PAA47 loaded with thiocyanomethylthiobenzothiazole (TCMTB) biocide. Crew-cut

micelles of PS197-b-PAA47 are prepared in dioxane by slow water addition. The micelles size is 26 nm by TEM and
50 nm by DLS. The micelles are loaded afterwards with the hydrophobic antibacterial agent – TCMTB. The efficiency of
micelles loading is measured by the UV-vis technique. Maximum loading of biocide in micelles is around 30 wt%.
Loaded micelles are exposed to bacteria (E.coli) and their deactivation is evaluated. SEM shows that the micelles
adsorb on the surface of the bacteria; also, distinct differences are seen between bacteria treated with empty micelles
and those treated with biocide-loaded micelles. Deactivation of the bacteria by TCMTB biocide is studied by exposing
E-coli BL-21 bacteria to the loaded micelles. The deactivation is measured using a UV-vis technique. The absorbance
of bacteria deactivated by loaded micelles is compared to the absorbance of bacteria in water and to those exposed to
solutions containing empty micelles. It was found that E-coli bacteria do not grow with time in the presence of TCMTB
loaded micelles; they are deactivated. Empty micelles of PS197-b-PAA47 do not affect the growth of the E-coli
bacteria; the bacteria behave similarly to those exposed to a food-water solution.
141. Validity of various relationships available for determining surface tension of solids

Samad Ahadian, Siamak Moradian and Mohammad Amani Tehran, Amirkabir University of Technology, Tehran, Iran
The contact angles of various solids and four probe liquids (i.e. diiodomethane, formamide, glycerine and water) were
varied in the range 0-180 degrees by the aid of different approaches such as the equation of state (i.e. the Neumann's
equation), the Owens/Wendt, the harmonic mean, the van Oss et al. and the combined mean relationships. All the 11
possible 2, 3 and 4 combinations of the liquid mixtures were used. These contact angles were then employed to
calculate the corresponding surface tensions by the aid of the mentioned relationships. For each solid/liquid
combination, the acceptable range of contact angles for calculating the real as compared to the imaginary surface
tension of solid or its components was determined. Generally, the Neumann's equation of state showed the widest
range of acceptable contact angles as compared to the others. In contrast, the van Oss et al. relationship had the
narrowest range. Additionally, the most valid range of the Neumann's equation of state was when all the probe liquids
were polar. On the other hand, for other relationships, the valid range occurred when at least one of the probe liquids
was apolar.
142. Polyelectrolyte Gel-Surfactant Complexes with Shape Memory Effects

Guoqin Liu, Henan University of Technology, Zhengzhou, China and Chunlong Guan, Henan University of
Technology,, Zhengzhou, China
The complex of Poly(acrylic acid-co-acrylamide) gel with cetyltrimethylammonium bromide (P(AA-co-Am)-C16TAB) was
synthesized. It has shape memory behavior due to the formation of thermodynamically homogeneous structure. A
specific feature of this type of shape memory complex is that the transition temperature at which the complex abruptly
becomes soft and deforms can be controlled by changing the degree of cross-linkage, which enables one to adjust the
shape memory effect at desired temperature. Mechanism and process of the shape memory behaviors were discussed.
143. Statistical and mathematical investigations for determining the binding constants of
micelle with reactants molecules from kinetic data
Rabah A. Khalil, College of Science, University of Mosul, Mosul, Iraq, Mosul, Iraq
The research concerns with the determination of binding constants of bimolecular reactants with micelle from kinetic
data. Recently, we have developed a statistical method based on multiple linear regression for determining those
parameters and according to the following source equation:
where . In the present work, we have derived further two statistical equations
from the above source equation using multiple linear regression method. A substantial difference has been found
between the results of those equations and also with that of the recent one. This strongly indicates that the statistical
procedures are not valid for such purpose. In other word, the available statistical and graphical methods in the literature
are also not suitable for such treatment.
A mathematical procedure using iterative method for evaluating the binding constants has been employed. An
equation for such treatment has also been derived from the above source equation. The method was based upon that
hypothetical values of and could estimate at various C. The correct values of and must give
constant values of at these C. A computer program for this purpose using Visual Basic 6 software has been written.
Application of the method to the kinetic data has been found to be quite successful through giving a minimum value of
the variance. A characteristic feature of the last method is its inability to give a minimum variance if there is an error in
the introduced experimental data. It has been concluded that the presented mathematical method is simple, reliable and
accurate.

144. Synthesis of new amine oxide type surfactants having dual function of cleaning and
softening effects and their physical properties
JongChoo Lim 1 , JunSeok Park1 , In-Sik Cho2 , KiMoo Lee2 , GyeongYup Chi 2 , DongSung Han2 and KyungMin Yoo 2 ,
(1)Dongguk University, Seoul, South Korea, (2)Aekyung, Daejeon, South Korea
It is very important to ensure mildness of detergents to the skin in the fields of all household products, as detergents
are to be in direct or indirect contact with the human body. As surfactants are the major components in detergent
formulations, many studies have been performed to develop surfactants of improved biodegradability and mildness. In
this study, amine oxide type surfactants having a dialkyl amide chain were synthesized mainly for detergent formulation
purposes and their physical properties such as critical micelle concentration (CMC), surface tension, contact angle, and
viscosity were measured. Since these newly synthesized amine oxide surfactants are the bulky amphoteric surfactants,
they can serve as dual function surfactants by a single molecule through the interconversion of cleaning and softening
effects depend on pH variations of the aqueous solution. In a general laundry process, cleaning is accomplished in an
alkaline condition, pH gradually decreases after rinsing steps, and then softening is accomplished in a neutral pH
condition. The newly synthesized surfactants shows not only detergency but also softening effect since they show
characteristics of a nonionic surfactant in an alkaline condition, while showing characteristics of a cationic surfactant in
a neutral condition. Their dual function characteristics depending on pH of the aqueous solution were investigated and
their related cleaning and softening effects were measured. In addition to cleaning and softening effects, phase behavior
of the newly synthesized surfactants were studied.
145. Preparation of two dimensional silver nanoparticles in aqueous solution

Zusing Yang, Tai-Chia Chiu and Huan-Tsung Chang, National Taiwan University, Taipei, Taiwan
We have developed a new and simple one-pot synthetic approach for the preparation of single-crystalline rose-, spike-,
and snowflake-shaped silver nanoparticles (NPs) in aqueous solution. We obtained these variously shaped Ag NPs by
carefully controlling the nature and concentration of the stabilizers, which included sodium acetate, sodium citrate, and
poly(ethylene glycol). To the best of our knowledge, this paper is the first to describe the preparation of rose-shaped Ag
NPs, also called Ag nanoflowers (NFs), through such a simple synthetic route. The thus-prepared Ag NFs exhibited a
specific surface area of 15.6 m2 g-1, a contact angle of 97.6 °" 2.2¢X, high conductivity (1.97 „e 106 S/cm), and
efficient optothermal conversion efficiency (the temperature rose 23.03 °" 0.21 ¢XC after laser irradiation at 808 nm for
3 min). The snowflake-shaped Ag NPs allowed the enhancement of Raman scattering (SERS) signals of rhodamine 6G
by a factor of 2.4 „e 106, with a detection limit of 10 nM
146. Gel diodes: Unidirectional current response of an ionic junction between

polyelectrolyte aqueous gels
Suk Tai Chang, Oliver J. Cayre and Orlin D. Velev, North Carolina State University, Raleigh, NC
Electronic components based on organic materials are of interest because they possess a number of potential
advantages over traditional silicone-based junctions. Here, we demonstrate unidirectional ionic current flow across a
fixed junction between two aqueous agarose gel phases containing oppositely charged polyelectrolytes. The promising
feature of this new type of rectifying junction is that it is operates on the basis of water-borne ions. We show that the
non-linear current response of the interface between the cationic and anionic gels originates directly from anisotropy in
the mobile charges within the system. The current densities in the forward bias and current rectifying ratios in these gel
diodes are higher or comparable to those using ionic carries and junctions built from conductive polymers. The devices
are extremely simple, inexpensive and possess good long-term stability in both DC and AC conduction modes. Such
devices based on aqueous gel phases can easily be fabricated and could be used in numerous applications requiring
flexible and biocompatible electronic components.

147. Effect of surfactant on mechanical properties of a nanoparticulate gel

Jiong Liu, Saran Poovarodon and John Berg, University of Washington, Seattle, WA
An aluminum oxide hydroxide AlO(OH) nanoparticulate sol was synthesized using a Yoldas process. The AlO(OH)
nanoparticle was found to catalyze the ring-opening and condensation reactions of a glycidoxypropyltrimethyloxysilane
(GPS) gel derived from an aqueous solution. FT-IR and SEM results showed that the nanoparticles participate in
forming the network structure of the gel. The effect of a Pluronic surfactant on the mechanical properties of the
nanoparticulate AlO(OH)/GPS gel was investigated. It is found that the connectivity of the network structure decreases
slightly with the addition of a small amount of surfactant, which leads to a significant increase in fracture toughness of
the gel materials.
148. A Systematic Study of Triglyceride Molecular Structure Effects on Surfactant-oil

Interactions
Tri T. Phan, Jeffrey H. Harwell and David A. Sabatini, University of Oklahoma, Norman, OK
Triglyceride molecules, with their unique structure of three ester groups and three long chains, are among the most
challenging oils with which to form a microemulsion. While triglyceride microemulsion formation has been reported, the
impact of molecular triglyceride structure on interactions with surfactants is poorly understood. In the present study,
surfactant-oil interactions were evaluated by comparing optimum salinities, interfacial tensions (IFTs) and Equivalent
Alkane Carbon Number (EACN) values of individual triglycerides with various chain lengths and degrees of saturation.
The results revealed that the chain length showed less effect on EACN and IFT as compared to the degree of
saturation. An increase in the chain length from C14:1 (trimyristolein) to C18:1 (triolein) resulted in an increase in EACN
from 18 to 19 while IFTs remained similar (10-3 mN/m). In contrast, an increase in the number of double bonds (e.g.
from one in triolein, C18:1, to three in trilinolenin, C18:3) led to an increase in EACN to 22 (versus 18) and IFT
increase to 10 -1 mN/m. This can be explained by the more complicated spatial arrangement resulting from the double
bonds caused a steric hindrance to the oil-surfactant parallel arrangement.
149. Adsorption of nano-sized TiO2 particles onto surface of algae exemplified by

Pseudokirchneriella subcapitata
Ming-Yu Lin, David M. Metzler and C. P. Huang, University of Delaware, Newark, DE
Nano-sized titanium dioxide (TiO 2 ) has wide industrial applications with considerable chance of exposure to humans
and ecosystem. As a photocatalyst, nano-sized TiO2 has been used in various environmental remediation applications
implying its potential environmental impact. In order to better understand the interaction between nano-sized TiO2 and
phytoplankton in the aquatic environment, we first studied the adsorption of nano-sized TiO2 (Degussa P25) onto the
algae exemplified by Pseudokirchneriella subcapitata. P. subcapitata were exposed to TiO2 in a series of
concentrations and at various pH and ionic strength. The sedimentation experiments were conducted to determine the
TiO2 adsorption density using turbidity and dynamic light scattering measurements. Results show that the kinetics and
the extent of TiO2 adsorption are highly dependent on pH, which indicates the electrostatic nature of the interaction.
The maximum adsorption density occurred (9x10 5 particles per cell) at pH 5.5. As the ionic strength increased, the rate
of adsorption increased but the saturation adsorption density remained relatively unchanged. The adsorption was multi-
layered and the presence of isotherm plateau suggested that the adsorption energy between layers decreased toward

the outer layer. The flocculation of algae was observed. At pH 4.6, the aggregate size reduced from hundred microns to
a few microns as the number ratio of TiO2 to algae increased from 3 x 10 5 to 10 6 . The decrease in aggregate size can
be explained by the increase in stability due to charge reversal on the algal surface brought by TiO2 adsorption.
150. Effects of noble metal particles and salts on the light stability of Safranin O
Moonsuk Han, Young-ho Lee, Dae-wook Kim and Seong-geun Oh, Hanyang university, Seoul, South Korea
Organic dyes are used in many industrial and chemical analytic fields. They are easily degraded under severe light and
heat owing to be organic materials even though they could have good chromogenic ability. If the colors of organic dyes
were faded or discolored, the dyes would be no use as coloring agents by degradation. While inorganic materials have
strong light and heat stability in their own properties, organic materials usually have poor fastness of light and heat.
Each material used in this research has remarkably different physical and chemical properties. Hence It was
investigated how organic dye as organic materials would be affected by noble metals as inorganic materials. In this
study H2O2 were added to the Safranin O aqueous solution. H2O2 might serve a part as pseudo catalyst of dye
degrading reaction. We applied noble metal nanoparticles such as Ag, Au, Pt in colloidal condition and AgNO3, HAuCl4,
H2PtCl6 as the noble metal salts. The Safranin O solutions containing noble metal and H2O2 were irradiated by UV
lamp (wavelength=254nm). The effects of noble metal nanoparticles and salts on the light stability of Safranin O were
investigated. Effect of pH was also considered. HCl and NaOH were used to control the pH of the solution. Optical
properties of the noble metal and organic dye were investigated by UV-vis spectroscopy and naked eyes as time went.
The complexes between noble metals and the organic dye were confirmed by TEM and Raman spectroscopy.
151. Affect of Boric Acid on the Temporal Evolution of Siliceous Nanoparticles formed in
Aqueous Solutions of Tetraethylammonium Hydroxide
Nathan D. Hould and Raul F. Lobo, University of Delaware, Newark, DE
A thorough understanding of the formation of crystalline materials from solution is crucial to predicting the final structure
and properties of the resulting solids such as zeolites. One system that is particularly interesting is an aqueous solution
containing of tetraethyl orthosilicate (TEOS), tetraethylammonium hydroxide (TEAOH), and boric acid, which is known to
lead under hydrothermal conditions to zeolite-Beta (BEA), a material with many industrial applications due to its unique
microporous structure. The current study is aimed at understanding the mechanism of formation of the nanoparticulate
precursors that are formed in clear gel solutions of similar composition to those which yield beta. Data shows that these
model systems have a critical aggregation concentration above which the silicate species in solution aggregate into
nanoparticles. This critical aggregation concentration is sensitive to the concentration of boric acid in the solution gel
due to its dissociation to form B(OH)4–. We have investigated the structural evolution of the nanoparticles, at elevated
temperatures with Small Angle X-ray Scattering.
152. Effects of Particle Additions on the Rheological Properties of Polyacrylate /

Polyacrylamide Hydrogels
Bryan A. Baker 1 , Rebecca L. Murff2 and Valeria T. Milam2 , (1)Georgia Institue of Technology, Atlanta, GA, (2)Georgia
Institute of Technology, Atlanta, GA
Polyacrylamide-based hydrogels are popular materials that have been extensively studied for their applications in the
field of biomaterials due to their permeability and biological compatibility. A major limitation of this polymeric material,
however, in biological applications stems from their limited mechanical stiffness. In order to increase the mechanical
stiffness of these hydrogels, colloidal particles are added to act as interactive filler and reinforce the soft hydrogel matrix.
Various surface chemistries are being explored to alter the nature of particle-matrix adhesion. The current study
examines the effects of the surface chemistry and volume fraction of particles on the mechanical properties of
polyacrylamide-polyacrylate-based hydrogels using oscillatory rheology.
153. Synthesis and characterization of PEG-grafted silica particles by one-step novel

method
Hyojung Jun, Yong-Geun Lee, Chul Oh and Seong-Geun Oh, Hanyang University, Seoul, South Korea

The development of new organic-inorganic hybrid materials is a great interest with respect to obtaining their special
properties and the sol-gel process has provided new possibility for preparing the composite materials. Poly(ethylene
glycol) (PEG) is a non-toxic flexible polyether with chemical structure HO-(CH2-CH2-O)n-H. It has hydrophilic heads
comprised of hydroxyl groups providing a good water-solubility at low temperature. PEG has been widely used in
various pharmaceutical and biological applications as well as in many commercial products. For instances, drug delivery
research has obtained from singular pharmacokinetics and biodistribution. In our previous work, PEG-grafted silica
particles were prepared through sol-gel processing using a W/O emulsion as the reaction media. By utilizing a sol-gel
method in a W/O emulsion, spherical PEG-grafted silica particles were obtained. However, the emulsion method has
the complicated steps to prepare silica particles and PEG-grafted particles. In this study, we prepared PEG-grafted
silica particles in water phase without catalyst by using a new and simple method. To graft PEG onto the surface of
silica particles, poly(ethylene glycol) methyl ether (PEGME) polymers of various molecular weights were reacted with 3-
(triethoxysilyl)propyl isocyanate (IPTES). PEGME-IPTES conjugates with urethane groups were synthesized by reacting
the isocyanate group of IPTES with the hydroxyl group of PEGME. The synthesis of PEGME-IPTES and the PEG-
grafted silica particles were confirmed using FT-IR spectroscopy. The surface morphology of particles was investigated
by FE-SEM, TGA and OM. Through BET adsorption isotherm, surface characteristics were measured after calcinations
of samples over 600°C.
154. Dynamic interactions between nanoparticles during confinment
Younjin Min 1 , Mustafa Akbulut 1 , Yuval Golan2 , Joseph Zasadzinski1 and Jacob Israelachvili1 , (1)University of
California, Santa Barbara, Santa Barbara, CA, (2)Ben Gurion University, Beer Sheva, Israel
Using a surface forces apparatus (SFA) we have measured the normal forces between mica surfaces across various
types of nanoparticles consisting of ZnS cores coated with a monolayer of physisorbed surfactant, dissolved in organic
solvents. We focused on the effects of nanoparticle size, shape and concentration on the force-distance profiles. Forces
were exponentially repulsive when the surfactant layers were strongly bound to the nanoparticles; and were roughly
linear when there was adhesion between the nanoparticle cores, i.e., when the surfactant layers detached from the
nanoparticles. In both cases, the range and magnitude of the forces were dependent upon the particle size and solution
concentration. Fine details in the otherwise smooth force-distance profiles indicate specific effects due to particle
chemistry and geometry, and the existence of first-order disorder-order phase transitions upon confinement.
Understanding and controlling the effects of particle shape, size and concentration on particle-particle and particle-
surface interactions should be important for the processing of nanoparticles into ordered nanostructured materials.
155. Dual-Functional Cancer-Targeted Delivery Carriers based on Poly(amino acid)

derivatives
Hyun Jin Lee, Kwang-Suk Jang, Hee-Man Yang and Jong-Duk Kim*, Korea Advanced Institute of Science and
Technology, Daejeon, South Korea

We report self-assmebled nanocarriers of poly(amino acid) derivatives loaded with superparamagnetic iron oxide
(SPIO) nanoparticles for magnetic resonance imaging (MRI) and anticancer drug for chemotherapy. Hydrophobically
modified synthetic poly(amino acid), poly(2-hydroxyethyl L-aspartamide) grafted with octadecyl chains (PHEA-g-C18)
which self-assemble into spherical micellar aggregates in aqueous phase, was synthesized. For cancer-targeted
system, cyclic RGD peptide was conjugated to the polymer system. Synthesis and molecular composition were
confirmed with 1H-NMR and elemental analysis. SPIO nanoparticles well known as strong signal enhancer of T2-
weighted MRI were synthesized with four different diameters, 4, 6, 8, and 10 nm, as previously reported by Sun et al.
and characterized with XRD, TEM, SQUID magnetometer and FT-IR. The surface of nanoparticles is highly
hydrophobidized with oleyl chains and the nanoparticles can be solubilized in nonpolar solvents. Solution of SPIO
nanoparticles in mixture of chloroform/dimethylchloride was added into polymer solution in water and the mixture was
vigorously vortexed to form microelusion. By remove of organic solvents and unloaded nanoparticles, stable micellar
carriers loaded with SPIO nanoparticles were prepared. Physicochemical characteristics with variables of nanoparticle
size and SPIO/Polymer ratio were studied by with DLS, TEM, ICP-AES and T2 mapping. Anticancer drug, doxorubicin
(DOX), was successfully co-loaded by addition of DOX solution in THF into the carrier solution. Loading and in vitro
release behavior of DOX was studied with UV/Vis spectroscopy. Since they show the great stability in aqueous phase
and the high efficiency in enhancing MR contrast etc., their potential use as advanced delivery carriers is highly
expected.
156. Reversibly-swelling polyelectrolyte-surfactant microgel spheres by electrospraying

Matthew E. Helgeson, Yakov Lapitsky, Kristie N. Grammatikos and Eric W. Kaler, University of Delaware, Newark, DE
Polyelectrolyte-surfactant microgel particles can be made by electrospraying of cationic N,N,N-trimethylammonium-

derivatized hydroxyethyl cellulose (JR-400) into an oppositely charged surfactant solution. The electrospraying process
exhibits several modes of behavior, which produce drops (and ultimately gel particles) of diameters ranging from less
than 1 um to over 1 mm. Sub-micron particles are produced by Cuolombic rupture of electrosprayed droplets as
observed by high speed videography. The particles are rendered stable over a broad range of conditions by covalently
cross-linking the polyelectrolyte, and are colloidally stable due to the excess of charge on the gel network. Optical and
scanning electron micrographs suggest that the sub-micron gel particles have a hollow core-shell morphology, which is
confirmed by estimates of the shell thickness from viscometry and densitometry measurements. Quasi-elastic light
scattering is used to obtain the final size distribution of the microspheres, which undergo reversible swelling in the
presence of excess surfactant in solution. Such attractive physical properties make the particles ideal for encapsulation
and release on the colloidal scale.
157. Investigations of large scale structure in shear thickening silica suspensions by flow-
USANS
Dennis P. Kalman and Norman J. Wagner, University of Delaware, Newark, DE
Shear thickening in particle suspensions is a problem in processing and coating industries; shear thickening fluids have
also been utilized with ballistic fabrics in protective armor applications. Shear thickening is known to occur via the
formation of load bearing hydroclusters from theory, simulations, flow-SANS experiments, and indirect rheological
measurements. Here, a flow-USANS experiment is performed in the radial direction (1-3 or flow-vorticity plane) in the
low q regime of 3.3x10 -5 to 3.3x10 -3 Å-1 on a model monodisperse, ~0.5µm diameter, near hard-sphere silica
suspension in polyethylene glycol. A dilute measurement is used to determine the particle form factor, which is used to
quantitatively model the structure of 3 concentrated samples (Φ=0.213, 0.419, and 0.520) under static conditions. In
addition, the structural changes under flow in the shear thinning, Newtonian plateau, and shear thickening regimes
were investigated for all 3 suspensions. Evidence of shear-induced clusters of finite size are apparent in the scattering
from samples in the shear thickened regime. A substantial degree of shear-induced order is observed for this highest
volume fraction sample, which is observed to dissolve into an amorphous, hydroclustered structure upon shear
thickening. The results provide new information about the structure of the hydroclustered microstructure in shear
thickened colloidal dispersions and aid in the development of STF-based technologies.
158. Noro and Frenkel generalized law of correspondent states in attractive colloidal
systems: thermodynamics and dynamics
Giuseppe Foffi, Ecole Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland and Francesco Sciortino,

Universita' di Roma La Sapienza, Roma, Italy
It is well established that the range of the attraction is a key parameter for both the thermodynamical and dynamical
properties in short ranged attractive colloidal systems. I will show the effect of going to an extremely short range, a limit
that is the basis of the celebrated Baxter (or adhesive) model, where the range is taken to the zero limit. I will discuss
the reason of the success of the Baxter model, showing that the equivalence of all the short range potential systems
(the Noro and Frenkel "generalized law of correspondent states"), can be explained in the rigorous PEL thermodynamic
formalism as arising from the multiplicative contribution that each bond add to the vibrational entropy and from the
possibility of separating vibrational and floppy contributions (a condition which requires a small bond width). Incidentally,
I will show how our approach allows to count the fraction of floppy modes in a system of bonded particles. The case of
non isotropic interaction potentials will be discussed as well as the connection to the dynamical properties of the short
ranged attractive colloidal systems and the gel transition.
159. Thermodynamic Equilibrium of ZSM-5 Formation

Dustin Fickel, University of Delaware, Newark, DE
Understanding zeolite growth mechanisms is important for futher advancement in zeolite science. This work focuses on
the formation of ZSM-5 through non-organic synthesis. To understand the formation of this zeolite, thermodynamics is
used to quantify the relationship between the resulting zeolite and the supernatant remaining after synthesis. A
complete range of Si/Al ratios for ZSM-5 formation, between approximately 10 and 50, is studied so that a complete
phase equilibrium diagram can be formulated. In accomplishing this thermodynamic equilibrium equations along with
regular solution theory are used. The techniques of x-ray diffraction, NMR, ICP, and small angle x-ray scattering are
used in this research. Our research has shown a direct correlation between the amount of aluminum in the synthesis
gel and that in the resulting ZSM-5. We have also shown that the supernatant contains exceedingly small amounts of
aluminum, which implies that it is expended rapidly during the synthesis. Overall the results of this research will help in
the understanding of ZSM-5 formation.
160. Thermodynamic stability in binary mixtures of eye lens proteins
Nicolas Dorsaz 1 , Giuseppe Foffi 1 , Anna Stradner2 , George M. Thurston 3 and Peter Schurtenberger 2 , (1)Ecole
Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland, (2)University of Fribourg, Fribourg, Switzerland,
(3)Rochester Institute of Technology, Rochester, NY
The eye lens consists of a solution of mainly three classes of water soluble proteins called alpha-,beta- and gamma-
crystallins. A uniform packing of crystallins guarantees the correct index of refraction necessary for the eye
transparency. Local aggregation or phase separation of these proteins, however, can increase dramatically the
scattering of light with a consequent loss of transparency of the lens leading to cataract disease. We studied
numerically the binary alpha-gamma mixture by molecular dynamics simulations of a coarse-grained model of these
proteins. Combining our numerical results with experimental neutron scattering data, the interactions between the
proteins has been devised. We have then started a systematic study of the thermodynamic stability of binary mixtures
via Barker-Henderson perturbation theory. Within this approach, the instability surface of the alpha-gamma asymmetric
mixture was determined for the whole concentration-density parameter range. The stability of these high concentration
crystallin mixtures was found to depend on the alpha-gamma attraction in a manner that is both extremely sensitive
and non-monotonic in agreement with the experimental and numerical results. Such high sensitivity enforces the
possible implication of thermodynamic instabilities in some forms of cataract. The present results also suggest
mechanisms to tune the stability of more general colloidal solutions and binary mixtures.
161. Selective Hydrogenation on Zeolite-Supported Bimetallic Catalysts

Wei Huang, Raul F. Lobo and Jingguang G. Chen, University of Delaware, Newark, DE
Novel catalysts have been synthesized and evaluated by supporting Pd-based bimetallic nanocatalysts on zeolites to
achieve higher selectivity for the selective hydrogenation of acetylene in a stream containing excess ethylene at
relatively low temperatures (300-339K). Low-temperature hydrogenation offers the opportunity of using competitive
adsorption to achieve preferential hydrogenation of acetylene. Previous work from our group has found that bimetallic
catalysts favor low temperature hydrogenation. Results from many other groups have also shown that Pd is a good

catalyst for the selective hydrogenation of alkynes in excess ethylene. Therefore the strategy of the present work was
to modify Pd catalysts and to embed bimetallic nanoparticles in an environment that is highly selective for acetylene
hydrogenation. Cation-g interaction offers the potential for selective adsorption of acetylene on the zeolite supports. In
the current work we used the ion-exchanged â-type zeolite as the support of the bimetallic catalysts. The zeolite
structure should have multiple dimensions and contain large pores, in order to house the bimetallic nanoparticles inside
the pores. Flow reactor studies using GC, batch reactor studies using FTIR, EXAFS and CO-Chemisorption evaluation
have been performed. Our results indicate that the Pd-Ag bimetallic catalyst has a much higher selectivity for acetylene
hydrogenation in excess ethylene than either Pd or Ag. Modeling of reactions in FTIR shows significant differences in
the hydrogenation rate constant, adsorption equilibrium constant, as well as the selectivity of the ã-Al2O3 supported
catalysts and â-zeolites supported catalysts, with â-zeolite supported catalysts showing much higher selectivity than the
ã-Al2O3 supported catalysts.
162. Ozone/Ultrasound Oxidation of Single-walled Carbon Nanotubes (SCNTs) in Water

Minghua Li, Thomas P. Beebe and Chin-Pao Huang, University of Delaware, Newark, DE
Functionalization of carbon nanotubes (CNTs) is critical for enhancing its application, processability and performance in
various fields. Changes of surface characteristics can also affect the fate, transport and effects of these particulates in
the environment. A clean and simple wet chemical oxidation method involving only ozone and ultrasound (US)
processing in water was used to functionalize single-walled CNTs (SCNTs). SCNTs were disintegrated, oxidized and
even shortened by O 3 or O 3 /US treatment for 24 hr. After treatments, the solubility and aqueous phase stability of
SCNTs were improved. Oxygen functional groups were formed on the SCNTs surface. Surface oxygen to carbon ratio
increased by more than 600% after 72 hr of O 3 treatment based on the X-ray photoelectron spectroscopy (XPS)
results. XPS showed evidence for surface C-OH, C=O and COOH groups as oxidation products. The effective particle
length was reduced from initial 5000 to 300 and to 150 nm, respectively after 24 hr of O 3 and O 3 /US treatments,
indicating SCNTs shortening during the oxidation process. The surface potential of SCNTs decreased from 5 to -29 mV
(at pH 2) after 2 hr O 3 US treatment. Results of sedimentation and turbidity measurements were consistent with that of
XPS analysis. An oxidation pathway was proposed and results were fitted with various kinetic models to identify the
pertinent oxidation kinetic parameters. The oxidation state of the SCNTs can be controlled by the O 3 /US exposure time
without any additional treatments; this aqueous phase oxidation offers the potential for use as a low-cost CNTs surface
process.
163. Molecular Dynamics Simulations of Surfactant and Nanoparticle Self-assembly at

Liquid-Liquid Interfaces
Mingxiang Luo and Lenore L. Dai, Texas Tech University, Lubbock, TX
We have performed molecular dynamics (MD) simulations to investigate self-assembly at water-trichloroethylene (TCE)
interfaces with the emphases on systems containing modified hydrocarbon nanoparticles (1.2 nm in diameter) and
sodium dodecyl sulfate (SDS) surfactants. The nanoparticles and surfactants were first distributed randomly in the water
phase. The MD simulations have clearly shown the progress of migration and final equilibrium of the SDS molecules at
the water-TCE interfaces with the nanoparticles either at or in the vicinity of the interfaces. One unique feature is the
“attachment” of surfactant molecules to the nanoparticle clusters in the water phase followed by the “detachment” at the
water-TCE interfaces. At low concentrations of surfactants, the surfactants and nanoparticles co-equilibrate at the
interfaces. However, the surfactants, at high concentrations, competitively dominate the interfaces and deplete
nanoparticles away from the interfaces. The interfacial properties, such as interfacial thickness and interfacial tension,
are significantly influenced by the presence of the surfactants, but not the nanoparticles. The order of the surfactants at
the interfaces increases with increasing surfactant concentration, but is independent of nanoparticle concentration.
Finally, the simulation has shown that surfactants can aggregate along the water-TCE interfaces, with and without the
presence of nanoparticles.
164. Redox Transformation of Organic Contaminants Mediated by Black Carbon

Nanoparticles
Pei Chiu and Seok-Young Oh, University of Delaware, Newark, DE

Black carbon is a collection of carbon-rich nanoparticles that are ubiquitous in the environment. Black carbon plays a
pivotal role in controlling the fate and transport of hydrophobic organic contaminants. The current dogma states that
geosorbents such as black carbon can act as contaminant adsorption sites, and the adsorbed molecules are immobile
and nonreactive. However, our data suggest that black carbon can serve as both an adsorbent and a mediator of redox
reactions. We showed that molecules adsorbed to black carbon have dramatically higher reductive reaction rates. We
hypothesize that this is because black carbon contains microscopic graphitic domains in its structure and thus can
conduct electron and atomic hydrogen from a reductant to adsorbed contaminant molecules. This study will
demonstrate the adsorptive and catalytic roles of black carbon and will attempt to elucidate the mechanism for black
carbon-mediated degradation of organic contaminants. Experiments were conducted using graphite and soot as model
black carbons to assess the reduction of black carbon-bound nitroaromatic and heterocyclic nitramine explosives in the
presence of an environmentally relevant reducing agent, such as thiol and sulfide. Our presentation will demonstrate
this previously unrecognized role of black carbon and will discuss the potential impact of natural and synthetic black
carbon on the fate of organic contaminant in aquatic and terrestrial systems.
165. Controlled crossflow of liquids within particle-stabilized bicontinuous emulsions

Kathryn A. White, Eva M. Herzig, Andrew B. Schofield and Paul S. Clegg, Edinburgh University, Edinburgh, United
Kingdom
Recent theoretical work[1] has led to new soft-solid materials consisting of bicontinuous emulsions stabilized by colloidal
particles[2]. The ‘jamming' of these particles at the liquid-liquid interface prevents an otherwise unstable emulsion from
coarsening, and effectively freezes the interpenetrating fluid networks in a metastable sponge-like configuration. The
result is a microporous material with a characteristic channel size; this is referred to as a bicontinuous interfacially
jammed emulsion gel, or ‘bijel'.
Given that such a material contains a considerable interfacial area between two immiscible liquids, a number of
possible applications exist, one of which is as a crossflow microreaction medium. An attractive property of bijels is that
the structure is preserved when exposed to an excess of either of the two component liquids. Using custom-built flow
cells, we study the properties under flow conditions of particle-coated flat liquid-liquid interfaces as models for the more
complicated bijel, and the bijel itself. Here we present results on the transfer of fluorescent species across the
interface, and demonstrate the influence of variables such as flowrate, channel size and interfacial tension on the
stability and rheology of the bijel.
[1] K. Stratford, R. Adhikari, I. Pagonabarraga, J.-C. Desplat and M. E. Cates. Science 309, 2198 (2005)
[2] European Patent Application EP05761568.4 (M. E. Cates, W. C. K. Poon, S. Egalhaaf, P. S. Clegg)
166. Coupled effects of attachment and straining on retention of colloids under unfavorable
conditions
Chongyang Shen1 , Yan Jin1 and Yuanfang Huang 2 , (1)University of Delaware, Newark, DE, (2)China Agricultural
University, Beijing, China
This study examines effects of solution chemistry on the straining of colloids in porous media under unfavorable
conditions. Saturated column experiments were conducted with various sizes of latex particles and glass beads at
different ionic strengths. A two- or three-step procedure was used for colloid attachment and release, following
dissection of the columns to determine distribution profiles of retained colloids. The effluent breakthrough curves and
spatial distributions of the retained colloids in the columns were modeled with a convective diffusion equation including
terms of attachment and straining. Results show that (i) straining increases with the decrease of glass beads diameter
(dc) and with the increase of colloid diameter (dp); (ii) fitted straining coefficient increases with the increase of
attachment rate (or ionic strength); (iii) the threshold of dp/dc (above which straining occurs) determined using glass
beads as porous media is much larger than those determined by sand grains. Our study indicates that a deeper
secondary minimum depth facilitates colloids wedged and retained in straining sites, and the irregular shapes of natural
porous media (e.g. sand grains or soil) play critical roles in the straining (i.e., grain-to-grain contact) of colloids when
dp/dc is small.
167. Initial stages of titanium nitride deposition on Si(100): Importance of the Ti-N bond

scission during the adsorption of tetrakis-(dimethylamino)-titanium

Juan Carlos F. Rodríguez-Reyes and Andrew V. Teplyakov, University of Delaware, Newark, DE
Tetrakis-(dimethylamino)-titanium (TDMAT) is a deposition precursor for titanium nitride and titanium carbonitride
diffusion barriers. We investigated the reaction of TDMAT with the Si(100) surface because of its crucial impact on the
growth of diffusion barrier films and on the interface formation. A combination of density functional calculations and
infrared (IR) spectroscopy suggests that TDMAT dissociatively adsorbs on Si(100). Such process involves the formation
of a Ti-Si bond upon cleavage of a Ti-N bond. The reactivity of the Ti-N bond was also observed during TDMAT
adsorption on ammonia-covered surfaces, where our spectroscopic results indicate that transamination reactions occur.
In addition to the possibility of Ti-N scission during the first stages of adsorption, the cleavages of both a C-H bond and
a C-N bond are considered as alternative pathways of adsorption. Spectroscopic evidence of Si-H bond formation upon
TDMAT adsorption indicates that scission of the C-H bond is possible, although as a minor channel. In contrast, we did
not find any experimental evidence of Si-CH3 bond formation, in agreement with the theoretical prediction that scission
of the C-N bond is thermodynamically stable but kinetically hindered. Due to the current importance of zirconium-,
hafnium-, and tantalum-containing compounds for technological applications, the dissociative adsorption of their
alkylamino compounds is investigated by theoretical methods and compared to TDMAT. Elucidation of the first stages of
adsorption will allow a better control of thin film growth processes.
168. Desorption of Polyelectrolyte Coatings from Nanoscale Fe0 Used for Environmental
Remediation
Hye-Jin Kim, Tanapon Phenrat, Navid Saleh, Kevin Sirk, Robert D. Tilton and Gregory V. Lowry, Carnegie Mellon
University, Pittsburgh, PA
Zerovalent iron nanoparticles (NZVI) are an emerging technology for ground water remediation of dense nonaqueous
phase liquids (DNAPL). Polymeric surface coatings are required for mobility in the subsurface and can afford the
particles an affinity for DNAPL. The ultimate fate of the particles depends in part on the stability of the surface coatings.
One often observes effectively irreversible adsorption of high molecular weight polymers on solid surfaces. This study
reports desorption rates of commercially available polyelectrolytes, including polyaspartate (MW=2.5k and 10k),
carboxymethyl cellulose (MW=90k and 700k), and polystyrene sulfonate (MW=70k and 1M) from NZVI used for in situ
degradation of DNAPL in groundwater. The initial adsorbed masses of polyelectrolyte ranged from 1.5 to 4.0 mg/m 2 .
For a given polyelectrolyte, the adsorbed mass was independent of molecular weight. Desorption was very slow, with
less than 30% of each polymer desorbed after 4 months. Quartz crystal microbalance (QCM) data confirmed the
presence of polymer on the particle surfaces by comparing the attachment of bare and modified particles to a silica
surface. Transport experiments also indicate that the polymer coating is still on the surface of NZVI. Based on these
results, polymer modified nanoparticles will potentially remain mobile for long times after they are injected into the
subsurface. Other factors that might affect coated NZVI fate, especially the potential for microorganisms to degrade the
polymer coatings, must still be evaluated.
169. Preparation of multiple-functionalized surfaces with precise spatial resolution

Moniraj Ghosh 1 , Christina Alves1 , Kathleen J. Stebe2 and Konstantinos Konstantopoulos1 , (1)johns Hopkins
University, Baltimore, MD, (2)Johns Hopkins University, Baltimore, MD
Patterned surfaces presenting one or two functionalities are widely used in studies ranging from patterned
electrodeposition of materials to the studies of cell adhesion. These surfaces are often made using microcontact printing
followed by backfilling, allowing the creation of functionalized regions of submicron dimensions. Here, we generalize this
technique to allow the creation of multifunctional surfaces using a novel combination of microcontact printing, backfilling
and microfluidics to present multiple functionalities (proteins, antibodies, surfactants) and lengthscales (sub-micron and
above) over areas of large extent. First, microcontact printing is used to place an active species in desired locations of
the surface. The open regions are passivated by backfilling with a blocking agent, e.g. PEG via suitable surface linkers.
This substrate is then used as a lid to a microfluidics device to form several channels. Species of interest are pumped
through the channels to adsorb on to the active regions. Alternatively, a PEGylated surfactant can be microcontact
printed to form a lattice pattern with open adherent regions. Thereafter, microfluidics can deliver desired functionalities
to these open areas. The feature size on the printing stamp determines the size (i.e. resolution) of the printed species.

The width and the geometry of the microfluidics channels determine the number of patches presenting a particular
functionality. The nature of the functionalization is guided by suitable surface chemistry. These patterned multifunctional
surfaces are of particular interest in material manufacture and bioassays. Examples of multifunctional surfaces for cell
adhesion studies are shown.
170. INTERFACIAL INTERACTIONof SPENT SHALE with WATER in OIL PRODUCING

INDUSTRY
Toomas Tenno and Karin Hellat, University of Tartu, Tartu, Estonia
In retorting process of Estonian oil shale more than half of the sulfur occurring in the feed shale remains in the solid
residue, where the sulfur is mainly in the form of calcium and iron sulfides. CaS formation is connected with limestone
basement of the North East of Estonia and FeS originates from pyrites in the feed oil shale. The process of interfacial
interaction of CaS and FeS with water is taking place in the spent shale dumping sites. The dissociation of calcium and
iron sulphides in water produces sulfide ions and as a result of S2- interaction with water, HS - and H 2 S will be formed
and the pH of the water phase will be raised. As the solubility product of FeS is very low (6.3*10-18 ), in the first
approximation the role of FeS is not taken into account when calculating the concentrations of Ca2+ and S2- ions in the
system containing solid CaS and FeS. The system under investigation of solid CaS in equilibrium with water phase will
contain six species in significant levels: Ca2+ , S2-, HS -, H 2 S, OH - and H 3 O + . As there are no data available for
solubility product of CaS, the equilibrium concentrations of Ca2+ ions and of sulfur containing species are taken for the
-
bases of modeling the balanced system. The mass-balance expression for the system is [Ca 2+ ] = [S 2-/sup>] + [HS ] +
[H2 S]. For calculation the concentrations of the components of balanced system five equations were derived and simultaneously solved.
171. Interfacial Phenomena in Proton-Exchange Membrane Fuel Cells
Douglas Aaron1 , Sotira Yiacoumi 1 , Costas Tsouris2 , David J. Keffer3 , Shengting Cui 3 , Junwu Liu 3 , Myvizhi E.
Selvan3 , Brian J. Edwards 3 and William V. Steele3 , (1)Georgia Institute of Technology, Atlanta, GA, (2)Oak Ridge
National Laboratory, Oak Ridge, TN, (3)University of Tennessee, Knoxville, TN
The operation of proton exchange membrane fuel cells (PEMFC) is highly dependent on interfacial phenomena
occurring at the anode, cathode, and polymeric membrane. This work is focused on better understanding the effects of
humidity, feed pressure/ratio, and temperature on the fuel cell performance. Experimental work is being performed to
investigate the effects of these operating parameters on the power output of the cell. Current work is focused on
employing electrochemical impedance spectroscopy (EIS) to understand specific resistances at interfaces of the cell
components. The results from EIS experiments can be compared with those from molecular modeling to better
understand transport limitations at the interfaces. Molecular modeling focused on the structure and properties of a
Nafion membrane at various levels of hydration is also being performed. The hydration level in the PEM affects ion
transport at the interface between the electrodes and PEM, as well as ion transport through the PEM from one
electrode to the other. Our findings show that there is virtually no wetting of a graphitic electrode by water hydrating the
PEM. There is significant wetting of Pt nanoparticles in close proximity to the PEM. This provides a molecular-level
picture for the role of humidity at the electrode/electrolyte interface. If the system is too dry, only Pt nanoparticles
immediately adjacent to the PEM can contribute to conductivity. If the system is too wet, the Pt nanoparticles can wet
entirely and become inaccessible to gaseous hydrogen.
172. MEASUREMENTS of the Permeability of Oxygen through the Air-Water Interface at Low
Concentration of Surfactants in Water Phase
Toomas Tenno, Erik Mölder and Taavo Tenno, University of Tartu, Tartu, Estonia
Oxygen diffusion through the air-water surface layer at various surfactant concentrations in the solution was
investigated. Experimentally was established that at very low concentrations of surfactant (about 0,0001 mol/l)
permeability of oxygen through air-water interface reduces about 40%, when at the same time surface tension
decreases only about 0,1% from it's maximum value. The original technique for measurement of oxygen mass transfer
through the air-water interface was applied. The measuring device, which is based on an electrochemical oxygen
sensor measures decrease of oxygen concentration in the small volume of the measuring chamber, which is in contact

with deoxygenated solution of surfactant. Experimental data obtained were incorporated into mathematical model, which
allows calculate the oxygen mass transfer coefficient in the air-water surface layer. In addition to permeability
measurements the surface tension of the same solutions containing surfactant was measured. On the bases of Gibbs
adsorption isotherm equation the amount of adsorbed surfactants was calculated using surface tension data. For
preparing solutions of surfactants isomers of butanol [1- butanol, 2-butanol, 2-mehylpropanol (isobutanol), 2-methyl-2-
propanol (tert-butanol)] were used.
173. DNA-separation using Self-assembled Peptide monolayers

Vikas P. Jain and Prof. Raymond S. Tu, City College of New york, New York, NY
The phenomenon of counterion-mediated DNA-condensation is fundamental to most DNA related activity in the cell,
from chromosome packaging to control over translational mechanisms. Developing synthetic systems to manipulate
DNA-condensation is essential for the development of biotechnologies for gene encapsulation and DNA-separation.
The main purpose of this study is to elucidate the cooperative process of DNA-condensation with a set of self-
assembling peptide building blocks, particularly studying the effect of charge distribution. The peptide that has been
designed is a b-hairpin (two b-strand “legs” connected by a b-turn). The design incorporates the alternating periodicity,
where hydrophobic and hydrophilic residues are presented on either face of the b-strand. This periodicity gives a planar
amphiphilic character to each hairpin. Also, the b-turn of the hairpin is constructed from the inclusion of residues D-Pro
and Gly, and the peptide is positively charged because of an abundance of lysine amino-acids. The secondary structure
is characterized by using circular dichroism spectropolarimetry and its behavior at the air-water interface is investigated
by using pendant drop/bubble method. We characterize the peptide behavior as a function of salt (electrolyte), which
should provide the information about the effect of charge on the self-assembled structure of the peptide. We expect
observe similar behavior for the peptide as it complexes with negatively charged DNA.
174. Energy Storage through Electrical Double Layer Formation in Nanostructured Carbon-
based Materials
Chia-Hung Hou 1 , Patricia L. Taboada-Serrano 2 , Sotira Yiacoumi 1 and Costas Tsouris3 , (1)Georgia Institute of
Technology, Atlanta, GA, (2)Georgia Institute of Technology, Oak Ridge, TN, (3)Oak Ridge National Laboratory, Oak
Ridge, TN
Electrical double layer (EDL) formation or electrosorption in nanostructured carbon-based materials is critical to many
electrochemical processes, such as energy storage and water purification. Cyclic voltammetry experiments show that
mesopores and micropores exhibit significantly different behaviors in an electrosorption process. This phenomenon is a
result of the occurrence of EDL overlapping, which has a major influence on the mass transfer rate of ions and the
number of ions inside the pores at equilibrium. Cyclic voltammetry revealed that the relationship between the pore size
of nanoporous electrodes and the dimension of ionic species can determine the capacitance of nanoporous carbon in
electrolyte solutions. In addition to experimental information, an extended EDL model based on the classical Gouy-
Chapman theory indicates that the pore size distribution plays an important role in the determination of the EDL
capacitance. Monte Carlo simulation techniques have also revealed the EDL behavior in the presence of multivalent
and monovalent ions confined to a charged nanopore. Simulation results demonstrate the mechanisms of
electrosorption in terms of pore size and ionic species. This work presents the fundamental aspects of EDL formation in
nanostructured carbon-based materials via a combination of electrochemical experiments and molecular and
macroscopic modeling. Novel carbon materials of controlled porosity are also presented and discussed in light of energy
storage applications.
175. Removal of Waterborne Viruses Using Nano-scale Zerovalent Iron and the Effect of
Organic Matter on the Removal
Liping Zhang, Pei P. Chiu and Yan Jin, University of Delaware, Newark, DE
Microbial pathogens (bacteria, protozoa, and viruses) in waters present serious threats to public health. Viruses are
particularly problematic because they are smaller, more mobile in the environment, and more resistant to chlorination
and filtration. Our previous studies showed that viruses were efficiently removed from water by zerovalent iron particles,
which was mainly achieved through reactions with iron oxidation products formed through corrosion of iron. It is

therefore expected that nano-scale iron will have a greater viral removal capacity given its larger specific surface area
than granular iron particles. This hypothesis was tested through batch experiments using two bacteriophages, φX174
and MS2, as model viruses. The effect of natural organic matter (NOM) on the removal of viruses was also evaluated.
Results show that removal of both φX174 and MS2 followed a first-order reaction and that the removal rate coefficients
are similar to that when 10X (mass basis) of Peerless TM iron granules were used. The mechanisms of virus removal by
nano-scale iron and the potential of using nano-scale iron in applications related to water treatment under relevant
environmental conditions (e.g., presence of varying levels of NOM) will be discussed.
176. Multithiolated dendrimers as linkers for DNA immobilization on gold surfaces

B. Scott Day, Huan Cao and Michael L. Norton, Marshall University, Huntington, WV
Modification of surfaces with DNA is an area of increasing importance to many scientists and engineers. Interest is
driven by the fact that fabrication of DNA ‘chips' with both a high density of probe sites and a large number of probe
molecules per site will allow numerous high quality experiments to be conducted on a single substrate. DNA chips have
been fabricated using a variety of substrates and attachment strategies. One of the more common strategies employed
to construct DNA chips relies on gold-thiol bonding, where thiolated DNA is attached to the surface of gold coated
substrates via self assembly. Fabrication of DNA arrays on gold surfaces is fitting because the materials necessary to
construct them are relatively inexpensive and readily available. One of the major disadvantages of using the thiol-gold
bond is the limited long term stability of the probe molecule attachment. To overcome this limitation we have developed
a relatively simple synthetic approach to place multiple thiol groups on a single DNA strand to increase the long term
stability of the DNA probe attachment. We react N-succinimidyl 3-(2-pyridyldithiol)-propionate) (SPDP) with the primary
amine groups of a generation 3 dendrimer, polyamidoamine. The disulfide groups are next reduced. In the last step of
probe synthesis, acrylamide-modified DNA is reacted with the dendrimers. This synthesis places a multithiolated head
group on the DNA for robust attachment to gold surfaces. We have observed this immobilization strategy to display
superior stability when compared to analogous single thiolated DNA strands.
177. Protonation of adsorbed phosphate on oxides and its effect on adsorption behaviors
Xiao Huang and Gregory D. Foster, George Mason University, Fairfax, VA
This study attempts to identify the adsorption behaviors which are characteristic of protonation of adsorbed phosphate
on oxides. We have experimentally observed the following three characteristic behaviors for P adsorption on alumina:
1) an adsorption maximum at pH 4.0-4.5 at final P concentration of > 200 µmole l-1; 2) a plateau from pH 3.5 to 6.5 at
final P < 100 µmole l-1 and an adsorption maximum at pH 5.5 at the extremely low concentration of 10 µmole l-1; and
3) intersection of adsorption isotherms at the pH ranges of 2.5-4.5 and 5.5-6.5. Using surface complexation theory, we
have linked Behavior 1 to the phosphate being adsorbed as di-protonated monodentate complex; Behavior 2 to the
adsorption as mono- and de-protonated monodentate complex; and Behavior 3 to the transition of phosphate from
being adsorbed as di-protonated to mono-protonated monodentate complexes. Our analyses indicate that phosphate is
adsorbed as a monodentate rather than a bridging bidentate complex; the three surface P complexes that have been
spectroscopically identified are di-, mono-, and de-protonated monodentate complexes, respectively.
178. Multi-sectioned Cylindrical Porous Polymeric Materials

Jung Hun Song, Graduate Center and City College of City University of New York, New York, NY and Ilona
Kretzschmar, City College of City University of New York, New York, NY
Control of the three-dimensional periodicity of porous polymeric materials (PPMs) has enormous potential for photonics,
separations and tissue engineering. Controlled pore sizes and porosity of PPMs have shown to be essential
characteristics in all of these fields.1 Our work is concerned with the fabrication of three-dimensionally periodic PPMs
that have well-defined sections with different pore sizes using colloidal templating.
Colloids of different sizes are convectively assembled inside capillaries. A liquid polymer is used to fill the interstitial
spaces formed by the colloidal assembly. Subsequently, the polymer is cured to form a solid colloid-polymer matrix. An
inverse opal structure forms upon dissolution of the colloids from the matrix, leaving behind a multi-sectioned PPM. We
have assembled 0.5, 2.4, and 9.6 µm sized sulfate-polystyrene (PS) colloids in 50 µm inner-diameter
polymethylmethacrylate (PMMA) capillaries with various sequences. The hexagonally close-packed crystals formed

have been infiltrated by a UV curable prepolymer, which has been cured subsequently under a long-wave UV light (365
nm). Treatment of the cured colloid-polymer matrix with organic solvents leads to porous polymeric materials with a
controlled pore size distribution.
We have investigated the structure of colloidal assemblies and the resulting PPMs using scanning electron microscope
and will present our findings. Further, knowledge of properties and characteristics of these PPMs are critical in practical
applications, therefore, a preliminary tensile strength and UV-Vis analysis will be also presented.
(1) Xia, Y.N.; Gates, B.; Yin, Y.D.; Lu, Y.; Monodispersed colloidal spheres; Old materials with new applications.
Advanced Materials 2000, 12, (10), 693-713.
179. Cooperative networks: Viscoelastic control in solutions of wormlike micelles and

polymers
Matthew W. Liberatore and Nathan Work, Colorado School of Mines, Golden, CO
Mixtures of polymers and surfactants in solution are important in a wide range of applications including detergents,
personal care products and oil recovery fluids impacting the chemical, pharmaceutical and petroleum industries. The
objective of this project is creating synergy between the polymers and wormlike micelles allowing the properties of the
solution, especially the rheology, to be tuned. Maintaining the wormlike micelle state of surfactant aggregation in the
presence of an entangled polymer network is a viable challenge. Experimental protocols for studying the polymer-
micelle mixtures include flow and oscillatory rheology, rheo-optics, scattering and phase mapping. Using theoretical
models from surfactant and polymer science, this experimental characterization allows tremendous insight into important
length scales and time scales of the co-entangled network. Exploitation of solution conditions to increase the overall
length of the wormlike micelles creates either entangled or branched networks, which changes the viscosity of the
solution. Preliminary studies have identified solution conditions that change the rheology from weakly shear thinning to
strongly shear thinning to shear thickening. Overall, experimental control of pressure, temperature, macromolecule
concentration and other variables allows structure-property relations of wormlike micelle-polymer cooperative networks
to be measured, thus enhancing the theoretical understanding of surfactant-polymer interactions.
180. Surface Anisotropic (Patchy) Particles by Glancing Angle Deposition

Amar B. Pawar and Ilona Kretzschmar, The City College of City University of New York, New York, NY
Inducing directionality in the self–assembly process has great potential in present day ‘bottom-up' approaches for the
generation of supramolecular entities. Surface anisotropic (patchy) particles introduce directionality in self–assembly by
specific interactions between patches. Not only just relying on the physical forces between the patchy particles, these
particles can be directed into a desired assembly through linker molecules, which covalently bind to the patches. Here
we present our results from the application of “Glancing Angle Deposition” for the production of patchy particles.
Vertical vapor deposition onto close-packed monolayers of colloids is a commonly used technique for the production of
Janus particles. The tilting and rotating of the colloidal monolayer allows the angled deposition of patches onto the
particles. The angle of the source with respect to the monolayer and the orientation of the particles in the monolayer
determines the shape of the “patch” on the particles. Characterization of the patch size and geometry is crucial for
further applications of these patchy particlesin the self–assembling of target structures.
This is the first time we report data on the geometry of the patches generated on the particles as a function of the
angle of deposition. The experimental results are compared with the results obtained from a mathematical model used
to predict the patch geometry. Towards application of these patchy particles for self–assembly using linker molecules,
we will present preliminary results on attaching organic linker molecules to the patches on the particles.
181. Like-charge interactions in membrane-coated colloidal monolayers

Esther W. Gomez, Nathan G. Clack and Jay T. Groves, University of California, Berkeley, CA
Colloidal particles, near a like charged wall, have been observed to exhibit a long-range attraction under certain
circumstances. The observed attraction in these systems contradicts the Poisson-Boltzmann mean field theory, which
predicts that similarly charged particles will repel each other. Here, we study an electrostatically levitated two

dimensional colloid in which the underlying planar surface and the particles are coated with lipid membranes. This
coating allows for the surface potential of the underlying substrate and particles to be varied continuously. By exploring
a wide range of surface compositions and solution ionic strengths we find that anomalous long-range like charge
attraction only occurs between negatively charged particles.
182. Self-assembly of surface anisotropic (patchy) microspheres

Jing-Qin Cui and Ilona Kretzschmar, the City College, the City University of New York, New York, NY
Self-assembly has been shown to play an important role as a bottom-up approach in nanofabrication. However, most
currently used approaches are unable to produce structures with precise spatial positioning of particles when using
isotropic particles. [1] On the contrary, anisotropic particles may self-assemble into ordered structures taking advantage
of their asymmetric functionalization. Recent work by Hong et al.[2] has shown that charge-asymmetric particles form
clusters due to strong electrostatic interactions between particles in good agreement with MD simulations.
Here we present data on the self-orientation of surface-anisotropic microspheres with differing patch roughness via
continuous convective assembly. [3] Surface-anisotropic spheres are harvested and re-suspended in DI-water. A specific
volume of re-suspended anisotropic spheres is added to a cell consisting of a Teflon ring with a 1-cm inner diameter
mounted on a piece of cleaned silicon (110) wafer. The solvent is allowed to evaporate and the orientation of the
patchy particles in the resulting monolayer is studied.
The sulfate-terminated polystyrene (sPS) spheres (2.4 µm) used in the experiments are asymmetrically modified with
silver using either template-aided electroless deposition [4] (rough surface) or physical vapor deposition (smooth
surface): and. The two processes give different morphology thus it is suggested that they show different orientation
preference during self-assembly.
1. B. D. Gates, Q. Xu et al, Chem. Rev. 2005, 105, 1171-1196
2. L. Hong, A. Cacciuto et al, Nano Letters, 2006, 6, 2510-2514
3. A. S. Dimitrov, K. Nagayama. Langmuir 1996, 12, 1303-1311
4. J.-Q. Cui, I. Kretzschmar, Langmuir, 2006, 22, 8281-8284
183. Zeta Potential Measurments via a Rotating Disk

James Hoggard, Paul Sides and Dennis C. Prieve, Carnegie Mellon University, Pittsburgh, PA
Measurement of the zeta potential of large planar surfaces is important in studies of membranes, proteins, polymers
and surfactants. A novel method, called ZetaSpin, for measuring the zeta potential of disk shaped samples with radii on
the order of centimeters is presented. When a disk with a surface charge is rotated in solution, a streaming potential is
generated in the bulk solution on the order of micro- to millivolts depending on the solution conductivity and the zeta
potential of the surface. This streaming potential can be measured between a pair of electrodes located in the bulk
solution. The theory relating the streaming potential to the zeta potential is presented. An advantage of the rotating disk
is that the entire disk surface is uniformly accessible to mass transfer. This combined with the fact that measurement of
the zeta potential can be made on the order of 10 second enables studies of adsorption or desorption of ions,
surfactants, proteins, etc. on solid surfaces not possible with a capillary measurement.
184. Biological interactions with nano-patterened surface by gold nanoparticles

Jun Zhang, Sudhanshu Srivastava, Vincent Rotello and Maria Santore, University of Massachusetts, Amherst, MA
Mixed monolayer protected gold clusters (MMPCs) functionalized with quaternary ammonium chains were employed to
pattern the surface on a 10-nanometer length scale. The gold nanoparticles were randomly deposited on silica surfaces
under diffusion-limited conditions and the deposition quantity was precisely controlled by varying the solution
concentration and the flow time. The resulting surfaces imposed a complex field of attractions and repulsions on
approaching objects. In our study, silica particles were used to reveal the underlying adhesion physics with these

surfaces and to act as simple models of biological systems such as cells and bacteria. Using near-Brewster
reflectometry, we measured the the adhesive interactions between the nano-pattereded surface and the silica particles.
The surface patteren possess a substantial random component and is expected to give rise to adhesive selectivity at
the micron scale. These surfaces, therefore, can form the basis for cell discriminating and sorting systems.
185. Structure and Dynamics of PEG-containing Surfactants/Copolymers on Hydrophobic

and Hydrophilic Surfaces
Pazit Ofir Bar-Yosef, University of Massachusetts Amherst, Amherst, MA and Maria M. Santore, University of
Massachusetts, Amherst, MA
The adsorption behavior of different surfactants and polymers on surfaces of varying hydrophobicity, employing Near-
Brewster angle reflectometry and Total Internal Reflectance Fluorescence (TIRF) was investigated. Using these
techniques we were able to study the adsorption kinetics and adsorption reversibility of commercially available
surfactants and tailor maid copolymers, which were adsorbed on three different substrates: acid etched microscope
slides, C16 self assembled monolayers and Polypropylene films (PP). This data alone provide insight into the adsorbed
layer structure: the integrity of the PEG brush and the continuity of adsorbed hydrophobic domains. We have further
investigated the extent to which these pre-adsorbed surfactant/copolymer layers affect subsequent fibrinogen
adsorption. Data are interpreted in terms of the extent to which the copolymers are displaced by the adsorbing protein
or merely tolerate modest protein adsorption. This work provides design rules for copolymer coatings in biomaterial
applications.
186. Optimization of pMHC/antibody microarrays for T cell binding and cytokine detection
Chaofang Yue1 , Megan Balog 2 , Michael Paulaitis 1 , Jonathan Schneck3 and David Vanderah 4 , (1)Ohio State
University, Columbus, OH, (2)Ohio State University, columbus, OH, (3)Johns Hopkins School of Medicine, Baltimore,
MD, (4)National Institute of Standards and Technology, Gaithersburg, MD
For peptide-major histocompatibility complex (pMHC)/antibody microarrays to be a quantitative and reliable assays for
the simultaneous capture of T cells and detection of secreted cytokines, multiple variables related to the surface
architecture and the printing process need to be optimized. We compared two different types of slide substrates: one
fabricated using novel surface patterning techniques to form gold/SAM (self-assembly monolayer) layers, and the other
a commercially available hydrogel layer. Using neutron scattering, we characterized the multi-component, multi-layer
structure of gold slide. For both surfaces, we investigated the effects of various additives on spot morphology and
intensity.
T cell crossreactivity is a fact that we must take into consideration when we use microarray to characterize a T cell
population. We propose a mathematical model to describe T cell crossreactivity as it occurs on microarray, which is
different from that in vivo.
187. POLY(DEAEMA-co-PEGMA): A NEW pH-RESPONSIVE COMB COPOLYMER

SURFACTANT FOR DISPERSIONS AND EMULSIONS
Brian R. Saunders and Sheikh Shahalom, The University of Manchester, Manchester, United Kingdom
Stimulus responsive copolymers are an important class of surfactants that are attracting growing attention in the
literature. When used to stabilise colloids they confer responsiveness to an otherwise non-responsive system. This
provides added versatility to the dispersions and enables new possibilities for application. Triggered release of actives
within paint films is an area in which this behaviour is particularly sort. We sought to design a copolymer surfactant that
would show a major conformational change within the pH range which is applicable to surface coatings. The pH of a
paint dispersion is usually about 8, whereas that of the corresponding film is about 5. In this work a pH-responsive
comb copolymer surfactant is introduced that has a pKa of about 6.5. The copolymer is poly(DEAEMa-co-PEGMa),
where DEAEMa and PEGMa are diethylaminoethyl methacrylate and poly(ethylene glycol) methacrylate. The copolymer
enables preparation of fine particulate dispersions and emulsions. The dispersions used are based on carbendazim,
which is a common fungacide used in paints. The oil-in-water emulsions discussed contain tetradecane. The
dispersions and emulsions remain as fluids above the pKa with evidence of flocculation. Interestingly, the emulsions
completely phase separate when the pH is decreased to low values, releasing the oil phase. The mechanism for the

pH-triggered behaviour and the implications for polymer colloid applications are discussed.
188. Morphology controls of self-assembled nanoparticles by the secondary structures of

poly(amino acid)s
Go Un Han, Jae Hyun Jeong, Hyun Jin Lee and Jong-Duk Kim*, Korea Advanced Institute of Sciences and
Technology, Daejeon, South Korea
Poly(2-hydroxyethyl aspartamide) (PHEA) containing amine group in the side chain (PHEA-NH2) was prepared by
aminolysis of poly(succinimide) (PSI) with 2-aminoethanol and 1,6-hexanediamine. PHEA-g-oligo(L-lysine) was
successfully synthesized by living polymerization of á-amino acid-N-carboxyanhydrides (NCA) of L-lysine using PHEA-
NH2 as a macroinitiator. Self-assembled nanoparticles of PHEA-g-oligo(L-lysine) in an aqueous solution was
fabricated. The morphology changes of self-assembled nanoparticles were induced by the pH- or temperature-
responsive conformational transition of specific poly(amino acid) group, which is grafted oligo(L-lysine) segment. The
conformational transition of secondary structure, the change between á-helix and â-sheet, of oligo(L-lysine) was
confirmed by CD (circular dichroism). The morphology of self-assembled nanoparticles is studied by TEM and DLS. The
surface plasmon resonance (SPR) biosensor has been widely used to investigate binding event occurring on biological
surfaces by the detection of a refractive index change on a gold surface without the need to label molecules. We also
verify physicochemical properties of conformational transition of poly(amino acid) through the SPR study.
189. Surface Enhanced Raman Scattering of Energetic chemicals on colloidal nanoparticles

of Ag/TiO2
Edwin De La Cruz Montoya, universidad de puerto rico mayaguez, mayaguez, PR
Silver nanoparticles coated with titanium dioxide was synthesized via simple route, where, the reduction of Ag+ to Ag0
and the controlled polymerization of TiO2 on the surface of silver crystallites take place simultaneously. The prepared
nanoparticles were characterized by UV-visible absorption and by Energy dispersive X-ray spectroscopy-EDAX. The
spectrum of the suspension of Ag nanoparticles had a surface plasmon of 420 nm arising from the particles, in which is
characteristic of Ag colloidal dispersion. Similar surface plasmon absorption due to Ag nanoparticles was observed for
the suspension of titania-coated Ag nanoparticles at longer wavelength than for the suspension of Ag nanoparticles.
This absorption shift is caused by refractive index of titania and suggests coverage of Ag nanoparticles with titania.
Ag/TiO2 colloids were used to measure FT-Raman spectra by capillary tube method in different excitation sources to
observe the enhancement of the Raman signatures of solution of TNT to different pH. The pH 10.30 showed an
increase of the NO2 stretching mode at the 1365cm-1 in comparison with the other pH and the solution without
colloids. Additionally the band 1213 cm-1 and NO2 band are shifted to higher wavenumbers.
Keywords: TNT, colloids, Titania.
190. Sticky mixture models of phase separation of eye lens gamma and alpha crystallin
proteins
Maurino Bautista, Hossein Shahmohamad, David S. Ross and George M. Thurston, Rochester Institute of Technology,
Rochester, NY
We apply an extension of the Baxter sticky-sphere model to mixtures of highly concentrated aqueous solutions of the
bovine eye lens proteins gamma-B crystallin and alpha crystallin, which show enhanced phase separation[1] likely due
in part to their effective radius ratio of close to 4.5. Gamma-B crystallin is smaller and is modeled with a temperature-
dependent stickiness parameter that reproduces static light scattering near its upper consolute point[2], and small-angle
neutron scattering at scattering vector magnitudes below 2 inverse nanometers[3]. Alpha crystallin is modeled as a
larger, hard sphere, consistent with its scattering properties. With these choices together with hard-sphere gamma-B-
alpha crystallin interactions, the Barboy-Tenne mixture extension of the Baxter model[4] predicts considerably higher
phase separation temperatures than are observed. This is consistent with recent findings from molecular dynamics
simulations applied to model small-angle neutron scattering data, that hard-sphere gamma-B-alpha interactions would
lead to mixture instability[5]. We examine the consequences of alternative gammaB-alpha interactions for phase
separation and scattering.

[1] Thurston GM, J. Chem. Phys., 124, 134909 (2006) [2] Fine B.M., Lomakin A, Ogun OO, et al. J. Chem. Phys.,
104(1):326-335 (1996) [3] Stradner A, Thurston GM, and Schurtenberger P, J. Phys. Cond. Matt. 17:1-12 (2005) [4]
Barboy B and Tenne R, Chem. Phys. 38(3):369-387 (1979) [5] Stradner A, Foffi G, Dorsaz N, et al, to be submitted.
191. Characterization of metal-based nanofluids generated via laser ablation
Daniel M. Kuntz 1 , Lynn M. Walker 1 , Lee R. White 1 , Rakesh K. Gupta 2 , Yee Soong 3 and Phuoc X. Tran3 , (1)Carnegie
Mellon University, Pittsburgh, PA, (2)West Virginia University, Morgantown, WV, (3)U.S. Department of Energy National
Energy Technology Laboratory, Pittsburgh, PA
Metal nanoparticulate materials generated via laser ablation in solution have been characterized using a variety of
techniques (DLS, UV, TEM, electrophoretic mobility measurements) to determine particle size, stability and surface
properties. Information is being used to optimize and improve the laser ablation technique. The laser ablation technique
produces silver-based nanofluids of reasonable stability and controllable particle dimensions. The use of other metals
(aluminum or brass) results in nanofluids that are not as stable the silver-based nanofluids. However, the ability to
adjust nanofluid stability in all three systems by varying pH has been demonstrated. Characterization is being used to
optimize the solution conditions for the laser ablation that will give rise to stable nanoparticle suspensions.
192. Synergy among Surfactants in Solution and on Particles in Suspensions

Shaohua Lu and Ponisseril Somasundaran, Columbia University, New York, NY
Surfactant mixtures are widely used in detergent, personal care, enhanced oil recovery and flotation applications.
Adsorption of nonionic/cationic/anionic (ex: n-dodecyl-â-D-maltoside(DM), and sodium dodecyl sulfonate) on solids
such as alumina was studied in this work at different solution conditions of pH, mixing ratio and salt contents along with
the wettability and zeta potential. Solution interactions were studied by analytical ultra centrifuge, surface tension, small
angle neutron scattering and cryoTEM. It was found that surfactant adsorption is dramatically affected under certain pH
conditions. The effects of pH, however, are reduced by synergistic interactions in the case of nonionic/anionic mixtures.
Surface tension results reveal a negative interaction parameter suggesting that there are synergistic interactions
between them. Importantly, only one peak indicative of one type of micelle was identified using analytical
ultracentrifugation in the case of the above anionic/nonionic mixtures, while two types of aggregates were observed in
the case nonionic/nonionic mixtures. The above information on surfactant aggregation helps to reveal the mechanisms
of interactions between surfactants as well as their efficient application in various industrial processes.
. Structure & dynamics of nanoparticle glasses

Xinhui Lu, Simon Mochrie, Suresh Narayanan, Alec Sandy and Michael Sprung, Yale University, New Haven, CT
Even after decades of study, understanding the glass transition remains a grand challenge for condensed matter
science. Especially interesting then are so-called mode coupling theory (MCT) predictions that there can exist two
distinct glass phases in systems with short-ranged attractive interactions. The present experiments were carried out to
explore this and related predictions. we report an x-ray photon correlation spectroscopy study of the re-entrant glass
transition of colloidal suspension. The system is a suspension of silica spheres of 3900 Angstrom diameter in the binary
fluid of water and 2,6- lutidine. By changing the temperature, the system is observed switching between two different
types of glass state.The transition exhibits a logarithmic dynamics as predicted.
. Solvent-reversible poration in ionic liquid copolymers

Feng Yan and John Texter, Eastern Michigan University, Ypsilanti, MI
Microemulsions comprising methyl methacrylate (MMA) and a polymerizable ionic liquid (IL)-based surfactant, 1-(2-
acryloyloxyundecyl)-3-methylimidazolium tetrafluoroborate (IL-BF4) water and cosurfactant,1-propanol, have been
polymerized via thermal initiation in microemulsions. The resulting polymer hydrogels can be transformed to porous
polymers by anion exchange of BF4¯ by PF6¯ in the IL moiety. The pore size of the polymer varies with crosslinker
content in the precursor microemulsions. The converted porous polymers can be transformed to solvogels by imbibing
solvents such as dimethyl sulfoxide (DMSO), dimethyl formamide (DMF) and alcohols. These polymer solvogels can be
reversibly transformed to porous polymers again by treatment with water. The basis for this reversible poration process

appears due to spinodal decomposition of the solvogel composition into the open cell nanoporous material, induced by
addition of a poor solvent (e.g., water) for the ionic liquid surfactant blocks of the copolymer.
193. Gelation versus liquid crystal phase transitions in suspensions of charged colloidal
platelets
H. N. W. Lekkerkerker, Utrecht University, Utrecht, Netherlands
The liquid crystal phase behaviour of suspensions of charged gibbsite (Al(OH)3) platelets is investigated. We study the
competition between sedimentation, gelation and liquid crystal formation at different initial concentrations and salt
strengths. By variation of the ionic strength we are able to tune the effective thickness-to-diameter ratio of the platelets
in suspension. This enabled us to experimentally test the liquid crystal phase transition scenario that was first predicted
a decade ago by computer simulations for hard platelets, that is the isotropic (I) nematic (N) and isotropic to columnar
(C) phase transitions in one colloidal suspension. In addition to the shape-dependent thermodynamic driving force, the
effect of gravity is important. For example a biphasic (I-N) suspension becomestriphasic (I-N-C) on prolonged standing.
This effect is described by a simple osmotic compression model. Finally we discuss the possibility to produce photonic
crystals from the iridescent columnar phases of Gibbsite nanoparticles.
194. pMHC microarrays for characterizing protein-protein interactions in diverse T cell

populations
Chaofang Yue 1 , Megan Balog 2 , Michael Paulaitis 1 and Jonathan Schneck3 , (1)Ohio State University, Columbus, OH,
(2)Ohio State University, columbus, OH, (3)Johns Hopkins School of Medicine, Baltimore, MD
High-throughput protein microarrays for screening protein-protein interactions have promising applications in
biotechnology, medical diagnostics, vaccine development, and the treatment of cancer, autoimmunity and infectious
diseases. We are using this technology to rapidly screen diverse populations of T cells to characterize human influenza-
specific immune responses. An important early molecular recognition event that triggers an immune response is the
interaction of a T cell receptor (TCR) on the surface of the T cell with its complementary major histocompatibility
complex (MHC) on the surface of antigen-presenting cells. This protein-protein interaction is mediated by a small
peptide (the antigen) 8-10 amino acids in length that is bound to the MHC, such that the amino acid sequence of the
peptide antigen determines the specificity of the TCR/peptide-MHC (pMHC) interaction. Individual T cells are also
characterized by a unique TCR; therefore, microarrays printed with the MHC containing peptides with different amino
acid sequences serves to distinguish T cells by their characteristic TCR/pMHC interactions. In addition, co-printing
antibodies against cytokines secreted by the captured T cells enables an antigen-specific functional analysis of T cell
activation across this population. We show that pMHC microarrays can selectively capture and enumerate antigen-
specific T cells in diverse populations at high sensitivity, and that this information provides insights into the general
principles governing early molecular recognition events in human immune responses. Results on the functional diversity
of the human immune response will also be presented.
195. Role of solubility enhancers in the study of crystallization conditions for improving
crystal hits
Rajendrakumar A. Gosavi, Sasidhar Varanasi, Constance A. Schall and Timothy C. Mueser, University of Toledo,
Toledo, OH
Abstract: Biomolecular crystallography strives to explore the appropriate growth conditions leading to diffraction quality
crystals for structure determination. Various commercially available crystal screens are often used to search for
optimum crystallization conditions. These screens consist of combinations of buffers, salts, precipitant and additives
resulting in a large number of possible combinations of crystallization conditions. Increasing the solubility of the protein
in its buffer to an optimum level favors crystallization over precipitation. A recent study determined that using solution
conditions which enhanced protein solubility lead to better quality crystals in most cases examined. An enhancement in
the solubility lowers the attractive forces between the protein molecules and crystal-liquid interfacial tension. This lowers
the energetic barrier to nucleation of protein crystals as determined through nucleation kinetic data. Excessive
enhancement in the solubility may lead to the near elimination of the barrier thus leading to precipitation. This work
focuses on analyzing the effect of various solubility enhancers on the crystallization of selected proteins. The use of

organic solvents such as ethanol, ethylene glycol, glycerol and 2-methyl-2,4-pentane diol as solubility enhancers for
selected proteins in their optimized buffer conditions is evaluated.
196. Charge and ionic strength dependence of phase separation and liquid structure of
solutions of the eye lens protein, gamma-B crystallin
George M. Thurston 1 , Kenneth Desmond2 , Dawn Carter 1 , Anna Stradner3 and Peter Schurtenberger 3 , (1)Rochester
Institute of Technology, Rochester, NY, (2)Emory University, Atlanta, GA, (3)University of Fribourg, Fribourg,
Switzerland
We are studying liquid structure, phase separation and cluster formation in aqueous solutions of the bovine eye lens
protein, gamma-B crystallin, as functions of charge and ionic strength. The role of charge in lens protein phase
separation is important for understanding cataract, since changes in lens protein charge, known to occur during aging,
are expected to affect solution stability. At 0.24M ionic strength, decreasing pH from 7.1 to 5.5 and thereby increasing
net protein charge from +2 to +6 lowers the gamma-B upper consolute temperature by 8 degrees C. Further increasing
gamma-B charge to +9 at pH 4.5 changes effective gamma-B interactions from attractive to repulsive at accessible
temperatures, as observed by small-angle neutron scattering, and no phase separation is observed. Lowering ionic
strength at pH 4.5 further increases repulsive interactions. Low-angle neutron scattering from gamma-B crystallin near
phase separation is well-fit by the Baxter sticky-sphere model, but larger-angle scattering may reflect anisotropy of
protein features and interactions. We compare small-angle scattering results for gamma-B crystallin at low ionic
strength to evidence for lysozyme cluster formation under analogous solution conditions.
197. Hydration of proteins and weak protein-protein interactions
Dilip Asthagiri 1 , Amit Paliwal 2 , Abraham Lenhoff 3 , M. Hamsa Priya4 and Michael Paulaitis 4 , (1)Johns Hopkins
University, Baltimore, MD, (2)Johns Hopkins University, (3)University of Delaware, Newark, DE, (4)The Ohio State
University, Columbus, OH
The structure and solution thermodynamic property of a protein is intimately tied to the structure of water around it, and
an extant goal of experiments, theory, and simulation is to understand this inter-relation between the solvent water and
the solute protein. We pursue this question by modeling the hydration contribution to the osmotic second virial
coefficient, B2 , of protein solutions. We adopt a quasi-chemical description in which a protein with the water molecules
associated with it is treated as a distinct solution component. These associated water molecules are identified through
molecular dynamics simulations. We examine this quasi-chemical view of hydration by predicting B2 and compare our
results with those derived from light-scattering measurements of B2 for staphylococcal nuclease, lysozyme, and
chymotrypsinogen at 25°C as a function of solution pH and ionic strength. We find that short-range protein interactions
are influenced by water molecules strongly associated with a relatively small fraction of the protein surface. We find that
these water molecules reduce the surface complementarity of highly favorable short-range interactions, and therefore
play an important role in mediating protein-protein interactions. Thus specific hydration effects need to be taken into
account for an accurate description of B2 . We also observe remarkably similar hydration behavior for these small
globular proteins despite substantial differences in their three-dimensional structures and spatial charge distributions,
suggesting a general characterization of hydration for such globular proteins.
198. Biomolecules in water: From hydrophobic to hydrophilic hydration and interactions

Shekhar Garde, Rensselaer Polytechnic Institute, Troy, NY
Water structure and dynamics play an important in protein structure, dynamics, and function. Water packing,
orientations, and dynamics in the vicinity of proteins are affected by protein surface roughness as well as the chemically
heterogeneous nature of protein surface, which ranges from hydrophilic to hydrophobic in character. We use molecular
dynamics simulations of model solutes with varying sizes and charge densities to understand how they affect the vicinal
water structure and dynamics. Water-mediated interactions between solutes of varying charge densities yields (for the
first time) "molecular volcano" relationships observed in experimental data on salt pairs in solution. We make
connections of fundamental understanding of charge-density-dependent hydration obtained for model solutes with
hydration of proteins through complementary simulations of several proteins in explicit water. Together, these studies
are beginning to provide molecular level insights into protein-X interactions (where X = ligands, chromatographic

displacers, and interfaces).
199. Proteins as model colloids: enhanced stability of eye lens protein mixtures through
mutual attraction
Giuseppe Foffi 1 , Anna Stradner2 , Nicolas Dorsaz 1 , George M. Thurston 3 and Peter Schurtenberger 2 , (1)Ecole
Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland, (2)University of Fribourg, Fribourg, Switzerland,
(3)Rochester Institute of Technology, Rochester, NY
Understanding interparticle interactions in protein solutions is of central importance to gain insight into the origin of
protein condensation diseases. While the study of such condensation diseases has traditionally focussed on a
molecular view point based on specific, detailed properties of the molecules involved, considerable progress has also
been made using statistical and colloid physics, in which the formation of condensed protein phases can be
quantitatively analyzed in terms of a subtle interplay between interprotein attractions, repulsions, and entropy. The
analogy between colloids and proteins has not only been driven by biological and biomedical research. Globular
proteins have also drawn great attention in the colloid physics community due to their suitability as model colloids. Here
we demonstrate the importance of this approach for the lens crystallin proteins, which are vital for eye lens
transparency and for understanding cataract, a clouding of the eye lens due to increased light scattering. By combining
small-angle neutron scattering (SANS) experiments and molecular dynamics (MD) computer simulations, we
demonstrate that transparency of lens crystallin protein mixtures at high concentrations, comparable to those in the
living eye lens, is greatly enhanced by weak, short-range attractions between two of the prevalent mammalian
crystallins, alpha- and gamma-crystallin. Provided they are not too strong, such mutual attractions considerably
decrease the critical temperature and corresponding opacity due to light scattering, and are thus essential for lens
transparency.
200. Brownian and colloidal interactions in protein crystal growth

Jack Lum, Johns Hopkins University, Laurel, MD
Brownian dynamic simulations are used to elucidate some of the underlying transport processes of protein molecules in
protein crystallization. The dominant forces are modeled from colloidal interactions between a lysozyme molecule
(sphere) and tetragonal lysozyme crystal (wall), both heterogeneously charged. The electrostatic portion is obtained by
solving the linearized Poisson-Boltzmann equation with a boundary elements method; the van der Waals force is
treated as a function of only the Hamaker constant and sphere-wall separation. Simulation results show that protein
molecules have greater translational diffusivity and are more concentrated near a highly charged crystal surface than
near a weakly charged one. This suggests that ordered protein assembly as a precursor to crystal growth is more likely
to occur at the crystal surface than in bulk solution.
201. Keynote: Surface chemistry of carbon on Ni and Ni-alloys: carbon-tolerant

hydrocarbon reforming catalysts from molecular insights
Suljo Linic and Eranda Nikolla, University of Michigan, Ann Arbor, MI
Reforming of hydrocarbon fuels is one of the most important heterogeneous catalytic processes. Particularly appealing
is potential development of catalysts that could be used as direct, reforming anodes in solid oxide fuel cells (SOFCs).
Current reforming catalysts such as Ni, however, suffer from two major problems: (i) carbon-induced deactivation and
(ii) sulfur poisoning of the catalyst. We have utilized Density Functional Theory (DFT) calculations to study the surface
chemistry of carbon atoms and carbon fragments on Ni. These studies demonstrated that there is a strong
thermodynamic driving force to form sp2-bonded carbon networks. These extended carbon networks diminish the
reforming activity of Ni. We have further utilized DFT to search for Ni-containing alloys that are more carbon-tolerant
than monometallic Ni, i.e., that have a lower propensity to form the carbon networks. These studies have yielded a few
promising alloy formulations. Subsequent steady-state reactor studies validated the predictions of the DFT calculations.
Aside from the steady-state reactor tests, the catalysts were characterized with multiple spectroscopic and microscopic
tools.
1. E.Nikolla, A. Holewinski, J. Schwank, S. Linic; “Controlling Carbon Surface Chemistry by Alloying: Carbon Tolerant
Reforming Catalyst”, Journal of the American Chemical Society, 2006; 128(35); 11354-11355.

202. Stability of Subsurface 3d Metals in Bimetallic Cathode Electrocatalysts

Carl Andrew Menning and Jingguang G Chen, University of Delaware, Newark, DE
For the cathode of a proton exchange membrane fuel cell (PEMFC), the current leading industrial electrocatalyst is
pure platinum for the oxygen reduction reaction (ORR). The ORR reduces a stream of gaseous oxygen over an
electrocatalyst to form water and complete the electrical circuit. Even though platinum has been found to have the
highest activity for the ORR for pure catalysts, this activity is orders of magnitude lower than that found for other
general electrode reactions such as the hydrogen oxidation reaction (HOR). It has been shown previously in literature
that the activity can be increased if the 2nd layer of a platinum surface is replaced with a 3d transition metal giving a
subsurface bimetallic catalyst. In the current study, we attempt to quantify the stability of the Pt-3d-Pt(111) subsurface
electrocatalysts under an oxygen environment. Experiments were performed for the Pt-Ni and Pt-Co bimetallic systems
using ultra-high vacuum (UHV) techniques. The segregation of Ni and Co was verified using high-resolution electron
energy loss (HREELS). The activation barrier for the segregation of the 3d transition metal to the surface was
determined using Auger electron spectroscopy (AES). The remaining Pt-3d bimetallic systems were compared using
predicted thermodynamic stability calculated using density functional theory (DFT). Kinetically, the Pt-Ni subsurface
configuration was determined to be more stable than the Pt-Co subsurface configuration when exposed to oxygen.
Thermodynamically, the Pt-Ni subsurface configuration has been predicted to be the most stable of the Pt-3d
subsurface configurations when exposed to oxygen.
203. Unsupported Ir catalysts to probe for structural and size effects in surface chemistry
Wenhua Chen 1 , Timo Jacob2 and Theodore E. Madey 1 , (1)Rutgers, The State University of New Jersey, Piscataway,
NJ, (2)Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin-Dahlem, Germany
Clean planar Ir(210) and clean nano-faceted Ir(210) with tunable sizes have been prepared from the same crystal in
situ, which allows us to investigate structure sensitivity and size effects in surface chemistry on unsupported iridium
without switching from sample to sample. A series of chemical reactions have been carried out on clean planar and
clean faceted Ir(210) using temperature programmed desorption (TPD) measurements. We have found clear evidence
for structure sensitivity in decomposition of acetylene, nitric oxide, ammonia and hydrogen, and for oxidation of CO on
planar Ir(210) versus faceted Ir(210). Our measurements of CO oxidation over planar and faceted Ir(210) are supported
by our DFT calculations of the energetics of adsorption and diffusion of oxygen; the results suggest that surface
diffusion may play a role in controlling CO oxidation over Ir. In addition, ammonia decomposition on faceted Ir(210)
exhibits size effects on the nanometer scale, which is the first observation of size effects in surface chemistry on
unsupported monometallic catalyst with well defined structure and controlled size.
204. A unified modeling framework for design of multi-site catalysts: application to NH3
decomposition for H2 production
Vinay Prasad, Altaf Karim, Niket Kaisare, Danielle Hansgen and Dionisios G. Vlachos, University of Delaware, Newark,
DE
Challenges in using ammonia decomposition for hydrogen production include increasing catalyst activity and developing
cheaper catalysts. While Ru is the best single metal catalyst, multi-site catalysts, including bimetallics, offer possible
improvements. We aim to develop a unified modeling framework for understanding and designing multi-site catalysts to
meet these challenges.
Microkinetic models typically assume a homogeneous catalyst surface. A catalyst consists of various crystallographic
planes, steps and defects, and multiple chemical components (different metal islands), which form multiple, interacting
sites. The kinetics on different sites and their interactions must be captured in predictive models for these spatially
distributed situations. These interactions ‘couple' microkinetic models; we show that coupling is subject to
thermodynamic constraints, and we develop appropriate multi-site models to compute reaction rates. The applicability of
such mean-field models is assessed via kinetic Monte Carlo simulations.
We show an example for ammonia decomposition on a bimetallic catalyst containing Pt and Ru, which have the same
rate-determining step and fall on the same side of the “volcano curve”. Fig.1 shows ammonia conversion as a function

of Ru fraction. Both non-interacting and weakly interacting (adsorbed species can diffuse to and react on the other
catalyst surface) cases are shown. Pure Ru is the best catalyst, as expected for this situation. This approach is being
extended to a library of catalysts and best bimetallic catalysts will be discussed. The effect of steps will also be
illustrated to underscore their relative importance.
205. Reactions of Complex Epoxides on Silver Surfaces

Adrienne C. Lukaski and Mark A. Barteau, University of Delaware, Newark, DE
Direct oxidation processes, such as ethylene epoxidation to ethylene oxide, have been researched extensively due to
their commercial significance. Despite the importance of epoxide production, the mechanistic details of olefin
epoxidation remained obscure until recently and the majority of significant advances in Ag-catalyst development
occurred primarily through empirical methods. Recent surface science studies of ethylene oxide and 1-epoxy-3-butene
have identified an oxametallacycle species as the active intermediate in Ag-catalyzed epoxidation of both ethylene and
1,3-butadiene; expansion of the epoxide ring to incorporate surface silver atoms forms the oxametallacycle species.
Oxametallacycles have been isolated by ring-opening ethylene oxide, 1-epoxy-3-butene, and styrene oxide on Ag(111)
and 1-epoxy-3-butene on Ag(110). Surface science techniques and density functional theory were used in this study to
investigate the interactions of styrene oxide and isoprene oxide with Ag-surfaces. In agreement with previous studies of
olefins on Ag(110) and Ag(111), these complex epoxides undergo activated ring-opening to form stable surface species
on silver; these intermediates reform their parent epoxides during subsequent temperature-programmed desorption.
Because the molecular forms of both styrene oxide and isoprene oxide desorb molecularly from silver below 250 K, the
intermediate species derived from the these epoxides are most likely surface oxametallacycles. Preliminary density
functional theory calculations predict that cleavage of the epoxide ring occurs at the carbon bearing the substituent
group to form surface oxametallacycle intermediates.
206. Spatio-temporal Forcing of a non-linear Surface Reaction - Oxidation of CO on Pt(100)

Danny Bilbao and Jochen Lauterbach, University of Delaware, Newark, DE
The oxidation of CO on Pt(100) exhibits complex non-linear behavior, such as reaction rate oscillations and spatio-
temporal adsorbate patterning. The current focus of our work is to investigate the dynamics of this system when it is
subjected to external forcing. Using gas microdosing to locally introduce reactants onto the catalytic surface and EMSI
(Ellipsomicroscopy for Surface Imaging) to image changes in adsorbate activity, unique behavior has been observed for
systems at pressures of 1x10 -4 Torr.
The local dosing of several gasses (e.g., CO, O 2 , NH3 , etc.) onto the catalytic surface modifies the surface in such a
way as to lead to the formation of a ring shaped pattern generated by preferential adsorption of CO. An investigation of
this ring formation concluded that the appearance of the ring depends on the surface temperature at the time of
microdosing as well as the time elapsed between dosing and the introduction of CO into the reactor.
External forcing was used to drive small areas of the surface residing in a monostable, CO covered state into an
oscillatory state. Initial Reaction conditions were adjusted to produce a CO covered surface, lying close to the point at
which the surface would become O saturated. Oxygen was then microdosed onto the surface creating an adsorbed O
island that was eventually reacted away to leave the surface covered again with only CO. Decrease of the global CO
pressure lead to the onset of oscillations, which were spatially restricted to the previously dosed regions.
207. Mechanism of Assembly of Short, Highly Ordered, Single-Walled Mixed-Oxide

Nanotubes

Sankar Nair, Sanjoy Mukherjee, Keesuk Kim and Suchitra Konduri, Georgia Institute of Technology, Atlanta, GA
Nanotubes are important ‘building block' materials for nanotechnology, but a synthesis process for short (sub-100-nm)
nanotubes with structural order and monodisperse diameter has remained elusive. To achieve this goal, it is critical to
possess a definitive mechanistic framework for control over nanotube dimensions and structure at very small length
scales.
While no general strategy has thus far been proposed, we are interested in a unique model system that offers
mechanistic insights into the assembly of nanotubular objects that could lead to a more general synthesis process. We
have employed solution-phase and solid-state characterization tools to elucidate the mechanism governing the
formation of short (20 nm), ordered, monodisperse (3.3 nm diameter), aluminum-germanium-
hydroxide(‘aluminogermanate') nanotubes in aqueous solution. We show - via mechanistic synthesis experiments,
dynamic light scattering, UV-Vis/Raman/IR spectroscopy, microscopy, and diffraction techniques - that the central
phenomena underlying this mechanism are: (1) the generation (via pH control) of a precursor solution containing
aluminate and germanate precursors chemically bonded to each other, (2) the formation of amorphous nanoscale (~ 6
nm) condensates via temperature control, and (3) the self-assembly of short nanotubes from the amorphous nanoscale
condensates.
Simultaneously, atomistic simulations reveal that the formation of ordered monodisperse nanotubes is strongly related to
the existence of unique energy minima in the nanotube structure as a function of diameter. This provides an additional
handle for directing the assembly of metal oxide nanomaterials towards energetically favorable structures. Our
mechanism provides a model for controlled low-temperature assembly of small, monodisperse, ordered nanotube
objects.
208. NOM Induced Dispersion and Disaggregation of n-C60 Aggregates in Water

Bin Xie, Zhihua Xu, Wenhua Guo and Qilin Li, Rice University, Houston, TX
C60 fullerene and its derivatives have been used in a number of consumer products and their potential applications in
biomedical and environmental engineering are being actively pursued. Existing toxicity data indicate that industrial-scale
production of C60 fullerene poses a potential threat to the environment. Understanding the fate and transport of C60 in
the environment is necessary to evaluate its environmental impact. Although natural organic matter (NOM) is known to
stabilize colloids, its influence on C60 behavior in aqueous phase has not been studied. Our study aims to determine
the effect of aquatic NOM on the formation and physicochemical properties of aqueous C60 suspension, also referred to
as n-C60 due to the aggregate nature of the particles formed. The effects of two major NOM components, humic acid
(HA) and fulvic acid (FA), were investigated using n-C60 samples prepared by two methods: emulsification of C60
solution in toluene with water followed by sonicating volatilization of toluene, and directly mixing C60 dry powder with
water. Dynamic light scattering (DLS), atomic force microscopy (AFM), and transmission electron microscopy (TEM)
were employed to analyze particle size and morphology. Particle surface zeta potential was determined by
electrophoretic mobility measurement using phase analysis light scattering. NOM was found to induce disaggregation of
preformed n-C60 particles. Moreover, directly mixing C60 dry powder with water containing NOM formed stable n-C60
suspensions with particle sizes of 2-4 nm. These results indicate that NOM may play a critical role in transport and
toxicity of C60.
209. Molecular modeling of the interactions of sarcosine and AMPA with montmorillonite
Lorena Tribe, Amanda J. Rennig and Annette K. Slutter, Penn State Berks, Reading, PA
The interactions of glyphosate molecules with montmorillonite clay have been studied with theoretical methods, ranging
from molecular mechanics to ab initio quantum mechanical calculations to explore the ways in which this herbicide may
bind to the interlayer surfaces of the mineral in natural soils. Free glyphosate is moderately biodegradable, due mostly
to soil microorganisms. Two pathways have been reported for its degradation in soils, one using the intermediate
aminomethylphosphonic acid (alpha-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid, AMPA) and the other using
the intermediate sarcosine. In this work we extend the previous theoretical study of glyphosate adsorption on
montmorillonite surfaces to sarcosine and AMPA. The environment of the glyphosate, sarcosine and AMPA molecules
in the present calculations is the interlayer of the clay and the surrounding water molecules and cations, with a rough
energy landscape. The search for the global minima is not stressed in these conditions but rather a reasonable

structure for the molecules in solution determine is determined. A molecular modeling calculation was performed where
the molecules were placed in the montmorillonite interlayer and were allowed to move freely, without constraints. The
goal of these calculations was to establish if one of the three functional groups (COOH, NH2+ or PO3OH) is
consistently closer to the montmorillonite in the final state. The final distances between atoms of these moieties and
atoms of the surface are reported here for several trials with random initial configurations.
210. Nanostructural analysis of poly(N-isopropylacrylamide) grafted on solid surface in

aqueous solutions
Naoyuki Ishida, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Japan and Simon
Biggs, University of Leeds, Leeds, United Kingdom
It is well known that poly(N-isopropylacrylamide) (PNIPAM), PNIPAM chains show a phase transition from a coil to
globule state at a lower critical solution temperature (LCST). A similar response is expected for surface grafted PNIPAM
and such layers may have a number of interesting applications including drug delivery, permeation-controlled filters and
controlled/sustained release. In order to control the structure of such layers effectively, it is important to investigate in
detail the structural behaviour of immobilized PNIPAM chains responding to stimuli from external environment. In this
study, structural changes of PNIPAM chains immobilized on solid surfaces were investigated in aqueous solutions with
an atomic force microscope (AFM) and a quartz crystal microbalance with dissipation (QCM-D). By AFM imaging, the
transition of the grafted PNIPAM chains from brush to mushroom state was clearly visualized; the surface images of the
plate were featureless at temperatures below the LCST, whereas a large number of hemi-spherical structures whose
size was order of 100nm were found on the surface above the LCST. Both frequency and dissipation signals obtained
using QCM-D showed significant change at around LCST, indicating that PNIPAM underwent a collapse by the
dehydration of the chains. A complementary investigation indicated that a similar transition could be observed in
solutions of high concentration electrolytes. It was also found that the grafting density of the PNIPAM chains
significantly affected significantly the sharpness of the phase transition behaviour of them responding to change in
environmental conditions.
211. Uniform Mechanically oscillating PNIPAM Particles with Covalently Bound Ruthenium
BZ Catalyst
Zhengdong Cheng 1 , Srinivasa Pullela 1 , Jingyi Shen 1 and Manuel Marquez 2 , (1)Texas A&M University, College
Station, TX, (2)Phillip Morris USA, Richmond, VA
Uniform PNIPAM gel particles with covalently bound tris(bipyridyl)ruthenium(II) were synthesized via coordination
chemistry between a ruthenium complex and a monodispersed poly(N-isopropylacrylamide) (PNIPAM) gel bearing
bipyridine ligand. UV-Vis spectroscopy, X-ray photoelectron spectroscopy (XPS) and confocal microscopy were
employed for the characterization of the gel particles. Loading of the tris(bipyridyl)ruthenium(II) complexes and the
uniformity of the particle size were confirmed. The Mechanical oscillation of these particles was measured in a range of
the BZ reactants' concentrations. Temperature change of the oscillation frequency and oscillation induction time
revealed activation energy of the nonlinear chemical reactions and the role of the polymeric network. These particles
have potential application in the study of the Belousov-Zhabotinsky (BZ) reaction facilitated annealing of colloidal
crystals.
212. Protein-stabilized colloidal particles

Maurice Mehagnoul, Peter Versluis, Johan Hazekamp, Eli Roijers, Ruud den Adel, Gert-Jan Goudappel and Krassimir
Velikov, Unilever Food & Health Research Institute, Vlaardingen, Netherlands
Colloidal particles find many applications in the formulation of paints, agricultural and home & personal care products, in
drug delivery, foods, and as a precursor for advanced nanostructured materials. Preparation and stabilisation of colloidal
particles in complex systems is a challenging task. To increase the stability of colloidal particles very often surface
active molecules are used to absorb on the particle surface. As being surface active, proteins are another large class of
molecules that can provide stabilisation effect in colloidal dispersions. Here we present results on the wet chemistry
synthesis and characterisation of colloidal particles from sparingly soluble minerals in the presence of proteins.
213. Preparation of Melamine-Formaldehyde-Polyvinylpyrrolidone (MFP) novel resins, their

structural with IR-NMR and Friccohesive characterizations with Survismeter, and their
Hydrodynamics
Man Singh and Vinod Kumar, Chemistry research lab., Deshabndhu college, university of delhi, new delhi, india, new
delhi, India
Cutting edge nanotechnological based material sciences have revolutionized the focus of research in all forefronts of
physicochemical and medicochemical and electronic industries. Frontier of science and technology are tens for evolving
ecofriendly, green chemistry and micro scale the devices for applications of them and a competition is being generated
for cutting edge research in materials. In continuation of such efforts novel polymer resins of melamine-formaldehyde-
polyvinylpyrrolidone (MFP) in 0.5:16:1 (R1), 1:16:1 (R2) and 0.5:10:1(R3) ratios have been prepared with condensation
polymerization. Their average viscosity molecular weights (`Mv) determined with Mark-Houwink and Friccohesity, a
state of frictional-cohesive-adhesive forces with Man Singh equations, respectively. The viscous flow time (t) and drop
count (n) data for Man Singh equation were obtained with Survismeter respectively. Structural determinations were
made with IR and H1 NMR where specific proton singlet at ä 4.5 ppm, duplet at ä 3.13-3.17 and a quartet at ä 1.5-2.2
ppm infer the positions of protons of methylen (-CH2 -) bridging groups, pyrrolidone and polyvinyl constituents of the
resins. The 3389.25, 1290.38 and 1655.28 cm-1 stretching frequencies of –O----H-CH-, -C-O and –C=N- groups
respectively infer its preparation. The`Mv of R1, R2 and R3 resins are 11,995, 12,250 and 11,709 g mol-1, structural
and physicochemical behavior is studied with survismeter to for adhesive properties. The viscosities and surface tension
will be elaborated at deliverance of the lecture.
214. Keynote: Colloid Retention in Porous Media at Different Scales: Processes and Models
Scott A. Bradford1 , Saeed Torkzaban 2 , Sharon L. Walker 2 and Jirka Simunek 2 , (1)USDA-ARS, Salinity Laboratory,
Riverside, CA, (2)University of California, Riverside, CA
An understanding and ability to predict the transport and deposition of colloids in porous media requires knowledge of
processes and interactions that occur at different spatial and temporal scales. The flow field can be solved and mass
transfer processes can be quantified at the collector-scale. Here the potential for colloid attachment in the presence of
hydrodynamic forces is determined from a balance of applied (hydrodynamics) and resisting (DLVO) torques. Processes
of colloid mass transfer and retention can also be calculated at the pore-scale (ensemble of collectors). Differences in
collector- and pore-scale studies occur as a result of the presence of small pore spaces that are associated with
multiple interfaces and zones of relative flow stagnation. Illustrative examples of colloid retention processes in the
smallest regions of the pore space (straining locations) will be presented from micromodel studies and pore-scale
colloid transport simulations. Colloid deposition behaviour at the column-scale has frequently been reported to be non-
exponential with distance under unfavourable attachment conditions. Profile shape has been demonstrated to be
strongly dependent on the colloid size, pore structure, colloid concentration, hydrodynamics, and solution chemistry. To
adequately simulate non-exponential deposition profiles, processes related to variability of the pore structure and flow
field, surface charge heterogeneity of colloids and porous media, and/or colloid-colloid interactions need to be
considered. Various deterministic and stochastic modeling approaches to quantify non-exponential deposition profiles
and to test hypothesis with regard to colloid retention will be summarized.
215. Colloid-colloid Interactions Influence Deposition in Porous Media

Huilian Ma and William P. Johnson, University of Utah, Salt Lake City, UT
Colloid-colloid interactions are often neglected in the past studies of particle deposition in porous media. Apart from the
complexity involved in accounting for such interactions, this neglect may largely result from limitations of traditional
colloid transport theories, which predict no attachment under unfavorable situations (i.e., in the presence of an energy
barrier to deposition due to same-charged surfaces). Recent advances in understanding the mechanisms of colloidal
retention in the presence of energy barrier provide a basis for inclusion of colloid-colloid interactions in predictions of
particle deposition. Here, simulations incorporating colloidal interactions into a Langragian particle trajectory model are
presented. Results show that despite their mutual electrostatic repulsion, colloid-colloid interactions can mitigate or
enhance retention in porous media depending on the fluid velocity and chemical conditions. The simulations reproduce
blocking and ripening phenomena observed in experiments performed in the presence of an energy barrier to
deposition.

216. Resolving the Coupled Effects of Hydrodynamic and DLVO Forces on Colloid Retention
in Porous Media
Saeed Torkzaban 1 , Scott A. Bradford2 and Sharon Walker 1 , (1)University of California, Riverside, Riverside, CA,
(2)USDA-ARS George E. Brown, Jr. Salinity Laboratory, Riverside, CA
Transport of colloidal particles is governed by the rate at which the colloids strike and stick to collector surfaces.
Filtration theory has classically neglected the influence of hydrodynamic forces and pore structure in the calculation of
collision efficiency, as well as non-idealities associated with natural porous media such as non-spherical collectors and
rough surfaces. Computational simulations will be presented that consider the influence of hydrodynamic and DLVO
forces on colloid attachment to variously shaped collectors, and colloid retention processes that occur in small pore
spaces formed by multiple collectors and rough surfaces. Our analysis indicates that hydrodynamic forces, collector
shape, and pore structure significantly influences the colloid collision efficiency. Colloid attachment is only possible in
regions of the pore space where the torque from hydrodynamic shear that acts on colloids adjacent to collector surfaces
is less than the adhesive (DLVO) torque that resists detachment. The fraction of the collector surface area on which
attachment may occur increased with solution ionic strength and decreasing flow velocity. Our results also show that the
collision efficiency is sensitive to collector features such as roughness and shape, and to the pore space geometry.
Simulation findings demonstrate that quantitative evaluation of colloid transport through porous media will require
nontraditional approaches accounting for physical (hydrodynamics, surface roughness, collector shape, and pore
structure) and chemical (DLVO forces) conditions.
217. Numerical Investigation of Colloid Retention and Transport in Saturated Porous Media
Jie Han, Hui Gao, Lian-Ping Wang and Yan Jin, University of Delaware, Newark, DE
Migration of colloids in porous media has been mainly studied through laboratory column experiments and simulation of
the resulting breakthrough curves. In recent years, visualization experiments using micromodels are used as a new
approach for investigating mechanisms of colloidal retention in porous media at the pore-scale. However, parallel
developments in conceptual models and related numerical methods are lacking. In this study, a particle-tracking
framework was developed and solved numerically, which allows simulation of a 2-D flow field and colloidal retention
and transport in a dense cubic packed medium. To conduct a simulation, the program is first run to establish steady-
state flow that is driven by a pressure gradient before colloids are introduced. The model considers the Stokes drag
force, Brownian force, colloid-grain and colloid-colloid interaction forces (including electrostatic double layer, van der
Waals, and acid-base forces) on every colloid and predicts the moving trajectory and deposition in a defined domain.
The differential equation of Newton's Second Law of Motion is solved numerically with the Adams-Bashforth-Moulton
method. Effects of hydrodynamics, solution chemistry and surface properties of colloids are examined by changing flow
velocity, solution pH and ionic strength, and surface hydrophobicity of colloids. Model analysis and simulation exercises
indicate that this 2-D model is a very useful tool that can provide mechanistic insight for improved understanding of
colloidal retention and transport processes and how these processes are affected by the relevant parameters. This
model can also be used for guiding the design of and providing simulation to micromodel visualization experiments.
218. Straining of colloidal particles in intergranular gaps

Elena Rodriguez and Steven L. Bryant, The University of Texas at Austin, Austin, TX
A better understanding of the risk of water contamination from viruses, bacteria or contaminants adsorbed on colloids
can be achieved by modeling the retention of colloidal particles in soils. Colloids transported by fluid remain in the soil
when they arrive at constrictions in pore space too small to admit them. Pore throats have been typically considered
the place where colloids are trapped. However, numerous column experiments offer unequivocal evidence of straining
of colloids that are smaller than the smallest pore throat in the column.
We propose to explain this observation in terms of a geometric mechanism, independent of physicochemical factors.
Our hypothesis is that colloids can be trapped not just in throats between three grains, but also in gaps between pairs
of grains. The occurrence of appropriately sized gaps in model soils, represented by computer generated dense
random packs of mono-dispersed spheres, is large enough to trap a considerable number of colloids. A geometric
analysis of throats and gaps in the model soils was combined with a new methodology to compute flow rates in gaps.
The results were input to an existent straining theory to study the dependence of straining rate on colloid size. The

analysis suggests that straining in a gap cannot be treated correctly without reference to the throat associated with the
gap. A purely geometric argument gives a reasonably accurate prediction of the scaling of straining rate with particle
size. Refining this argument to account for flow distribution within a throat and associated gaps improves the prediction.
219. Colloid Retention in Porous Media: CFD Flow Field Modelling in Colloid Trajectory
Simulations in Porous Media with Particular Consideration of Grain to Grain Contact
Marcin M. Niewiadomski1 , Cynthia L. Rakowski2 , Marshall C. Richmond 2 and William P. Johnson 1 , (1)University of
Utah, Salt Lake City, UT, (2)Pacific Northwest National Laboratory (PNNL), Richland, WA
Colloid retention in porous media in the presence of an energy barrier to deposition is strongly influenced by wedging
within the grain to grain contacts and retention in flow stagnation zones. Development of accurate near-surface flow
fields for colloid transport simulation is challenging, especially in grain to grain contact zones due to the fine
discretization required. This paper presents generation of a volumetric 3-D mesh for computational fluid dynamics
(CFD) and simulation of the fluid flow field. Simulated colloid trajectories will be compared between the CFD-generated
flow field and semi-analytical solutions for the flow field. These simulations will also be compared to experimental
results for colloid retention in the presence of an energy barrier.
220. Dynamical arrest in clay suspensions - From Wigner glasses to viscoelastic phase
separation
Andrey Shalkevich, Anna Stradner, Suresh K. Bhat, Francois Muller and Peter Schurtenberger, University of Fribourg,
Fribourg, Switzerland
We have systematically investigated the phase diagram of clay particles in water in order to understand the relation
between the local and macroscopic properties and the structure of clay suspensions. We focused in particular on
sodium Cloisite (CNa) particles at concentrations from 1 wt% to 4 wt%, and at an extended range of ionic strengths (10-
5 to 10-2 M NaCl). The suspensions have been characterized using rheology and a combination of scattering
techniques (neutrons, x-rays, light). We were able to demonstrate the existence of a liquid cluster phase at low clay
and intermediate salt concentration, and obtained new insight into the nature of the solid-like dispersions at low and
high ionic strength. In particular we were able to unambiguously demonstrate the existence of an arrested phase at low
concentrations and ionic strength that corresponds to the Wigner glass predicted on theoretical grounds for such
systems.
221. Minimal Models for Understanding Protein Crystallization

Sanat K. Kumar and Hongjun Liu, Columbia University, New York, NY
The crystallization of proteins is a topic of great interest since the availability of macroscopically large crystals
represents almost the only means available to characterize native protein structures by scattering techniques. Two
decades of experiments have shown an extremely simple phenomenology describes this crystallization process:
proteins crystallize if their second virial coefficients fall in a very small band [“crystallization slot”]. Since such universal
behavior has been observed it appears reasonable that simple models, such as spheres interacting through isotopic
interactions, are sufficient to understand these situations. We have employed a series of computer simulations to study
the validity of this simple model in describing protein crystallization: the results of this investigation will be discussed in
this talk
222. Proteins as model colloids exhibiting short-range attractions - The interplay between
spinodal decomposition and glass formation
Frédéric Cardinaux 1 , Thomas Gibaud2 , Anna Stradner 2 and Peter Schurtenberger 2 , (1)Heinrich-Heine-Universität
Düsseldorf, Düsseldorf, Germany, (2)University of Fribourg, Fribourg, Switzerland
Proteins interacting via a short-range attractive potential have been shown to serve as ideal model systems to study the
influence of such an attraction on the equilibrium and non-equilibrium phase behavior of colloidal suspensions. Their
size of only a few nm, their monodispersity, and the possibility to tune the attractive well depth simply by temperature,

make these proteins ideal for such studies. Here we report on a critical re-examination of the different scenarios
proposed for the interplay between phase separation and dynamical arrest in colloidal suspensions. We have used
aqueous solutions of the globular protein lysozyme as a model system for colloids with a tunable short-ranged
attraction. We were able to demonstrate that temperature quenches into the spinodal region and below an arrest
temperature lead to the formation of a bicontinuous network, where the dense phase undergoes dynamical arrest once
it reaches the glass line at this temperature. Microscopically, this corresponds to a coexistence of a dilute fluid with a
dense percolated glass phase. Finally, deep quenches below the glass line result in the formation of a homogeneous
glass phase. These measurements have allowed us for the first time to quantitatively locate the glass line in the
unstable region below the spinodal, and thus provide a new test ground for computer simulations and theoretical
calculations in the current attempt to understand and generalize dynamical arrest in soft matter.
223. Direct in-situ characterization of beta-hairpin peptide self-assembly into a hydrogel

network
Tuna Yucel, Joel P. Schneider and Darrin Pochan, University of Delaware, Newark, DE
In aqueous solution, MAX 1 peptide [(VK)4 VDPPT(KV) 4 ] is unfolded, freely soluble and does not self-assemble.
However, the peptide intramolecularly folds into a beta-hairpin conformation when the electrostatic interactions between
charged lysine residues are screened, through increasing the ionic strength at neutral pH. Beta-hairpin molecules
intermolecularly assemble via hydrophobic collapse and hydrogen bonding into a 3-D hydrogel network, consisting of
well-defined fibrils on the nanoscale. Self-assembly triggered in cell-culture medium leads to rigid and shear thinning
hydrogels, while the stiffness of the network recovers quickly when the stress is removed. Moreover, the hydrogels are
cytocompatible, showing future prospects for biological applications such as injectable 3-D cell encapsulants. By
combining the results of circular dichroism spectroscopy, cryogenic transmission electron microscopy, dynamic light
scattering, and oscillatory rheology, we observe that the self-assembly proceeds by nucleation of monodisperse beta-
sheet fibrils, that elongate and branch to form clusters of fibrils. Assembly kinetics at this early stage indicates power
law growth with assembly time, similar to diffusion-limited clustering of clusters. Eventually, clusters of fibrils fill up the
sample volume, and interpenetrate to form a percolated network, as evidenced by the increasing network rigidity. The
early stage assembly process will be discussed and compared to published gelation models. Ultimately, our goal is to
correlate the structural growth mechanism with in vitro cell function and response.
224. Rate of structural arrest in nanocolloidal suspensions undergoing gelation and aging
Hongyu Guo1 , Subramanian Ramakrishnan2 , Brian Chung 1 , Charles F. Zukoski3 , James L. Harden4 and Robert L.
Leheny1 , (1)Johns Hopkins University, Baltimore, MD, (2)Florida State University, Tallahassee, FL, (3)University of
Illinois, (4)University of Ottawa, Ottawa, ON, Canada
We report a combined x-ray photon correlation spectroscopy (XPCS) and rheometry study of the evolution of
concentrated suspensions of nanometer-scale colloids undergoing gelation and aging. The suspensions are comprised
of silica colloids, 45 nm in diameter, coated with octadecyl-hydrocarbon chains in decalin. At high temperatures the
chains form a solvated brush that stabilizes the colloids. At low temperature, the brush collapses leading to a weak,
temperature-dependent, short-range attraction between the colloids that drives a reversible ergodic to nonergodic
transition in the suspensions. Following a quench through this transition, the shear modulus grows exponentially with a
time constant that depends strongly on temperature. XPCS measurements following such a quench characterize the
evolution of the intermediate scattering function at wave vectors corresponding to interparticle length scales. The
intermediate scattering function displays two features, a plateau value that provides information about constrained local
dynamics in the suspensions and a terminal relaxation time that provides information about relaxation of residual stress.
Both the plateau value and the terminal relaxation time increase exponentially following the quench with a time
constant that closely matches the value for the growing shear modulus. Thus, a comparison between XPCS and
rheometry indicates how the arrest of the particle-scale dynamics correlates with the growth in elasticity. Further, a
comparison of intermediate scattering functions for suspensions with colloidal volume fractions ranging from 0.20 and
0.43 shows a qualitative variation in the temporal evolution that indicates a crossover from gel-like to glass-like
dynamical arrest with increasing volume fraction.
225. Using Triggered Gelation of Responsive Microgel Dispersions to Restore the

Mechanical Properties of Degenerated Soft Tissue

Brian R. Saunders and Tony Freemont, The University of Manchester, Manchester, United Kingdom
An interesting challenge for colloid chemists is to design injectable materials that enable the minimally-invasive repair of
damaged, load-bearing tissue. A key criterion for these materials is that they must be able to support biomechanical
loads. Degeneration of the intervertebral disc (IVD) is a major cause of chronic low back pain. Microgel particles are
cross-linked polymer colloid particles that swell in a good solvent. We hypothesised that a concentrated dispersion of
pH-responsive microgel particles that contained high carboxylic acid concentrations would give an injectable fluid at low
pH that would change to a gel at body pH capable of supporting loads similar to those experienced by IVD tissue in the
body. In this work model pH-responsive poly(EA/MAA/BDDA) (ethylacrylate, methacrylic acid and butanediol diacrylate)
microgel dispersions were used to investigated this hypothesis. The pH-triggered swelling of the particles was
investigated using photon correlation spectroscopy and rheology. Strong pH-triggered particle swelling and fluid-to-gel
transitions of the microgel dispersions occurred at pH values greater than 6.0 (Fig. 1a). The fluid-to-gel transition was
also triggered within IVDs after injection of the microgel into model degenerated spinal units (Fig. 1b). Uniaxial
compression data for degenerated IVDs containing injected microgel dispersions showed that pH-induced particle
swelling restores the mechanical properties of the IVDs to normal (non-degenerated) values. This work demonstrates a
new general approach that has long-term potential to restore the mechanical properties of damaged load-bearing
tissue.
226. Event-driven simulations of primitive models of Silica and Water: analogies between
gel-formation in patchy colloidal particles and glass-formation in network forming liquids
Cristiano De Michele, Università di Roma "La Sapienza", Roma, Italy
Recently we developed a novel algorithm for simulating hard objects of arbitrary shape, decorated on their surface with
spherical sites, that interact through an attractive step potential. Using this new algorithm, we simulated two recently
studied primitive models of network forming liquids — a primitive model for water and for silica. We evaluated the
isodiffusivity lines in the temperature-density plane to provide an indication of the shape of the glass transition line.
Except for large densities, arrest is driven by the onset of the tetrahedral bonding pattern (i.e. the bonding energy
controls arrest) and the resulting dynamics is strong in Angell's classification scheme. Notably patchy colloidal particles
of new generation may designated to closely resemble the primitive models of Silica and Water, thus it is intriguing to
think that this arrest mechanism driven by bonding energy, at low volume fractions, is the same that controls the gel
formation, entitling us to call glasses all arrested states, including the gel states.
227. Investigating complex fluids using a Quartz Crystal Microbalance

Simon Biggs and Christopher Hodges, University of Leeds, Leeds, United Kingdom
Complex fluids are widely used in personal care products, where the bulk fluid is usually made of many components
(non-ionic and ionic surfactants, long chain polymers, perfumes and sometimes nanoparticulates). These components
form a fluid that is usually highly viscous. There are very few techniques that are capable of discerning both the
interfacial adsorption and the bulk properties at the same time. One possible way to access these properties is to use a
Quartz Crystal Microbalance (QCM). A modern QCM can measure both the frequency response and the energy lost
(the dissipation) from a laterally vibrating quartz crystal [1]. The QCM is highly sensitive to both the bulk fluid properties
[2] and to any adsorption that may take place at the QCM crystal surface [3] and is thus ideally suited to complex fluids
adsorption. It is possible to monitor the changes in fluid response in real time such that the kinetics may be obtained.
We will present data showing how the QCM responds to (a) non-adsorbing viscous fluids, (b) specifically adsorbing
viscous fluids and (c) viscous micellar fluids that are not unlike the basis for many commercial products. These results
are dependent on (a) the adsorption taking place and (b) whether slip is occurring at the crystal-fluid interface or not.
[1] Rodahl M. and Kasemo B., Rev. Sci. Instrum. 67 (9) 3238 (1996) [2] Kanazawa K.K. and Gordon J.D. II, Anal. Chim.
Acta 175 99 (1985) [3] Webber G.B., et al., Farad. Discuss. 128 193 (2005)

228. Deposition and characterization of soluble surfactant along the solid-vapor interface
using an evaporative dip coating technique
Benjamin K. Beppler and Stephen Garoff, Carnegie Mellon University, Pittsburgh, PA
The structure of a cationic surfactant deposited from an evaporating thin film onto a hydrophilic, anionic substrate was
investigated using atomic force microscopy (AFM) and imaging ellipsometry. A vertical substrate is receded from
solution above a critical pulling speed, entraining a thin film on the substrate. The convective flow field near a contact
line typical of sub-critical withdrawal is replaced by benign plug flow in the wedge-like film. Confinement of surfactant
molecules in this constantly thinning film environment results in a non-trivial arrangement of molecules along the solid-
liquid and liquid-vapor interfaces into island self-assemblies (typically ~ few µm in lateral extent) along the solid-vapor
interface. AFM measurements show the heights of these assemblies are quantized in units consistent with the length of
the surfactant molecule, beginning with a bilayer. Increasing the film residence time alters the distribution of these
heights and eventually causes dewetting patterns devoid of islands to appear along the interface. Island coverage
increases with pulling speed and soak time prior to recede, independent of film residence time. Switching the solute-
substrate electrostatic interaction from attractive to repulsive by using an anionic surfactant does not inhibit island
formation, proving this technique could potentially be used to deposit a wide range of molecules.
229. Alternative Surfactant Characterization Method Using the Hydrophilic-Lipophilic

Difference (HLD)
Anuradee Witthayapanyanon 1 , Edgar Acosta2 , Jeffrey H. Harwell 1 and David A. Sabatini1 , (1)University of Oklahoma,
Norman, OK, (2)University of Toronto, Toronto, ON, Canada
Microemulsions have received widespread attention for industrial applications due to desirable low interfacial tension
and high solubilization properties. These unique characteristics can only be achieved at the optimum condition where
an equal balance between the surfactant-oil and surfactant-water interactions is obtained. The easiest way to attain the
optimum condition is by a proper surfactant selection. Thus, several empirical approaches (i.e. hydrophilic-lipophilic
balance (HLB), phase inversion temperature (PIT) or Winsor R-ratio etc.) have been proposed as convenient tools for
characterize surfactants. Although, these existing methods provide an approximate estimation of the hydrophilic-
lipophilic nature for most surfactants, they have some serious limitations. Recently, they have been proven inadequate
for characterizing a newly developed class of surfactants known as extended surfactants. Therefore, the goal of this
project is to develop an alternative indicator for characterizing extended surfactant. This new indicator is named as a
surfactant characteristic parameter or a sigma parameter (R) of the hydrophilic-lipophilic difference (HLD). Preliminary
results show a nice correlation between the sigma value and the hydrophilicity and lipophilicity of conventional
surfactants. Furthermore, the sigma parameter method has also proven applicable for characterizing the hydrophilic-
lipophilic nature of extended surfactants.
230. Quantification of bioparticle adhesion to polyamides with atomic force microscopy

B. Reginald Thio and Carson Meredith, Georgia Institute of Technology, Atlanta, GA
We present an update of a modified atomic force microscopy (AFM) technique for the measurement of adhesion forces
between synthetic polymers and bioparticulates implicated in asthma and indoor air pollution. We believe this would
allow us to better understand the mechanisms by which bioparticles are entrained in man-made carpeting and
upholstery. Polymers employed in our study were Nylon 6, Nylon 6,6, polyamide 12 and polystyrene (as a control). We
first describe the use of three previous models for interpreting AFM force-distance data and calculating work of
adhesion. We also discuss a square-pyramid-flat-surface (SPFS) model framework developed for calculating Hamaker
constants. We find that the SPFS model yields the most reliable estimates of contact radius. This model is applied to
calculate Hamaker constants for bioparticle-polymer interactions: E. coli with those of ragweed (A. artemisiifolia) and
the black mold (A. niger). Results of relative Hamaker constants between these three bioparticles and the four polymers
will be discussed in terms of their chemical surface features.
231. Polarization of Electrodes by Doped Nonpolar Media

James Hoggard, Dennis C. Prieve and Paul J. Sides, Carnegie Mellon University, Pittsburgh, PA

While double-layer repulsion of charged particles in water is well known, even nonpolar solvents with a dielectric
constant as low as two can contain charged ions; and particles immersed in nonpolar liquids can be electrostatically
stabilized. Electric current versus time was measured between two flat plate electrodes 2.5cm x 7.5cm separated by 1.2
mm of heptane doped with 0-15% w/w poly(isobutylene succinimide) (PIBS) having a molecular weight of about 1700.
The initial current yields the specific conductance of the solution whereas the initial rate of decrease in current yields
the Debye length of the solution. Thus we deduced Debye lengths of 30-170 nm which decrease with increasing
concentration of PIBS. Values of the Debye lengths were confirmed by performing independent measurements of
double-layer repulsion using TIRM. The charge carriers appear to be inverted PIBS micelles, having a diameter of 40
nm, containing a substantial amount of solubilized water. About 25% of these micelles have a single plus or minus
charge, independent of concentration of PIBS.
232. Characterization of Nano- and Microdispersions using Multisample Analytical

Centrifugation: Interparticle Forces, Deformability and Particle Size
Torsten Detloff, Titus Sobisch and Dietmar Lerche, L.U.M. GmbH, Berlin, Germany
The behavior of nano- and microdispersions, i.e. stability, flow, separation, packing behaviour, particle size distribution
and particle deformability are of fundamental importance for the application of the dispersions in diverse fields. The
present work reports on the use of multisample analytical centrifugation for the investigation of packing, compression,
demixing behavior and particle size distribution to characterize dispersed systems in the nanometer and micrometer
range. The new multisample approach uses the STEP-technology. Space and time resolved extinction profiles quantify
the alteration of particle concentration and packing behavior during centrifugation. The sedimentation kinetics of rigid
non-interacting particles (2 to 50 % v/v) can be exactly described by the phenomenological equations and the
corresponding flux density function, and exhibits the so-called type I and type II sedimentation. The packing density,
obtained after compression, is related to the total interparticle potential energy. By using different additives interaction
between particles can be shifted from nearly hard sphere behavior to strong attraction which results in flocculated
systems. Additional information is obtained about the strength and elasticity of particle networks by analyzing the
relative change in sediment volume after increasing/decreasing the excess pressure in multiple cycles. The paper
further covers the determination of the particle size distribution from space and time extinction profiles for dispersions,
with monomodal, multimodal and broad particle size distributions. An approach to account for effects of hindered
settling and multiple scattering in concentrated dispersions is presented. Experimental results from concentrated
suspensions and emulsions will be compared with those of other measurement techniques.
233. NMR as a tool to measure directly the Surface Area of Nanoparticulate Dispersions
David Fairhurst, Xigo Nanotools LLC, Morganville, NJ and Terence Cosgrove, University of Bristol, Bristol, United
Kingdom
The need to determine the surface area of materials is well established; it influences many aspects of product
performance. The most widely employed technique is that of (BET) gas adsorption but it is only useful for analyzing dry
powders. However, the overwhelming majority of manufactured products, including nanoparticulate systems, involve
suspensions of particulate materials in some fluid, either in the final state or at some stage of their production. Gas
adsorption is not well suited to such systems; drying takes time and will promote aggregation. We describe a
revolutionary instrument designed to measure the surface area of nanoscale particles or droplets dispersed in a liquid.
This new (patent pending) technique is based on nuclear magnetic resonance (NMR) and it offers many advantages in
comparison with conventional surface area instrumentation. The technique is based on the fact that liquid in contact
with, or “bound” to, the surface of a particle behaves differently from that of the bulk or “free” liquid. The NMR relaxation
time of bound versus bulk liquid is markedly different: the relaxation time of the latter is much longer. No assumptions
need to be made about the sample particle (distribution) or shape in the determination of the surface area; it is
measured directly. Suspensions and emulsions can be measured non-invasively, without dilution. The upper limit in
concentration is essentially unlimited; the lower limit is about 1-2%. The theory underpinning this new approach to
surface area measurement will be discussed and examples given to illustrate its wide applicability.
234. Keynote: Directional interactions with patchy colloids

ABSTRACT WITHDRAWN

Abstract not available
33. Keynote: Self-assembly of soft spheres

Randall D. Kamien, University of Pennsylvania, Philadelphia, PA
We propose a heuristic explanation for the numerous non-close-packed crystal structures observed in various colloidal
systems. By developing an analogy between soap froths and the soft coronas of fuzzy colloids, we provide a
geometrical interpretation of the free energy of soft spheres. Within this picture, we show that the close-packing rule
associated with hard-core interaction and positional entropy of particles is frustrated by a minimum-area principle
associated with the soft tail and internal entropy of the soft coronas. We find that the A15 lattice, known to be area
minimizing, is favored for a reasonable range of model parameters and so it is among the possible equilibrium states
for a variety of colloidal systems. We extend these ideas to diblock copolymers and find new, stable sphere-like
phases.
235. A surface resonance renders opaline photonic crystals ineffective

Florencio Garcia-Santamaria, Erik C. Nelson and Paul V. Braun, University of Illinois at Urbana-Champaign, Urbana,
IL
In this work we identify and study the presence of extremely intense surface resonances that frustrate the coupling of
photons to photonic crystals for crucial ranges of energy. The practical utility of photonic crystals demands the ability to
exchange photons with the external medium, therefore, it is of paramount importance to acknowledge the presence of
these surface resonances and eliminate them. Moreover, we demonstrate that these resonances lie in the regions of
photonic band gaps for two important photonic crystal structures that include the widely used artificial opals. This has
led others to conclude that the structures they were investigating were functioning well as photonic crystals when in
fact the optical properties being measured were due to surface resonances and not the bulk photonic properties. We
demonstrate that by modifying the surface geometry it is possible to tune the optical response or eliminate the
resonances to enable full exploitation of the photonic crystal properties.
236. Fluid-bicontinuous emulsions stabilized by colloidal particles

Eva M. Herzig, Paul S. Clegg, Andrew B. Schofield, Michael E. Cates and Wilson C.K. Poon, Edinburgh University,
Edinburgh, United Kingdom
Using controlled spinodal decomposition, we have created bicontinuous emulsions stabilized by interfacially jammed
colloidal particles (Fig.1). The colloids, silica modified to yield partial wettability, are initially dispersed in the single-fluid
phase. The sample is warmed (in the case of water-lutidine) into the two-fluid phase. The colloids become trapped on
the newly created interface; as the fluid domains coarsen the amount of interface decreases and the colloids jam
together arresting phase separation. The arrangement of domains reflects the demixing kinetics: warming through the
critical point leads to a bicontinuous structure. (Structures can also be created via an upper critical point which we
illustrate using silica colloids in alcohol-oil mixtures). We will present fluorescence confocal microscopy studies showing
the arrangement of domains, the stabilization by interfacial colloids over many weeks, and the changes in structure with
both sample composition and warming rate. We will give preliminary indications of the mechanical properties (Fig.2).
Our results demonstrate that by varying the fluid composition systematically, and hence the demixing kinetics, an
emulsion inversion occurs where the bicontinuous soft-solid is found at the inversion point.
Figure 1. A fluid-bicontinuous structure stabilized by silica colloids (white) imaged by fluorescence confocal microscopy
at 40C. The two fluid domains (black) are water-rich and lutidine-rich respectively. The scale bar is 100mm.
Figure 2. An ~8mm long copper wire supported against gravity by a fluid-bicontinuous gel. The wire remained in place
for the duration of the study (several days); this demonstrates that the colloid-stabilized structure has a significant shear
modulus.

237. Segregation of Defects at Grain Boundaries

Ahmed M. Alsayed, University of Pennsylvania, Philadelphia, PA and Arjun G. Yodh, University of Pennsylvania,
Philadelphia, PA
Interstitial impurity segregation at grain boundaries plays an important role in materials properties such as cohesion,
grain growth kinetics, and transport. Unfortunately, direct measurement of grain boundary composition is difficult in bulk
crystals and polycrystals. In this contribution we directly study impurity segregation at grain boundaries using a model
colloidal crystal. The polycrystals are made of temperature-sensitive micron size NIPA microgel particles. We add 100-
200 nm fluorescent polystyrene particles to this system to model interstitial impurities. The impurities are then tracked
using video microscopy close to and far from the grain boundaries. We find that impurities hop from one position to
another and diffuse anisotropically when far from the grain boundaries and they diffuse isotropically in the grain
boundaries. Upon increasing the temperature, the packing volume fraction of NIPA particles decreases and grain
boundaries start to melt. We also explored the effects of the segregated impurities on grain boundary melting.
238. Segregation and Self-Assembly of a Polydisperse Suspension of Colloidal Particles via

Dielectrophoresis
Prasad S. Sarangapani and Y. Elaine Zhu, University of Notre Dame, Notre Dame, IN
Control of colloid segregation and self-assembly is important for inkjet printing, precision coating, synthesis of
nanoporous materials, and a variety of other modern technologies. We explore the method of dielectrophoresis to
control the interaction of micro/nano-colloids in AC electrical fields and assemble them from a suspension into new
classes of colloidal crystals and membranes. By tuning the frequencies of imposed AC fields on polydisperse silica
micro/nano-spheres, we are able to effectively segregate particles with a size ratio of 5:2:1 and tailor 3-D self-
assembled structures, while monitoring the assembly process via confocal microscopy. Using high-speed fluorescence
imaging we also explore the mechanisms behind the AC colloid-dipole polarization and the multi-dipole interaction that
drives the assembly of colloidal crystals.

239. Mechanics of deformable colloids: Elastic moduli of cross-linked Pickering emulsion

drops
James K. Ferri1 , Nikolce Gorevski 1 , Andreas Fery2 and Philippe Carl2 , (1)Lafayette College, Easton, PA, (2)Max
Planck Institute for Collids and Interfaces, Golm, Germany
Growth in nanotechnology provides motivation for a comprehensive understanding of the strength of materials down to
nanometer lengths.
We describe a new experimental technique, colloidal probe atomic force microscopy (AFM) combined with reflection
interference contrast microscopy (RICM), and accompanying theoretical framework for the mechanical characterization
of soft materials with nanometer thickness; i.e. two dimensional continua. As a model system, a Pickering emulsion
droplet consisting of perfluorooctane/water/Cow pea mosaic virus nanoparticles.
The emulsion droplets are compressed via the colloidal probe tip of the AFM, the deformed drop shape is reconstructed
by RICM. To determine the elastic behavior of the material, equations of equilibrium are used to describe the shape of
the membrane in terms of the applied force, the contact radius and the membrane elastic parameters; the elastic
parameters of the material are then found by adjusting their values in the model until a minimum in the error between
theory and experiment is achieved.
Non-crosslinked nanoparticle monolayers display the behavior consistent with an aqueous/oil interface, i.e. constant
tension with increasing strain. When nanoparticles cross-linking is introduced on the surface, the material displays an
initial region of linear elasticity for low deformation. For small surface strains, the surface elastic parameter is constant
at approximately 0.7 N/m. As the strain increases further, the elastic parameter decreases, which indicates a loss of
structure for higher, albeit small, deformations.
240. Keynote: Scattering from Colloidal Gels and Microgels

David A. Weitz, Harvard University, Cambridge, MA
The results of light scattering measurements from colloidal gels and microgels will be reported. These measurements
provide insight into the dynamics and structures of these systems. I will describe recent results that help determine the
nature of the gelation process and the relationship of the properties of the gels to the control parameters used in their
formation. These stuctures are good models for stability of dispersions.
241. Probing Colloidal Dynamics with Diffuse Light

Frank Scheffold, Fribourg University, Fribourg, Switzerland
We discuss some recent advances in multiple light scattering probes, or Diffusing Wave Spectroscopy, applied to
colloidal systems: the DWS Echo technique allows recording the full intensity autocorrelation function with a single
experimental setup. This is achieved by putting a fast rotating diffuser in the optical path between laser and sample.
We show that the recorded (multi-speckle) correlation echoes provide an ensemble averaged signal that does not
require additional time averaging. We will further discuss applications of this technique in DWS microrheology and we
will present a new experiment that allows monitoring the drying of a colloidal thing film with high resolution.
242. Speckle-visibility spectroscopy study of bubble rearrangements in a coarsening foam

Douglas J. Durian, University of Pennsylvania, Philadelphia, PA and Alex S. Gittings, UCLA, Los Angeles, CA
Speckle-Visibility Spectroscopy is a dynamic light scattering technique capable of resolving fluctuating or unsteady
dynamics. Here we use it to study in detail the nature of bubble rearrangements in a coarsening foam. In particular we
measure the statistical distribution of event durations, speeds, and time between events. By constrast, usual methods
yield only the average time between events.
243. Temporal heterogeneity and spatial correlation of the slow dynamics of soft glassy
materials

Luca Cipelletti1 , Agnès Duri2 , David Sessoms 3 and Veronique Trappe 3 , (1)University of Montpellier 2 and CNRS,
Montpellier, France, (2)Deutsches Elektronen-Synchrotron (Hasylab), Hambourg, Germany, (3)University of Fribourg,
We investigate the dynamics of a variety of jammed soft materials, including strongly attractive colloidal gels,
concentrated surfactant phases, and charged platelets (Laponite). By using Time Resolved Correlation, a time-resolved
dynamics light scattering technique, we show that, quite generally, the dynamics of these systems are strongly
hetergogeneous in time, suggesting that they relax through discrete rearrangement events.. We measure the size of the
rearrangement events using a novel space- and time-resolved light scattering method: quite surprisingly, we find that
each event affects a volume much larger that the size of the system's constituent (particles or clusters). This finding is
in stark contrast with simulations and experiments on supercooled fluids, where spatial correlations of the dynamics
extend over a few particles at most.
244. Time and space resolved measurements of dynamical heterogeneities in coarsening

foams
David Sessoms 1 , Hugo Bissig1 , Veronique Trappe 1 , Agnes Duri2 and Luca Cipelletti2 , (1)University of Fribourg,
Fribourg, Switzerland, (2)University of Montpellier, Montpellier, France
We investigate heterogeneities in the dynamics of coarsening foams by performing both time and space resolved
diffusing wave spectroscopy experiments. In the transmission geometry, we record the speckle pattern in the far field
using a CCD-camera and process the images using the Time Resolved Correlation scheme [1]. In the backscattering
geometry, we record the speckle pattern at the exit plane of our scattering cell and process the images by calculating
the degree of correlation for different areas of the CCD-image. This latter technique allows us to construct spatially
resolved maps of the instantaneous dynamical activity of our foam and to follow its temporal evolution. Our results
suggest that the local intermittent rearrangements of bubbles typically observed in microscopy are not the only cause
for dephasing the scattered light. When the internal stress imbalances, that gradually build up as the foam coarsens,
become large enough, an event occurs that leads to a displacement of bubbles in a large portion of the sample. This
major event appears to effectively release the internal stress imbalances.
[1] L. Cipelletti, H. Bissig, V. Trappe, P. Ballesta, S. Mazoyer, J. Phys.: Condens. Matter 15, 257 (2003).
245. Time-resolved light scattering characterization of turbid colloidal suspensions and gels
Christian Moitzi, Hugo Bissig, Anna Stradner, Frank Scheffold and Peter Schurtenberger, University of Fribourg,
To characterize the structural and dynamic properties of (soft) materials, information on the relevant mesoscopic length
scales is required. Such information is often obtained from traditional static and dynamic light scattering (SLS/DLS)
experiments in the single scattering regime [1]. In dense systems, such as colloidal suspensions and gels, however,
these powerful techniques frequently fail due to strong multiple scattering of light. Here we review some of the recent
advances in light scattering from turbid fluid- and solid-like media that include 3D cross-correlation experiments to
suppress multiple scattering [2] and echo diffusing wave spectroscopy [3] to access dynamic and static properties of
extremely turbid media. We in particular focus on a novel multi-angle light scattering instrument that fully implements
the 3D cross correlation scheme and thus allows for time-resolved measurements on turbid suspensions. We show that
this technique provides access to the initial stage of aggregation and cluster formation in concentrated and turbid
destabilized colloidal suspensions.
References: [1] F. Scheffold and P. Schurtenberger, “Light scattering probes of viscoelastic fluids and solids”, Soft
Materials 1, 139-165, (2003) [2] Frank Scheffold, Andrey Shalkevich, Ronny Vavrin, Jérome Crassous, and Peter
Schurtenberger, “PCS Particle Sizing in Turbid Suspensions: Scope and Limitations”, "Particle Sizing and
Characterization", ACS Symposium Series 881, T. Provder and . Texter, Eds., pp 3 - 32 (2004) [3] P. Zakharov, F.
Cardinaux and F. Scheffold, "Multi-speckle diffusing wave spectroscopy with a single mode detection scheme", Phys.
Rev. E, 73, 011413, 2006
246. Keynote: Polyelectrolyte-colloid coacervation: meso- and macro-phase separation in

polycation-micelle systems
Paul L. Dubin1 , Anil Kumar 1 , Michael Hernon1 , Yajuan Li 1 and Werner Jaeger2 , (1)University of Massachusetts,
Amherst, MA, (2)Fraunhofer-Institut fur Angewandte Polymerforschung, Golm, Germany
Observable states for the polycation-anionic/nonionic mixed micelle system PDADMAC-SDS/TritonX-100 include:
soluble complexes, liquid coacervates, and precipitates. The corresponding transitions were studied as a function of
[SDS]/{[SDS]+[TX100]} = Y, temperature (T), ionic strength (I) and polycation MW. Phase separation (at Tφ) is induced
by an increase in T, a decrease or increase in Y or I, and is favored by high MW. At fixed I, the Tφ -Y boundary
comprises: (A) a coacervation domain exhibiting an LCST, and (B) a superimposed precipitation or high-density
coacervation domain. Region A is symmetrical around 0.2<Y*<0.6 where charge-neutralized complexes/aggregates are
at incipient phase separation. In region B (high Y) the dependence of the phase boundary on I, MW and Cp is
consistent with polycation collapse and counterion expulsion. Coacervates formed in region A, which were found to
undergo further phase separation at Tφ' (> Tφ) , were characterized by turbidimetry, light scattering and rheology, with
the following results: (1) Microphase separation along elongational shear lines is seen at (T φ'-T)=2oC - 8oC, where
coacervates are shear-thinning. (2) Coacervates display a dominant slow mode in DLS which increases as temperature
rises above Tφ', along with a low-intensity temperature-independent fast mode corresponding to nearly free micelle
diffusivity. (3) At T ca. 2-3oC above Tφ', a plateau appears in shear stress vs. shear rate curves. The results are
consistent with mesophase separation within the coacervates driven by the entropy of counterion release. The
enhancement of this process by shear is not yet fully understood.
247. Interfacial polyelectrolyte structures for tunable high capacity protein uptake
Andy Kusumo1 , Hongchen Dong 1 , Jinyu Huang 1 , Qiao Lin 2 , Krzysztof Matyjaszewski1 , Tomek Kowalewski1 , James
W. Schneider 1 and Robert D. Tilton1 , (1)Carnegie Mellon University, Pittsburgh, PA, (2)Columbia University, New York,
NY
Surface-bound polyelectrolyte structures are being designed for tunable protein uptake from solution. SPR
measurements indicate at pH 6 poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes end-grafted from gold
surfaces by atom transfer radical polymerization (ATRP) adsorb net-negatively charged bovine serum albumin (BSA) to
an extent equivalent to 10 BSA monolayers. The adsorbed BSA mass per unit volume in the brush is comparable to its
aqueous solubility limit in some cases. BSA uptake scales linearly with the surface concentration of grafted PDMAEMA,
regardless of the degree of polymerization and grafting density for all brushes examined; BSA is bound at a constant
ratio of 120 DMAEMA monomer units per BSA molecule. The adsorption is electrostatically driven. Desorption is
possible only by manipulating the pH and/or ionic strength to weaken the electrostatic attraction. Net positively charged
lysozyme is completely rejected by the brush. Quantitative structure-activity relationships between protein size and
electrostatically driven uptake in PDMAEMA brushes will be discussed. If instead of a brush, a lightly crosslinked
PDMAEMA hydrogel is attached to the surface, both the binding kinetics and the extent of BSA uptake are diminished.
BSA binding occurs at > 1000 DMAEMA units per BSA. This is attributed to the inability of crosslinked PDMAEMA
chains to adequately reconfigure to accommodate bound BSA. Lastly, current efforts to copolymerize PDMAEMA with
more hydrophobic segments in order to achieve thermally programmable protein uptake will be described.
248. Solution behavior of rod-like polyelectrolyte-surfactant aggregates formed through

polymerization of wormlike micelles
Daniel M. Kuntz and Lynn M. Walker, Carnegie Mellon University, Pittsburgh, PA
The solution behavior of a rod-like, water-soluble, polyelectrolyte-surfactant aggregate system (pC16TVB) is detailed.
These aggregates are generated by in situ polymerization of a cationic-hydrotrope wormlike micelle system. A feature
of the system is the fact that the monomer groups and the surfactant are present in ion pairs in the absence of added
salts or counterions, so the stoichiometry (with respect to charge) is 1:1 for the aggregates. Therefore, after
polymerization the surfactant acts as the counterion for the polyelectrolyte chains as other counterions (salts) are not
available. Despite being present in a 1:1 molar ratio, the aggregates are surprisingly stable in water (concentrations >
600 mg/mL). Structural analysis shows that the polyelectrolyte chain is trapped in a cylindrical “tube” formed by the
surfactant. As such, the amount of surfactant present in the “tube” impacts the conformation adopted by the confined

polyelectrolyte chain and the aggregate as a whole. The aggregate length can be adjusted by removing or adding
surfactant and disrupting the 1:1 molar ratio. A simple model for the structure is presented and the ability to manipulate
the aggregate structure demonstrated.
249. Properties and applications of surfactant and polyelectrolyte gels
Yakov Lapitsky1 , Tasneem Zahir1 , Molly S. Shoichet 1 and Eric W. Kaler 2 , (1)University of Toronto, Toronto, ON,
Canada, (2)University of Delaware, Newark, DE
Oppositely charged surfactants and polyelectrolytes undergo associative phase separation when mixed in near-
stoichiometric ratios. In recent years this phenomenon has been exploited to form ordered gel-like assemblies, whose
structure ranges from spherical particles (1 – 4000 µm in diameter) to cylindrical fibers and planar sheets. The stability
of these materials depends on the equilibrium phase behavior of the surfactant and polyelectrolyte mixture, while their
structure is governed by the method of their preparation. Here, we discuss the performance of these materials in
controlled release and tissue engineering applications: namely, the encapsulation of aromatic oil (cymene) for fragrance
release and cell guidance for regenerative medicine. Surfactant and polyelectrolyte gel particles release aromatic oils
into both aqueous and organic receiving solutions, with rates determined by the solubility and diffusivity of the oil in the
gel matrix. Likewise, cylindrical surfactant and polyelectrolyte gel fibers prepared from biocompatible components can
act as cell-adhesive scaffolds that guide cell growth.
250. Influence of protein on surfactant self-assembly in oil/water mixtures

Jun Y. Kim and Prof. Stephanie R. Dungan, University of California, Davis, CA
Proteins and surfactants coexist in biological and industrial systems, and have the potential to interact due to
electrostatic, steric and hydrophobic interactions. As a result, protein molecules may alter the interfacial energy of
surfactant monolayers, and thereby modify the phase behavior of surfactants. It is particularly interesting to study self-
assembly in equivolume mixtures of oil and water, in which the surfactant is free to form various nanostructures,
depending on the spontaneous curvature of the monolayer. Using SAXS, we have found that small amounts of the
water-soluble, globular protein alpha-lactalbumin markedly alter phase morphologies of the surfactant AOT:
transforming spherical water-in-oil (w/o) microemulsion droplets to large w/o ellipsoids, to inverted oil-in-water droplets,
and to liquid crystalline and gel-forming structures. As the protein to surfactant ratio increases, the aspect ratio of the
structures also increases, and self-assembly shifts from the organic to aqueous phase. In the presence of the protein
these morphologies are tuned by protein charge and ionic strength, with the protein/surfactant interaction now
apparently controlling the self-assembly. More subtle effects of protein on phospholipid self-assembly are also
observed, and suggest a significant role for molecular architecture.
251. Reversible aggregation of polyvinyl caprolactam in aqueous solutions above and

below the lower consolute temperature
Qiang Qiu, Unilever Research, Trumbull, CT, Larry Senak, International Specialty Products, Wayne, NJ and Brian A.
Pethica Sr., Princeton University, Princeton, NJ
Poly vinylcaprolactam (PVCL) is completely soluble in water at temperatures below the lower consolute temperature
(LCST) of ~32oC, above which a stable, non-sedimenting cloudy state is formed. Silica dispersions in PVCL solutions
are stable below the LCST, but rapid reversible flocculation and sedimentation occurs on raising the temperature above
the LCST. Adsorption of PVCL to silica dispersions, as measured by the classical depletion method, is massively
increased above the LCST, rising steeply with polymer concentration. The large adsorption and associated flocculation
(which appears as an adsorption from the depletion method) are both reversed on lowering the temperature below the
LCST. PVCL is known to form aggregates above the LCST . A further study of PVCL in aqueous solution by GPC, DLS
and MALLS over a range of temperatures across the LCST for two molecular weight PVCL preparations has been
made. The results indicate some aggregation below the LCST, rapidly increasing with temperature as the phase
boundary is crossed . Above and near the boundary, the aggregates are polydisperse, becoming monodisperse as the
temperature is raised further. Aggregation reaches a maximum, falling off at the highest temperatures studied. For
example, aggregates formed in a 3000ppm solution of a 70K PVCL preparation reach a maximum hydrodynamic
diameter of 1500nm at 40oC. The loss of PVCL from solution due to adsorption/flocculation observed with silica
suspensions above the LCST increases linearly with concentration with an approximately constant fraction of the added

polymer remaining in the supernatant.
252. Keynote: Particle-Assisted Wetting

Werner A. Goedel, Chemitz University of Technology, Chemnitz, Germany
In principle, one might easily prepare thin polymer membranes by copying the float glass process, but instead of molten
glass, one might wet a water surface with a polymerizable oil, solidify and lift it off the water as a thin freely suspended
membrane. However, few oils wet a water surface. This inability can not be overcome by adding most amphiphiles, but
can be by adding particles. In general, placing a particle into a liquid/liquid or liquid/air interface gives rise to a gain in
energy, which is largest if the interface-particle contact angle is close to 90 degrees. If oil-particle mixtures are applied
to a water surface, the oil might form wetting layers in which the particles penetrate through at least one of the
interfaces of that layer. Depending on the interfacial tensions and contact angles of these interfaces with the particles,
one can draw phase diagrams of particle assisted wetting. We developed a simple theory describing this phenomenon
and correlated it to experimental observations. Cross-linking the oil within the mixed layers indeed gives rise to
membranes comprising enbedded particles. Especially of interest are those membranes prepared using a volume of oil
sufficient to fill the space between the particles, but not fully cover them. If in these membranes the particles are
selectively removed, one is left with a microsieve: a membrane bearing sub-microscopic holes of uniform diameter and
thinner than the hole size; thus offering a minimum flow resistance and optimum selectivity in filtration applications.
253. Inversion of an Abnormal Emulsion produced by Continuous Stirring. Effect of the

Formulation on the Evolution of the Double Emulsion
Marianna Rondón-González 1 , Véronique Sadtler 1 , Lionel Choplin 1 and Jean-Louis Salager2 , (1)GEMICO, ENSIC-
INPL, Nancy, France, (2)FIRP, Universidad de los Andes, Mérida, Venezuela
Emulsion inversion, which is the change in emulsion morphology from oil-in-water (O/W) to water-in-oil (W/O) or vice
versa, is a handy alternative to produce fine and concentrated emulsions. It could result from the continuous stirring of
an abnormal emulsion, in which case the external phase is not the one favored by the surfactant affinity but the one in
higher volume proportion.
The inversion mechanism associated with continuous stirring often involves the formation of a multiple emulsion
(w/O/W), in which a portion of the (W) external phase is continuously included as (w) droplets in the dispersed (O)
phase drops. This inclusion is eventually opposed by droplet escape from the drops. When both phenomena are in
dynamic equilibrium, the inversion cannot take place, but if the inclusion dominates over the escape, the apparent
volume of the dispersed phase increases until a critical value is reached and the inversion is triggered.
In the nonionic-brine-kerosene system studied, the balance between the inclusion and escape is found to be affected
by the formulation (as the hydrophilic-lipophilic-deviation HLD) and by the alcohol concentration. The interface
composition influences the stability of both inner w/O and outer O/W emulsions, thus determining the kinetics of
inclusion and the stirring time required to trigger the inversion into the W/O final morphology.
254. The Validity of the Ward-Tordai Model to Describe Dynamic Surfactant Transport
through Fluid/Fluid Interfaces
C. J. Radke, University of California, Berkeley, Berkeley, CA
We compare the classic Ward-Tordai and the microscopic Smoluchowski models for the dynamics of surfactant
transport through fluid/fluid interfaces. The Smoluchowski model treats the interface as a free-energy field, whereas the
Ward-Tordai model treats the interface as an infinitesimally thin plane exhibiting adsorption and desorption kinetics.
Equivalence of the two models is established when the free-energy well underlying surfactant adsorption is flanked by
barriers that are larger than thermal energy. When energy barriers are non-existent, however, a finite interfacial width
must be introduced into the Ward-Tordai analysis to obtain physically meaningful results, i.e. non-negative desorption
rate constants. Recenty, we presented an experimental investigation into the adsorption dynamics of diblock copolymers
to a polymer/polymer interface and found them to be well described by the Smoluchowski model. Here, we show that
the experimental sorption dynamics are also captured by a finite-interfacial-width extension of the Ward-Tordai model,
whereas the classical model fails to predict the observed behavior.

255. Measurement and Interpretation of Line Tension in a Liquid Lens System

Robert David 1 , Stephanie M. Dobson1 , Saiedeh Tavassoli1 , M. Guadalupe Cabezas 2 and A. Wilhelm Neumann 1 ,
(1)University of Toronto, Toronto, ON, Canada, (2)University of Extremadura
Widely varying measured values of three-phase line tension have been reported in the literature. Experiments in solid-
liquid systems are subject to uncertainty caused by surface roughness and heterogeneity. These difficulties are avoided
in liquid-liquid systems.
We report new measurements of the line tension of the dodecane-water-air system in the liquid lens configuration.
Improved experimental technique produced better axisymmetry and equilibrium of the lenses than in past experiments
in our group. Using a new image processing algorithm (TIFA-AI), the liquid-vapour interfaces were fit to solutions of
the Laplace equation, rather than polynomials, as before. Line tension of +1.11 μN was obtained for lens radii in the
millimetre range.
We will discuss the interpretation of the data in terms of both the Neumann quadrilateral relation and an alternative,
empirical formulation, which was derived from trends observed in the literature data.
256. Cylindrical Particles at Fluid Interfaces: Controlling Orientation and Assembly

Eric Lewandowksi, Kathleen J. Stebe and Peter C. Searson, Johns Hopkins University, Baltimore, MD
The configurations and interactions of anisotropic micro- or nanoparticles at fluid interfaces depend strongly on the
particle geometry and the contact angle of the three phase contact line in the zero Bond number limit. Here we explore
cylindrical objects at fluid interfaces. First, the equilibrium configurations of an isolated cylindrical object at a fluid
interface are described. We identify conditions in which the particle can assume either an end-on or a side-on
orientation depending on the aspect ratio of the particle and the contact angle. The predictions compare favorably to
experiments in which functionalized gold nanorods are spread at aqueous-gas interfaces, immobilized using a gel-
fixation technique, and observed by scanning electron microscopy. Second, the directed assembly of cylindrical
particles in a side-on configuration is studied. Since fluid climbs the end faces of the cylinders, zero-mean curvature
menisci form at each end face. When menisci from different particles overlap, attractive capillary interactions are
created that drive end-to-end chaining. Experimental observations of this chaining are presented. Third, the orientation
and translation of cylindrical objects on curved interfaces are described; forces driving translation and torques driving
orientation are established that depend on the local curvature of the fluid interface. Video microscopy experiments and
analytic arguments are presented in which cylindrical objects are placed on (macroscopic) menisci formed by capillary
rise on a bounding surface. Particles on convex interfaces align perpendicular to the bounding surface, while particles
on concave interfaces align parallel to the bounding surface.
257. Thermodynamic understanding of alkanes' solubility in surfactant hydrocarbon layers

Jan van Stam1 , Sara Briscoe 1 , Bengt Kronberg 1 , Gunilla Carlsson 1 and Mikael Björling 2 , (1)Karlstad University,
Karlstad, Sweden, (2)University of Gävle, Gävle, Sweden
A crucial question concerning interfacial wetting phenomena is how an organic solvent interacts with a surfactant layer's
hydrocarbon chains. This interaction will, as an example, influence the swelling of the surfactant layer and, hence, the
curvature of inverted w/o micelles. We have chosen to use chromatographic measurements to study the interactions
between solvents and surfactants. The retention time, obtained by HPLC measurements, will be a measure on the
solubility of the solvent in the hydrocarbon chain layer. From measurements of the retention time's temperature
dependence and analyzing both the shift in retention time and peak tailing, an adsorption isotherm can be calculated.
Combining the experimental results with thermodynamic modeling opens for a molecular understanding of solvent-
surfactant interactions.
258. Molecular insights into self-perpetuating conformational changes of prions and

amyloids
Peter M. Tessier and Susan Lindquist, Whitehead Institute for Biomedical Research, Cambridge, MA

Protein conformational changes drive many biological processes. Few are as dramatic in terms of the structural
changes that occur, or the biological consequences they produce, as those governing the formation of amyloid fibers.
These highly ordered, beta-sheet rich structures were initially linked to several neurodegenerative disorders such as
Alzheimer's disease, but more recently they have also been linked to normal biological functions such as cell adhesion
and skin pigmentation. Prions represent a unique class of amyloid-forming proteins capable of switching to self-
perpetuating conformations that are infectious and can be transmitted between different organisms. Several prions in
the yeast S. cerevisiae have been identified, including Sup35, a protein involved in translation termination. Utilizing
variants of this protein we find that several outstanding questions related to prion biology and the formation of amyloids
can be investigated using arrays of short, surface-bound peptides. In this presentation I will discuss the use of peptide
arrays to identify small elements of amino-acid sequence within several prions that govern their self-recognition and
conformational conversion. Remarkably, we find that these same recognition sequences also govern the ability of the
prions to adopt not just one amyloid conformation, but a suite of related yet structurally distinct conformations, known as
prion strains. Further, our results suggest a mechanism that explains the previously perplexing relationship between the
abilities of prions to form specific amyloid conformations and to cross species barriers. In the future, peptide arrays may
enable the rapid analysis of the conformational conversion and assembly of other amyloid-forming proteins.
259. Solution Structure of an Amyloid-Forming Protein During Photoreversible

Oligomerization Revealed Through SANS
Andrea C. Hamill, Shao-Chun Wang and C. Ted Lee Jr., USC, Los Angeles, CA
Fibril formation in Alzheimer's disease is believed to result from the formation of unstable, slightly-unfolded protein
conformations, resulting in a cascading aggregation process from monomers to oligomers to short filaments and
eventually fully-developed amyloid fibrils. Recently, the prefibrillar intermediates have become viewed as the primary
pathogenic species. To investigate amyloid intermediates we have developed two complementary approaches: a means
to induce changes in protein folding and association in a controlled and photo-reversible manner, and a method to
determine the in vitro conformation of associated proteins at relatively high resolution. These methods utilize the
interaction of proteins with photosensitive surfactants that can be switched “on” or “off” with light. Light can be used to
reversibly bind the surfactant to the protein, leading to photocontrol of protein conformation. Shape-reconstruction
analysis applied to small angle neutron scattering (SANS) data is then employed to determine the conformation of
protein oligomers. With the photo-actived surfactant, expanded corkscrew-like hexamers are observed. Converting to
photo-passive surfactant causes hexamers to laterally aggregate, forming dodecamers with twisted conformations that
eventually result in fully-developed fibrils. Together, these results provide the first direct observation of the mechanism
of formation of the key intermediates in amyloid fibril formation, which could provide unique insight into the amyloidosis
disease pathway.
260. Fibrillation kinetics of recombinant human insulin with osmolytes: experiments and
kinetic modeling
Arpan Nayak1 , Chuang-Chung Lee2 , Mirco Sorci1 , Amit Dutta 1 , Robert Grassucci3 , Ingrid Hahn 3 , Joachim Frank 3 ,
Gregory J. McRae 2 and Georges Belfort1 , (1)Rensselaer Polytechnic Institute, Troy, NY, (2)MIT, Cambridge, MA,
(3)Wadsworth Center and Howard Hughes Medical Institute, Albany, NY
Amyloid fibrillation is the process of native soluble proteins misfolding into insoluble fibrils comprising of cross-â-sheets
and has received wide attention due to its substantial physiological relevance and the complexity of the underlying
physical and chemical reactions. At present, more than 20 amyloidogenic diseases including Alzheimer's disease,
Parkinson's disease, and prion–associated encephalopathies have been found to share fibril formation as the common
cause. Here, we investigate the influence of dissolved osmolytes (sugars) on the kinetics of insulin fibrillation. In the
presence of sugars, the fibrillation process (both the lag-time and the rate constant to form fibrils) is delayed and
appears to correlate with the heats of solution at infinite dilution thereby supporting a preferential exclusion mechanism.
With the recent focus on circular protofibrils and the suspicion that they may be toxic during amyloidosis, we have
conducted a series of exploratory experiments during the lag phase when protofibrils are thought to be formed. This has
included the use of small angle neutron scattering, sucrose gradient centrifugation, and cryo-electron microscopy to
investigate the kinetics of protofibrils formation. We also present a mathematical mechanistic model that simulates the
phenomena by incorporating the physical chemistry of nucleation and growth dynamics. Estimated by nonlinear least
square algorithms, we find rate constants that account for the ubiquitous sigmoidal responses of amyloidogenic proteins

when they misfold.
261. Structural characterization of polyelectrolyte-protein coacervates by DLS and neutron

scattering
A. Basak Kayitmazer 1 , Paul L. Dubin1 , H. Bohidar2 , Yajuan Li 1 , Christophe Tribet 3 , Sergey Vasenkov 4 , Shengqin
Wang5 and Jiang Zhao5 , (1)University of Massachusetts, Amherst, MA, (2)Jawaharlal Nehru University, New Delhi,
India, (3)ESPCI, Paris, France, (4)University of Florida, Gainesville, FL, (5)Chinese Academy of Sciences, Beijing,
China
Polyelectrolytes in the presence of oppositely charged small colloids may exhibit soluble complex formation or
precipitation, but an intermediate state of hydration involves the formation of a macroion-rich second liquid phase.
These dense, optically clear and often viscous coacervates exhibit unusual rheological and transport properties, in
particular colloid translational diffusivities that are remarkably large given the large macroscopic viscosities. For
coacervates of a protein (BSA) with polycations, dynamic light scattering and neutron scattering both provide evidence
of mesophase separation on the scale of a few hundred nm, a phenomenon also consistent with the results from a
number of other techniques (Cryo-TEM, rheology, FRAP, PFG-NMR and FCS). Marked differences between protein-
polyelectrolyte coacervates and micelle-polyelectrolyte coacervates correspond to different types of mesophases. In the
case of polyelectrolyte-protein coacervates, coacervate properties and stability are strongly influenced when chitosan
replaces PDADMAC, a synthetic polycation with the same structural charge density but smaller persistence length. For
chitosan-BSA coacervates, SANS clearly indicated the presence of a fractal structure in the range q<0.06 (1/nm).
Possible origins of mesophase structures will be discussed.
262. Development and evaluation of realistic microbioassays in freely suspended droplets

on a chip
Vinayak Rastogi and Orlin D. Velev, North Carolina State University, Raleigh, NC
We present a new biomolecular detection technique performed in microliter droplets freely floating on the surface of
perfluorinated oil. The droplets are captured and transported by dielectrophoresis using an electrode chip submerged in
the oil. Each droplet serves as a container where microbioassays are performed using the process of agglutination of
antibody-coated particles in the presence of analyte. Evaporation leads to the rapid collection of particles in the top
portion of droplets. The results are read out by the pattern of unaggregated gold nanoparticles collected on the droplet
surface (see Figure). We demonstrate and discuss two formats of microbioassays - GOAgg (Gold Only Agglutination)
and GLAgg (Gold Latex Agglutination). The performance of these microbioassays was evaluated by varying analyte
concentration, particle concentration and size, number of antigen binding sites per particle, incubation time and rate of
particle collection. Microbioassays for Ricin were designed and their performance was compared to the standard hand
held assays employed in biological defense. Our droplet microbioassays were found to be 10 times more sensitive in
terms of analyte concentration while requiring 100 times less sample volume. We developed a model for the
agglutination kinetics and mass transfer process taking place within the droplets, which correlates well with the
experimental data. These results could facilitate the development of immunoassays on a chip requiring even smaller
sample volumes.
263. Optimizing the dispersion of DNA-linked aggregates at a fixed temperature

Christopher K. Tison and Valeria T. Milam, Georgia Institute of Technology, Atlanta, GA
The controlled assembly of micron to nano-sized colloids using DNA has generated great interest in the past decade;
however, dispersion of these aggregates is currently achieved using temperature changes. By controlling the number
and affinity of duplexes between surfaces, weak, but complete particle aggregation is induced through primary

hybridization events. This aggregated suspension can then be redispersed through the addition of longer, competitive
secondary targets with greater propensity for duplex formation than the primary target. The efficiency of competitive
hybridization events is based upon the length of both the primary and competitive targets, the concentration of DNA
linkages between particle surfaces, and the accessibility of the surface duplexes to the competitive target. To minimize
the number of DNA linkages while simultaneously allowing competitive targets greater access, a system was developed
whereby restriction endonuclease AluI clips non-hybridizing or diluent strands immobilized to the surface. This approach
allows precise control on the surface coverage of active hybridizing probe while still obtaining the benefits of shorter
diluent strands with less steric hindrance. To the best of our knowledge, this study is the first to examine using DNA
hybridization events to both aggregate and disperse colloidal particles at a fixed temperature.
264. Amphiphilic block copolymer surface modification of nanoscale zero valent iron (NZVI)
for source zone DNAPL remediation
Kevin M. Sirk, Navid B. Saleh, Tanapon Phenrat, Hye-Jin Kim, Gregory V. Lowry and Robert D. Tilton, Carnegie
Mellon University, Pittsburgh, PA
Dense non-aqueous phase liquids (DNAPLs), such as trichloroethylene (TCE), are a persistent source of mobile
contamination at thousands of sites in the U.S. Current remediation technologies such as “pump and treat” only target
the dissolved phase plume, leaving the majority of the source pollutant intact. Nanoscale zero valent iron (NZVI)
particles have been shown to effectively dechlorinate TCE, but their poor colloidal stability and transport properties limit
their effectiveness as in situ treatment agents. Modifying the surfaces of these nano-iron particles could allow for an
aggressive source-zone targeting approach that should expedite site clean and lower cleanup costs. Using atom
transfer radical polymerization (ATRP), we have synthesized poly(methacrylic acid)-b-poly(methyl or butyl
methacrylate)-b-poly(styrene sulfonate) triblock copolymers as NZVI coatings. Adsorption of these triblock copolymer
amphiphiles on NZVI significantly enhances NZVI colloidal stability. Using quartz crystal microgravimetry (QCM) and
ellipsometry, we monitor the adhesion of NZVI particles with several different block copolymer surface modifiers on to
silica under varying ionic strength conditions that mimic those found in groundwater. In addition to stabilizing colloidal
suspensions, the polymeric coatings effectively eliminate NZVI adhesion to silica. The effect of silica hydrophobization
on nano-iron adhesion will also be addressed to estimate the ability of the block copolymer coatings to promote NZVI
adhesion on DNAPL (oil)/water interfaces.
265. Effects of the discrete Nature of Charge on the Behavior of Colloidal Particles in
engineered and natural Environments
Patricia L. Taboada-Serrano, Georgia Institute of Technology, Oak Ridge, TN, Sotira Yiacoumi, Georgia Institute of
Technology, Atlanta, GA and Costas Tsouris, Oak Ridge National Laboratory, Oak Ridge, TN
Colloidal particles are ubiquitous in natural and engineered environments. Processes like filtration, deposition,
aggregation, transport of colloidal particles and associated chemical species, phase behavior of colloidal suspensions,
and organization of large biomolecules such as DNA are governed by colloidal interactions. Traditionally, these
interactions have been described by the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. In the DLVO theory,
colloidal particles are modeled as uniformly charged surfaces embedded in solutions containing non-interacting ions that
lack size. Although the DLVO theory can be applied to cases within certain restrictions, many deviations between
experimental observations and theoretical predictions have been reported in the literature. For example, it has been
reported that deposition and remobilization of colloidal particles takes place at conditions predicted as unfavorable by
the DLVO theory. The effects of lifting the DLVO theory assumption of continuous charge is examined via a
combination of molecular modeling and atomic force microscopy in this work. The formation of the EDL, interactions of
approaching EDLs, and development of surface charge in solutions containing symmetric and asymmetric electrolytes
are investigated. Phenomena such as size exclusion effects, like-charge attraction, and surface charge heterogeneities,
not predicted by the DLVO theory, were detected by just considering the discrete nature of surface charge and charge
distribution within the EDL. The occurrence of these phenomena provides a plausible explanation for the deviations
between theory and experiments reported in the literature.
266. Pore Scale Simulation of Colloid Transport in Porous Media with COMSOL Multiphysics
Mehmet E. Cakmak1 , Yuniati Zevi 1 , Veronica L. Morales 1 , Daniel R. Fuka1 , Bin Gao 1 , John L. Nieber 2 and Tammo S.

Steenhuis1 , (1)Cornell University, Ithaca, NY, (2)University of Minnesota, St Paul, MN
Governing mechanisms in immobilization and mobilization of colloids in the unsaturated zone are not well understood.
Recent findings show that colloids attach to the air-water-solid (AWS) interface. The interaction of the various forces
and the flow field on colloids near the AWS interface is complex. In this presentation, we will determine the interaction
force conditions for attachment of colloids to the AWS for flow fields consisting of flow around solid grains in the
presence of and air-water system of fluids. The flow field is determined using COMSOL-MP to numerically solve the
Navier-Stokes equations. The viscous drag force for the moving fluid on the colloids is then quantified from this
numerical solution and the balance of this force with other field forces resulting from interfaces (solid-liquid and liquid-
air) is computed to determine the potential for attachment of colloids to the AWS interface. For the present study
spherical solid grains are considered, while in future studies we will consider solids grains of more realistic shape.
268. Influence of Humic Acid on the Aggregation Kinetics of Fullerene (C60 ) Nanoparticles
Kai Loon Chen and Menachem Elimelech, Yale University, New Haven, CT
Buckminsterfullerene C 60 is a nanomaterial with potential applications in the fields of optics, electronics, and biomedical
engineering. With the impending widespread utilization of fullerene in industrial and consumer products, fullerene
pollution of natural aquatic systems may become a major concern. Under aqueous conditions, hydrophobic fullerene
molecules bind strongly together to form negatively charged fullerene nanoparticles. To better understand the fate and
transport of these nanoparticles in natural aquatic systems, we investigate their aggregation kinetics in the presence of
Suwannee River humic acid and common monovalent and divalent electrolytes. In the absence of humic acid, the
aggregation behavior of the fullerene nanoparticles in the presence of sodium, magnesium, and calcium ions was
consistent with the classic DLVO theory. In the presence of humic acid and sodium or magnesium ions, humic acid
adsorbed onto the fullerene nanoparticles resulting in steric repulsion, which stabilized the nanoparticle suspension.
This increase in the nanoparticle stability was similarly observed in the presence of humic acid at low calcium ion
concentrations. However, enhanced aggregation occurred at higher calcium concentrations. Light scattering
measurements and TEM imaging of the fullerene aggregate structures indicated that bridging of the fullerene
nanoparticles and aggregates by the humic acid aggregates was the likely mechanism for the enhanced aggregation.
267. The role of colloids on the migration of air bubbles in porous media
ABSTRACT WITHDRAWN
The transport of colloids in subsurface environments has been investigated extensively in the last decade. Suspended
colloids in soil water or groundwater can be contaminants themselves and/or can serve as carriers of sorbed
contaminants on them. The presence of air-water interface in porous media can be an additional consideration when
the porous media is unsaturated. Therefore, the understanding the effect of air phase and colloid/air-water interface
interaction is needed to predict the movement of air phase and colloid transport in unsaturated porous media.
The movement of air phase in porous media can take place either as a continuous air phase or discrete air bubbles.
However, the present research focused on continuous air phase assumption and mass balance equations of individual
phases rather than taking into account the movement of air bubbles and colloid capture on discrete air-water interfaces.
This study presents a pore-scale study to model the migration of discrete air phase in the presence of bio/solid colloids
captured on air-water interface. The model is based on the pore-scale balance equation for forces acting on a bubble
rising in a porous medium in the presence of colloids. A dimensional analysis of the phenomenon is also conducted to
provide a more generalized methodology to evaluate the effect of individual forces acting on an air bubble. The
resulting governing equation is solved to predict the rise velocity of bubbles under a variety conditions.
269. Precipitation and aggregation of ZnS nanoparticles in the presence of thiol ligands
Heileen Hsu-Kim, Duke University, Durham, NC
ZnS and other metal-sulfide nanoparticles are known to persist as intermediates during precipitation and dissolution of
their respective mineral phases. However, the mechanisms that enable these nanoparticles to persist in surface waters
and sediment porewaters are unknown. Humic substances and other hydrophilic organics can stabilize ZnS
nanoparticles by adsorbing to particle surfaces and preventing aggregation. In this study, the stability of aqueous ZnS

nanoparticles was investigated by assessing the role of low-molecular weight organic ligands (oxalate, serine, cysteine,
and mercaptoacetate) during precipitation of ZnS. Zn(NO3 ) 2 and Na2 S were dissolved (2 uM each) in laboratory
aqueous solutions buffered at pH 7.5 and containing organic ligands. Particle formation and size was monitored over
time by dynamic light scattering. Zn speciation was measured by anodic stripping voltammetry to confirm that Zn was
coordinated to sulfide during the aggregation experiments and was not in the form of dissolved Zn-organic complexes.
The ZnS aggregate growth rates varied by orders of magnitude, depending on the type and concentration of organic
ligand in solution. Growth rates were slowest in the presence of thiol-containing ligands, cysteine and mercaptoacetate.
In contrast, ZnS aggregation rates were generally not affected by oxalate and serine, which contain carboxylate and
amine functional groups. Thermodynamic stability constants for Zn-thiol complexes are greater that those for the other
Zn-organic complexes. Thus, slow aggregation of ZnS nanoparticles may be caused by specific attachment of the thiol
on surface Zn sites. These results indicate that thiol-containing organics are important for stabilizing metal-sulfide
nanoparticles in the aquatic environment.
270. Influence of surface oxides on the aquatic stability, mobility and sorption properties of
carbon nanotubes
Billy Smith Jr., Hyun Hee Cho, Mi Shin, Matthew Hickin, William Ball and Howard Fairbrother, Johns Hopkins
University, Baltimore, MD
Surface oxides may become incorporated onto the surface of a carbon nanotube (CNT) following exposure to oxidizing
agents used in routine laboratory modification/purification strategies and water treatment processes. In aquatic
environments, surface oxides are expected to alter not only the CNT's sorption characteristics towards organic and
heavy metal contaminants but also the CNT's aquatic stability and transport properties. Oxidized CNTs may in fact act
as a Trojan horse, facilitating the unwanted transport of priority contaminate species. Consequently, the effect of
surface oxidation has potentially important environmental health and safety implications for carbon based nanomaterials.
To investigate these issues, a suite of CNTs with different levels of surface oxidation were prepared by refluxing CNTs
in HNO3 solutions of various concentrations; X-ray photoelectron spectroscopy (XPS) showed that the surface oxide
concentration increased from 3% for the pristine nanomaterials to 12.5% for CNTs treated in ~16M HNO3. Studies
conducted over a wide range of aquatic conditions have shown that well-defined relationships exist between the level of
CNT surface oxidation and their aquatic stability; specifically, more highly oxidized CNTs remain stable over a wider
range of aquatic conditions. As the level of surface oxidation increases, the sorption properties of CNTs also displayed
systematic variations: adsorption of 14C labeled-naphthalene decreased linearly while divalent heavy metal
contaminates like Zn2+ showed an increasing affinity towards more highly oxidized CNTs. Preliminary results will also
be presented on the influence that surface oxides exert on the transport properties of CNTs.
271. Influence of Grain Size and Flow Rate on the Transport and Retention of C-60 Fullerene
in Water-Saturated Soils
Yusong Li 1 , Yonggang Wang2 , Linda Abriola 1 and Kurt D. Pennell 2 , (1)Tufts University, Medford, MA, (2)Georgia
Institute of Technology, Atlanta, GA
Widespread production and application of manufactured nanomaterials will inevitably lead to the release of
nanoparticles into the environment. The current understanding of nanoparticle fate and transport in subsurface
environments, however, is quite limited. In this work, we seek to advance our understanding of the transport and
retention of C-60 fullerene (95 nm dia.) in water-saturated soils through a combination of experimental and
mathematical modeling studies. A series of transport experiments was conducted at several pore-water velocities in
glass columns packed with various size fractions of Ottawa sand. Effluent concentration and particle retention data
were simulated using a mathematical model that incorporated traditional filtration theory with rate-limited, nonlinear
surface blocking behavior. The numerical model successfully captured the characteristics of both the effluent
concentration and particle retention profiles. The experimental and simulation results suggest that C-60 fullerene particle
attachment is strongly dependent on porous media surface area and flow rate. Simulated attachment capacity
increased with increasing specific surface area, and for a given sand size fraction, simulated n-C60 attachment rates
were greater at higher flow rates. Extended Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, incorporating van der
Waals, electro-static repulsion, and hydrophobic interaction forces, was used to evaluate potential mechanisms
governing C-60 attachment. This analysis suggests that a sizable energy barrier of about 22 kT exists between C-60
fullerene particles and Ottawa sand surfaces and that there is a very small secondary minimum attraction region with

depth of 0.12 kT. Additional studies are being conducted to further elucidate the forces responsible for n-C60 particle
retention.
272. Slow Dynamics in Biphasic Colloidal Glasses and Gels

Douglas C. Viehman and Kenneth S. Schweizer, University of Illinois, Urbana, IL
Integral equation, simple mode coupling, and activated barrier hopping theories have been combined to study slow
dynamics in “biphasic” binary mixtures composed of hard and sticky spheres of identical diameters. Under structural
equilibrium conditions the theory has been employed to investigate how the addition of repulsive particles modifies the
ideal gelation transition and elastic modulus, and how attractive particles perturb the vitrification of hard spheres. The
total volume fraction dependence of the shear modulus is significantly changed relative to its analogous one-component
behavior. A two-dimensional nonequilibrium free energy controls particle displacements, and the associated transient
localization lengths and barrier hopping processes have been studied as a function of mixture composition and sticky
colloid adhesion strength and spatial range. Barriers for activated transport of the attractive and repulsive particles are
generally very different, implying a strong dynamical asymmetry. The corresponding quenched porous media problems
have also been studied. Ideal colloidal glasses in porous media form at much lower total volume fraction than for the
one-component hard sphere fluid. If the sticky particles are mobile in the quenched media, then very rich dynamical
behavior is found. For example, mobile colloids may undergo an ideal glass transition, an ideal gel transition, or both.
The signature of the latter behavior is a nonequilbrium free energy that acquires two local minima.
273. Cracking and collapse of vesicle depletion gels

Matthew L. Lynch and Tom Kodger, Procter & Gamble Company, Cincinnati, OH
The addition of polymer to a dispersion of vesicles can result in the formation of space spanning depletion gels.
However, the density mismatch between the vesicles and the polymer solution results in a gravitational stress that
leads to the collapse (or compression) of the gels. We have created kinetic phase diagrams in which the rate of
collapse was measured as a function of volume fraction of vesicles, polymer concentration and particle-polymer
asymmetry. At short times, the rate of collapse is framed in terms of the linear poroelasticity which balances viscous,
elastic and gravitational forces on the gel structure. Many of these gels, however, exhibit a curious “cracking” behavior
in which the gel structure fractures into layers, changing the paradigm altogether.
274. Highly oil-swollen Vesicle Gels with elastic Properties
Michael Gradzielski 1 , Claudia Oppel1 , Jens Poppig 1 , Sylvain Prévost 1 and Laurence Noirez 2 , (1)Technische
Universität Berlin, Berlin, Germany, (2)Laboratoire Léon Brillouin, Gif-sur-Yvette, France
Vesicle gels have been investigated that are based on mixtures of classical nonionic surfactants with small amounts of
ionic surfactants. Their rheological properties are largely controlled by the relative content of ionic surfactant in the
mixture and the elastic properties go through a pronounced maximum for relatively low amounts of ionic surfactant
content and depend in a systematic way on the total surfactant concentration. Depending on their composition their
elastic moduli are typically in the range of 50-500 Pa and they have a yield stress of 1-20 Pa. The vesicle gels studied
are able to solubilise large amounts of oils (up to more than 3 times the amount by mass of the surfactant) where the
solubility depends to a large extent on the polarity of the oil and on the relative charge density of the surfactant mixture.
We varied systematically the polarity of the solubilised oil and it is interesting to note that the maximum solubility occurs
for the most hydrophobic oils while it is much less pronounced for more polar oils. The structural characterisation of
these oil-swollen vesicle gels was done by means of static and dynamic light scattering, small-angle neutron scattering,
electric conductivity, NMR self-diffusivity and electron microscopy. The vesicles bilayers are first swollen but for higher
oil content the structure of individual vesicles is transformed into a bicontinuous structure. It is interesting to note that in
that process no macroscopic phase separation takes place and also that the elastic properties are retained.
275. Characterization of a model van der Waals gel system

Ryan C. Kramb and Charles F. Zukoski, University of Illinois Urbana-Champaign, Urbana, IL
Model colloidal systems in which the phenomenon of gelation can be studied by characterizing and varying the strength

and range of the interaction between the particles are not common. Those model systems that are well studied typically
fall into one of three categories – 1) proteins, especially lysozyme, 2) particles experiencing depletion interactions, 3)
and thermal gels composed of ocadecyl coated silica particles. However, in the vast majority of these systems the most
commonly found force resulting in gelation – van der Waals forces, is typically negligible. Our objective is to create a
fourth model system to characterize the phase behavior, microstructure, and gel mechanics in which van der Waals
forces are the dominant cause of the gel formation. In our system, monodispersed polystyrene latex particles 200-
600nm in diameter coated with the surfactant hexaethylene glycol monododecyl ether (C12E6) form gels through
reversible aggregation. Using these particles, we investigate the phase diagram as the back ground ionic strength is
raised. At very low ionic strengths the suspensions crystallize due to electrostatic repulsions. At intermediate ionic
strengths, the suspensions are fluids. At higher ionic strengths, the suspensions gel. The gels are reversible in that if
diluted with an electrolyte solution of the same ionic strength and same surfactant concentration, the gels fall apart and
single particles are observed. We report on the ionic strength-volume fraction gel line and the flow properties of the
suspensions approaching and within the gels. In addition we report on microstructures of the gels determined by small
angle neutron scattering.
276. Nanoparticle-Crosslinked Hydrogels as Separation and Ion Exchange Media

Bani Cipriano, Peter Thomas and Srinivasa R. Raghavan, University of Maryland, College Park, MD
A study of the absorption of ionic solutes using a new class of polymeric hydrogels is reported here. These hydrogels
are crosslinked using clay nanoparticles instead of the traditional crosslinking molecules. Some unique features of these
clay crosslinked gels that distinguish them from their conventional counterparts include larger pore sizes and increased
mechanical integrity. In addition, these particle crosslinked gels can be used as ion exchange resins since the
incorporation of clay nanoparticles introduces charges into the otherwise neutral polymer gel. In particular, these gels
have an extraordinary ability to soak up cationic solutes from solution due to the anionic surface of the clay platelets.
Furthermore, the absorbed molecules bind preferentially around the surface of the gel, leaving the rest of the gel free of
bound species. In contrast to covalently crosslinked gels, these particle crosslinked gels can be disassembled in the
presence of certain organic solvents due to the non-covalent interaction between polymer and particles. Upon
disassembly, these gels release the bound species which can be subsequently recovered. Finally, we describe our
efforts towards the separation of particles such as carbon nanotubes and colloidal silica by size. These separations
cannot be achieved using covalently crosslinked gels since their pore size is much smaller than the size of the particles
of interest.
277. Applications of Scaling Theories and Exact Results to Colloids and Polyelectrolytes
Lesser Blum, Rutgers University, Piscataway, NJ and Melvin Arias, University of Puerto Rico, Rio Piedras, PR
Charged systems obey exact asymptotic relations. Excluded volume for each ion is needed. These are included in the
Mean Spherical Approximation, thus this theory is exact for dense systems. A method that interpolates between the
MSA and the PY equation and is amazingly accurate for many systems (Blum Narten, J. Chem. Phys. 56, 5197
(1972)). The switching was done at a distance s such that all distribution functions were continuous everywhere. In the
present work we extend this theory to the general case of an arbitrary mixture of charged hard spheres, and obtain an
explicit analytical solution in terms of a few scaling parameters G : We use the new extended soft mean spherical
approximation (ESMSA). (Blum Arias, J. Phys. Cond. Matt. 18, S2437,(2006), Mol. Phys. 104,3801,(2006) that also
satisfies the low temperature and low density association limits.
In the ESMSA the closure of the Ornstein Zernike (OZ) equation near the excluded core region is divided in two
regions: For the inner region we can use an exponential closure, for example the Percus-Yevick (PY) or the contact
pair correlation function as derived in the BIMSA-EXP approximation ( Bernard and Blum,J. Chem. Phys. 104,
4746,(1996)). This leads to the correct exact limits of zero temperature and zero density. In the outer region far from
the central ion we use the Mean Spherical Approximation (MSA) closure. An explicit solution is obtained from the
continuity of the pair correlation function when the distances are additive. The thermodynamics and structure functions
are also discussed.
278. Mechanisms of assembly in nanoparticle based materials

Francis W. Starr, Wesleyan University, Middletown, CT

The formation of clusters or specifically ordered structures is common to many materials. We will focus on some
example systems where simulations are able to help elucidate ordering mechanisms. First, we will discuss the origins of
particle clustering in polymer-nanoparticle composites with highly symmetric nanoparticles. Our simulations emphasize
the importance of effective long-ranged polymer mediated interactions between nanoparticles that promote particle
clustering without the intervention of phase separation. Next we discuss how a recent model for assembly of DNA-
dendrimer molecules can be adapted to mimic the behavior of DNA-coated colloids that cluster due to "linker" DNA that
selectively binds the colloids. In this case, the concentration of linker DNA controls the number of bonds that a particle
can form, thereby offering the possibility to form clusters with a low coordination that inhibits phase separation. Lastly,
we will discuss how the interactions between patchy colloidal particles can be modified to promoted the formation of gel
structures on heating.
279. Self-Assembled moth-eye antireflection coatings
Nicholas Linn 1 , Chih-hung Sun 1 , Bin Jiang 2 and Peng Jiang1 , (1)University of Florida, Gainesville, FL, (2)Portland
State University, Portland, OR
Part of the light incident on all transparent materials is reflected. This reflection arises from the abrupt change in the
refractive index at the interface of two media. The cornea of some nocturnal moths has a structure with a repeating
pattern of less than 250 nm and a physical depth of less than 200 nm. These submicrostructured surfaces can greatly
reduce reflection, helping conceal the inset from hungry predators. We report a simple bio-inspired self-assembly
technique for fabricating artificial moth-eye antireflective coatings. Non-close-packed colloidal crystals with remarkable
large hexagonal domains are created by a spin-coating technology, which is based on shear-aligning colloidal silica
particles suspended in non-volatile triacrylate monomers. The resulting polymer-embedded colloidal crystals exhibit
highly ordered surface modulation and can be used directly as templates to cast poly(dimethylsiloxane) (PDMS) molds.
Polymer (e.g., PMMA and polystyrene) and glass antireflective coatings can then be molded against PDMS using
traditional polymerization and sol-gel technologies. The depth of the micropatterns can be adjusted by plasma-etching
of the original colloidal crystal-polymer nanocomposite. Using the above colloidal self-assembly and micromolding
techniques, large-area (up to 8-inch diameter, limited only by the substrate size) moth-eye antireflective coatings have
been created on both planar and curved substrates. The microstructured coatings exhibit much lower reflectivity than
bare films and the optical reflection matches with the theoretical prediction using effective medium theory.
280. Crystalline monolayers from convectively self-assembled non-spherical colloids

Ian D. Hosein and Chekesha M. Liddell, Cornell University, Ithaca, NY
Self-assembly of submicron particles into colloidal crystal structures offers a rapid, tunable and scalable process for
creating spatially periodic templates for nano-fabrication, micro-lens arrays and photonic crystals. Theoretical
calculations have shown that colloidal crystals from non-spherical particles could allow robust and complete photonic
bandgaps to open at lower refractive index contrasts, allowing a wider range of materials to be accessible for
fabrication. In the present work, 2D structures with a high degree of positional and orientational order from mushroom-
cap, pear and peanut shaped colloids were fabricated via convective assembly. Structure-optical property correlations
were made using SEM and optical diffraction spectroscopy. The ordered assembly process will be explained with
respect to particle concentration, solvent surface tension at the drying front, and geometric packing efficiency. The
structures were modeled using the diffraction grating equation. Structural phases were examined with thermodynamic
models from Monte Carlo simulations. Transitions between isotropic and ordered phases were followed using the
simulated osmotic pressure versus density curve and by visualization of the equilibrated system from the simulations.
281. Shape Selectivity in the Assembly of Lithographically-Designed Colloidal Particles
Stephane Badaire1 , Cecile Cottin-Bizonne2 , Joseph W. Woody 1 , Allen Yang 1 and Abraham D. Stroock 1 , (1)Cornell
University, Ithaca, NY, (2)Université Claude Bernard Lyon 1, Villeurbanne, France
The formation of a diversity of structures via the assembly of colloidal particles is hindered by the paucity of available
particles, the difficulty of attaining monodisperse samples, and the lack of tunable and selective interactions. We will
present the development of a controlled colloidal system based on photolithographically-designed particles of well-
defined size and non-spherical shape. We will discuss the fabrication and characterization of these particles and the
formation of controlled dispersions. With state diagrams (see figure - volume fraction of depletant vs. ionic strength) we

will elucidate the role of DLVO and depletion interactions in defining a diversity of assemblies. Finally, we will present
comparisons to theory and comment on the influence of surface roughness and steric stabilization in controlling the
observed phenomena.
282. Molecular Dynamics Simulation of Nanoparticle Self-Assembly at a Liquid-Liquid

Interface
Mingxiang Luo1 , Oleg A. Mazyar2 , Qing Zhu 2 , Mark W. Vaughn2 , William L. Hase 2 and Lenore L. Dai 2 , (1)Texas
Tech Umiversity, Lubbock, TX, (2)Texas Tech University, Lubbock, TX
We have used molecular dynamics simulations to investigate the in-situ self-assembly of modified hydrocarbon
nanoparticles (mean diameter of 1.2 nm) at a water-trichloroethylene (TCE) interface. The nanoparticles were first
distributed randomly in the water phase. The MD simulation shows the in-situ formation of nanoparticle clusters and the
migration of both single particles and clusters from the water phase to the trichloroethylene phase, possibly due to the
hydrophobic nature of the nanoparticles. Eventually, the single nanoparticles or clusters equilibrate at the water-TCE
interface, and the surrounding liquid molecules pack randomly when in contact with the nanoparticle surfaces. In
addition, the simulations show that the water-TCE interfacial thickness analyzed from density profiles is influenced by
the presence of nanoparticles either near or in contact with the interface but is independent of the number of
nanoparticles present. The nanoparticles, water molecules, and TCE molecules all exhibit diffusion anisotropy.
283. Co-Assembly of non-spherical colloids and nanoparticle depletants

Trina Ghosh Dastidar, Ian D. Hosein, Poorna Rajendran, Ulrich Wiesner and Chekesha M. Liddell, Cornell University,
Ithaca, NY
Several frontiers in photon-atom interaction require the development of inexpensive fine-scale and structurally complex
periodic materials. For example, the crystal structure and shape/complexity of photonic crystal bases greatly influences
the capability of the materials to exhibit superior electro-optic properties. The potential to alter the dynamics of
spontaneous emission processes has implications for the enhancement of photocatalytic reactions, which play an
important role in environmental remediation strategies, as well as for more efficient photovoltaic and solar cell devices.
Here, we study self-assembly of non-spherical mushroom-cap shaped colloids into ordered photonic crystal structures,
aided by fluorescent nanoparticle depletants. Core-shell nanoparticles (~30 nm in diameter) consisting of the organic
fluorophore tetramethylrhodamine isothiocyanate (TRITC) encapsulated in a silica shell were co-assembled with
polystyrene non-spherical particles using a convective approach. Colloidal phases were determined as a function of the
concentration ratio of nanoparticles to non-spherical colloids. The modification of dye emission characteristics due to
changes in the local density of photon states was explored in the reduced symmetry photonic crystal system (based on
mushroom-cap basis) and compared with similar effects in a simple sphere based photonic crystal.
284. Shear-aligned assembly of colloidal photonic crystals

Peng Jiang, University of Florida, Gainesville, FL

A versatile spin-coating technique for assembling wafer-scale colloidal photonic crystals, along with a large variety of
functional nanostructured materials has been developed. The methodology is based on shear-aligning concentrated
colloidal suspensions using standard spin-coating equipment. It enables large-scale production of both 3D and 2D non-
close-packed colloidal crystals as well as a wide range of nanostructured materials including 3D ordered polymer
nanocomposites, macroporous polymers, nanohole arrays, metallic surface gratings, attoliter microvial arrays, 2D
magnetic nanodots, metallic pyramid arrays, and more. The spin-coating platform is compatible with standard
semiconductor microfabrication, enabling parallel production of micropatterns for potential device applications. The spin-
coating process also provides a new route to study the fundamental aspects of shear-induced crystallization, melting
and relaxation. Different from simple shear flows in conventional shear cells, the flow in the spin-coating process is
inherently non-uniform. The application of assembled periodic nanostructures as surface-enhanced Raman scattering
(SERS) substrates will also be discussed.
285. Stability characterisation of nanoparticles Dispersion

Helene Dihang, Formulaction, L'Union, France and Jim Munhall, Sci Tec, Worthington, OH
The applications of nanoparticles in the industry are getting more and more important and concern many different fields
(drug delivery, nanotubes, screen technologies, etc.). In the last decades a vast amount of scientific research has been
developed to improve the understanding of these complex dispersions. Using a scientific approach and new analytical
techniques, it is now possible to control and tailor properties of suspensions and to get a better understanding of time
behaviour. Following this idea, stability measurements, which were commonly done by simple visual observations, can
now be performed automatically via an optical device.
This instrument is based on Multiple Light Scattering (MLS) and is associated to a vertical scanning of the sample. It is
like a high resolution electronic eye, enabling to identify and quantify instability phenomena before they are visible to
the operator (5 to 50 times earlier than the naked eye). Physical parameters and kinetics can be computed in order to
facilitate and improve comparisons between formulations. Moreover, it is possible to use the information contained in
the MLS signal to extract parameters such as particle mean diameter without the need of dilution, as often required with
diffraction techniques based on single scattering models. This measurement can be done on the finished product or, in
real time, during the process.
286. Trichloroethylene remediation using nanoscale Fe/silica aerosol particles

Tonghua Zheng, Jingjing Zhan, Jibao He, Gerhard Piringer, Gary L. McPherson, Yunfeng Lu and Vijay T. John,
Tulane University, New Orleans, LA
We describe a novel assisted aerosol process to prepare porous silica particles containing nanoscale zerovalent iron
which is a reactive species for the reduction of trichloroethylene (TCE). The environmentally benign silica particles
serve as effective carriers for nanoiron transport through soil. Encapsulation of iron into submicron silica particles
protects ferromagnetic iron nanoparticles from aggregation, and increases their mobility through sediments. Additionally,
the presence of surface silanol groups on silica particles makes it possible to control surface properties via silanol
modification using organic functional groups. Aerosol silica particles with functional groups such as ethyl tails on the
surface preferentially absorb hydrophobic TCE during environmental remediation. This increases the local concentration
of TCE in the vicinity of iron nanoparticles, thus promoting the degradation of TCE by iron. These nanoscale iron/silica
aerosol particles with controlled surface properties can be efficiently applied for in-situ remediation and permeable
reactive barriers construction.
287. Nano-emulsion preparation by low energy methods: studies on optimization and scale-
up
E. Beltran 1 , C. Pey 1 , A. Maestro1 , C. Gonzalez1 , Conxita Solans2 and J.M. Gutierrez 1 , (1)University of Barcelona,
Barcelona, Spain, (2)IIQAB, CSIC, Barcelona, Spain
Nano-emulsions are a class of emulsions with fine droplet size. Nano-emulsions with smaller droplet size can present
an aspect similar to microemulsions, but, as fundamental difference, nano-emulsions are not thermodynamically stable,
and, because that, their characteristics will depend on preparation method. In the so called low energy methods, fine
dispersion is obtained by chemical energy resulting of phase transitions taking place through emulsification path. The

adequate phase transitions are produced by varying the composition at constant temperature or by varying the
temperature at constant composition, phase inversion temperature method (PIT). In present work, an experimental
study about the influence of preparation variables, addition rate and agitation velocity, on nano-emulsions obtained by
varying composition method by water addition is carried on. The study is applied to two different systems with water as
continuous phase: Brij30/Brij97 as surfactants and isopropylmiyristate as oil; and span20/tween20 as surfactants and
liquid pararaffin as oil. Mean diameter of droplets is determined by dynamic light scattering. Preparation is carried out at
two different scales, 0.1 a 1.0 L, and in each experiment water addition rate and agitation velocity are fixed following
experimental designs. Results are fitted to give mean diameter of nano-emulsion droplets as a function of significant
terms of preparation variables. For small scale there is an optimum agitation velocity, while the lower the addition rate
the smaller droplet diameter. For 1.0 L scale droplet diameter is smaller than for smalls scale and does not present
significant variations with preparation variables.
288. Surface forces measured between gold surfaces coated with self-assembled
monolayers of thiols and xanthates in water
Roe-Hoan Yoon, Jan Christer Eriksson and Jialin Wang, Virginia Tech, Blacksburg, VA
Many investigators measured the forces between two hydrophobic surfaces in water, and observed long-range
attractions that were stronger and longer-ranged than the van der Waals attractions. Some believe that the stronger
attractions are due to structuring of water in the vicinity of hydrophobic surfaces, while others believe that they are
caused by nano-bubbles or by the correlation of mobile charged patches (or domains). The latter mechanism is possible
when using ionic surfactants that can physisorb and form mobile patches of self-assembled monolayers. In the present
work, AFM force measurements were conducted between gold surfaces coated with chemisorbing hydrophobizing
reagents such as n-alkane thiols and n-alkane xanthates. The equilibrium water contact angles of the treated surfaces
were in the range of 66 and 105o. In most cases, the force vs. distance curves exhibited long-range attractions with
decay lengths in the range of 16.5 and 26.0 nm. The force curves were smooth and showed no discontinuities (or
steps), excluding the possibility of nano-bubbles being responsible for the long-range attractions observed in the
present work. Based on the results obtained in the present work, possible origins of the long-range attractions will be
discussed.
289. Nano-emulsion preparation by the phase inversion composition method (PIC) in the
cationic system W / oleylammonium chloride - oleylamine - C12E10 / hexadecane
Isabel Solè 1 , Carmen Gonzalez 1 , Alicia Maestro1 , J.M. Gutierrez 1 and Conxita Solans2 , (1)University of Barcelona,
Barcelona, Spain, (2)IIQAB, CSIC, Barcelona, Spain
Nano-emulsions are a type of emulsions with droplets of very small diameter (20-500 nm). They are used in many
different applications related to chemical, pharmaceutical, and cosmetic fields. Their preparation methods can be
classified in two types: the dispersion or high-energy methods, in which mechanical energy is required to form them;
and the condensation or low-energy methods, which make use of the phase transitions that take place during the
emulsification process. In the present study, the low-energy emulsification method phase inversion composition (PIC)
has been used to prepare nano-emulsions in the system W / oleylammonium chloride - oleylamine - C12E10 /
hexadecane by addition of chlorhidric acid solutions in the mixtures formed by water, oleylamine, C12E10 and
hexadecane. In this way, the oleylammonium formed along the emulsification path acts as the cationic surfactant. The
results obtained, in terms of phase diagrams and nano-emulsion characteristics, are compared with those obtained in
the system with oleate as anionic surfactant and oleic acid as a cosurfactant. This study has been done in order to
extend the application range of the ionic nano-emulsions, not only in anionic systems, but also in cationic ones.
290. Effects of Aggregate Structure on Gelation and Mechanical Properties of Silane-based

Sol-gel Coatings
Saran Poovarodom, Jiong Liu and John Berg, University of Washington, Seattle, WA
Silane-based sol-gel coatings are commonly used as adhesion promoters. It is desirable to enhance the mechanical
properties of these materials by reinforcing them with nanoparticulates, particularly oxide particles. Aggregation of the
reinforcing particles is often associated with poor mechanical properties of the material. In this study, we evaluate the

effect of the degree of aggregation of reinforcing oxide particles on the mechanical properties of
glycidoxypropyltrimethyloxysilane (GPS) sol-gel coatings. The degree of aggregation is controlled by adjusting the
surface electronic properties of the particles using tetrasodium pyrophosphate (TSPP), which specifically adsorbs to the
particle surfaces. It is found that at small degree of aggregation (n aggregate < 50 primary particles), there is only a
negligible effect on the gel mechanical properties. However, large, loose aggregates caused by a more rapid
aggregation leads to incoherent coatings with numerous cracks. This is a result of the participation of the oxide
particles in the GPS gel network. Therefore, the structure of the gel formed is regulated by the structure of the oxide
aggregates present. Large, loose aggregates lead to a formation of a weak, low-density gel that is susceptible to
cracking during the drying process and poor mechanical properties.
291. A mathematical approach to calculate the precision and relative differences of various
relationships available to determine the surface tension of polymeric materials
Samad Ahadian, Siamak Moradian and Mohammad Amani Tehran, Amirkabir University of Technology, Tehran, Iran
The surface tension of polymeric materials commonly varies in the range 20-50 mJ/m2. Knowing this fact, the contact
angles of 31 polymeric materials were varied with four probe liquids (i.e. diiodomethane, formamide, glycerine and
water) in 1 mJ/m2 increment in the mentioned range by the aid of the equation of state (i.e. Neumann's equation). All
the 11 possible 2, 3 and 4 combinations of the liquid mixtures were used. The obtained contact angles were then
employed to calculate the corresponding surface tensions using different approaches such as the Owens/Wendt, the
harmonic mean, the van Oss et al. and the combined mean relationships. Additionally, the differential forms of the
mentioned relationships were used to rank the precision of each approach. The results illustrated that the relative
differences between the predicted surface tensions obtained from each approach as compared to the equation of state
were strongly dependant on the liquid system used. The predicted surface tensions calculated by the Owens/Wendt,
the harmonic mean, the van Oss et al. and the combined mean relationships were generally lower than the
corresponding values as calculated by the equation of state for low values of surface tension. This behavior was
inversed for the upper range of surface tension. Furthermore, the precision ranking of these relationships were in the
order of the equation of state> the harmonic mean> the combined mean> the Owens/Wendt> the van Oss et al.
292. NanoTextured Surfaces for the Sensing and Manipulation of Colloidal Scale Objects in
Microscale Flow
Ranojoy Dipak Duffadar 1 , Jeffrey M. Davis 1 and Maria Santore 2 , (1)University Of Massachusetts, Amherst, Amherst,
MA, (2)University of Massachusetts,, Amherst, MA
Selective tuning of the sizes, surface densities, and chemistries of 10-nanometer scale heterogeneities on planar
surfaces that interact with colloidal objects in shear flow allows control of the adhesion of the colloidal particles.
Motivated by the need to develop artificial pattern recognition constructs for microfluidic sensor applications, systems
have been developed that exhibit tunable dynamic behavior on renewable surfaces, which allows colloidal objects to be
distinguished by their characteristic adhesion signatures and rates. Adhesion is reversible in a substantial portion of
parameter space, and surface features can give rise to particle skipping and rolling on the surfaces. These dynamics
are captured by a new model that incorporates both hydrodynamic forces on the particles and the spatially varying
physicochemical interactions between the particles and heterogeneous surfaces. The adhesion is governed by the
matching of the length scales of the patch spacing and the interactive surface area between the particle and surface,
which is reminiscent of pattern recognition, although the patch distribution on the collector is random. Spatial
fluctuations in the patch density are shown to play a critical role in the dynamic adhesion and rolling behavior (e.g.,
allowing adhesion on a net-repulsive surface), which prevents this behavior from being predicted by a mean-field
approach. This talk highlights new developments in the experimental and modeling efforts and focuses on the
fundamental dynamics of particle interaction with these sensing surface features in shear flow at low Reynolds number.
293. Imaging Energy Landscapes with Concentrated Diffusing Colloidal Probes

Pradipkumar Bahukudumbi, Gregory E. Fernandes and Michael A. Bevan, Texas A&M University, College Station, TX
The ability to locally interrogate interactions between colloidal particles and energetically patterned surfaces provides
essential information to design, control, and optimize template directed self-assembly processes. Although numerous

techniques are capable of characterizing local physicochemical surface properties, no current method resolves
interactions between colloids and patterned surfaces on the order of the thermal energy kT, which is the inherent
energy scale of equilibrium self-assembly processes. In this talk, we describe video microscopy measurements and an
inverse Monte Carlo analysis of diffusing colloidal probes as a means to image three dimensional free energy and
potential energy landscapes due to physically patterned surfaces. In addition, we also develop a consistent analysis of
self-diffusion in inhomogeneous fluids of concentrated diffusing colloidal probes on energy landscapes, which is
important to the temporal imaging process and to self-assembly kinetics. Results of Monte Carlo and Brownian
Dynamics simulations will also be reported to verify the analysis and interpretation of experimental findings. Extension
of the concepts developed in this work suggest a general strategy to image multi-dimensional and multi-scale physical,
chemical, and biological surfaces using a variety of diffusing probes (i.e. molecules, macromolecules, nanoparticles,
colloids).
294. Coulomb Interactions in a Non-Polar Colloid

Sunil K. Sainis and Eric R. Dufresne, Yale Univeristy, New Haven, CT
We directly measure the electrostatic interaction between isolated pairs of microspheres (PMMA-PHSA) in solutions of
surfactant (NaAOT) in oil(hexadecane). At high surfactant concentrations, we find the familiar screened Debye-Huckel
form. However, at low concentrations of surfactant, we see an unscreened Coulomb potential. Our measurements
extract the particle charge and solvent ionic strength. We also study the particle charge as a function of bead size.
295. Effective interactions between like-charged colloids

Erik Luijten, University of Illinois at Urbana-Champaign, Urbana, IL
The effective attraction between like-charged colloids, as induced by multivalent counterions, has been the subject of a
variety of computational and theoretical investigations. Nevertheless, the topic is far from controversial, with
contradictory predictions and limited experimental observations. A major numerical complication is the dynamic
slowdown resulting from the large size asymmetry between the colloids and their counterions. We overcome this
problem by extending the generalized geometric cluster algorithm for colloidal suspensions to systems with electrostatic
interactions. Using this highly efficient method, we are able to study the onset of like-charged attraction as a function of
colloid size. Theoretical considerations for planar geometries predict that the minimum required colloidal charge
increases quadratically with colloid size, whereas strong-coupling theory predicts a linear relation. We resolve this
controversy by spanning a sufficiently large range in colloidal diameter. Furthermore, we demonstrate important
qualitative changes in the potential of mean force as the colloid size is increased.
296. Direct measurements of the effects of surfactant on interaction forces between

colloidal particles at the decane-water interface
Bum Jun Park 1 , Jan Vermant 2 and Eric M. Furst1 , (1)University of Delaware, Newark, DE, (2)Katholieke Universiteit,
Leuven, Belgium
The pair interactions of polystyrene particles were measured at the decane-water interface using laser tweezers. In the
absence of sodium dodecylsulfate (SDS) in the aqueous subphase, the particle interactions show a long-range
repulsion, consistent with models proposed by Hurd [1] and Aveyard et al. [2, 3]. As SDS is added to the sub-phase,
the repulsive force between particles decreases. Surprisingly, we find that the repulsive interactions also decrease with
time at fixed surfactant concentrations. This provides a possible mechanism for the reported flocculation behavior of 2D
suspensions [4]. Finally, as the repulsion decreases, a long-range attractive force emerges, creating a secondary
minimum in the potential. The attractive interaction is consistent with attractive capillary forces between particles.
Overall, our experiments demonstrate the richness of particle interactions at the oil-water interface, which can be
tailored to alter the stability and interfacial rheology of 2D systems.
[1] A. J. Hurd, J. Phys. A: Math. Gen. 1985, 18, L1055. [2] R. Aveyard et al. Langmuir, 2000, 16, 1969. [3] R. Aveyard
et al. Phys. Rev. Lett. 2002, 88, 246102-1. [4] S. Reynaert et al. Langmuir, 2006, 22, 4936.
297. Interactions between star polymers: Microspheres grafted with filamentous phage virus

Phil F. Huang 1 , Seth Fraden 1 , Karim Addas2 and Zvonimir Dogic 2 , (1)Brandeis University, Waltham, MA, (2)Rowland
Institute of Harvard, Cambridge, MA
We genetically engineered M13 bacteriophage, a long filamentous particle that forms liquid crystalline phases, and
coupled biotin groups to one end of the virus. Biotinylated virus particles were then conjugated to streptavidin-coated
polysterene spheres to form star complexes. The interparticle potential was measured between pairs of polystyrene
beads grafted with phage particles using an optical tweezer, and their behaviour in nematic M13 virus suspensions was
also studied.
298. Melting and Fluctuations in Two-dimensional Colloid Crystals and Colloidal ‘Anti-
Ferromagnets'
Yilong Han, University of Pennsylvania, Philadelphia, PA
We use digital video microscopy to investigate melting of colloidal crystals under strong 2-dimensional (2D) confinement
and frustrated colloidal ‘anti-ferromagnets' in weak 2D confinement. Our samples are composed of NIPA (N-isopropyl
acrylamide) microgel spheres whose diameter can be temperature-tuned, and whose pair potentials were measured to
be short-ranged and repulsive. The melting experiments revealed two first-order-like transitions from crystal to hexatic
phase and hexatic to liquid phase as a function of temperature-tunable volume fraction. The divergences of
translational and orientational susceptibilities were used to determine the phase transition points. This approach avoids
ambiguities inherent in other analyses and resolved a novel premelting stage in the crystal that traditional analyses
incorrectly associate with the hexatic phase. We will also show how these novel microgel spheres can be made to
mimic the behavior of frustrated anti-ferromagnets. In this case, we measured statistics of frustrated bonds and
collective fluctuations of the degenerate system in space and time. This work was carried out in collaboration with
Ahmed Alsayed, Na Young Ha and Arjun Yodh with support from the NSF (MRSEC DMR-0520020 and DMR-
0505048). I also thank Tom Lubensky and Yair Shokef for helpful discussions.
299. Keynote: Microscopic Theory of the Rheology of Colloid and Nanoparticle Glasses and
Gels
Kenneth S. Schweizer, University of Illinois, Urbana, IL
A microscopic statistical dynamical theory for the effect of deformation on the transient localization, shear modulus,
relaxation time, viscosity and other dynamic properties of glassy colloidal suspensions and entropic depletion gels has
been developed. The approach is built on single particle activated barrier hopping on a nonequilibrium free energy
profile as the elementary physical process in quiescent systems. External deformation distorts the confining free energy,
weakens the caging constraints, and accelerates dynamics. The roles of mechanically driven motion and thermally
activated flow have been studied. For glassy hard sphere suspensions power law and/or exponential dependences of
the modulus and yield stress on colloid volume fraction are predicted. For polymer-particle suspensions the caging
constraints and physical bond strength are quantified using PRISM integral equation theory. The absolute yield stress
collapses onto a universal master curve as a function of polymer concentration when scaled by its value at the ideal
mode-coupling theory nonergodicity transition, and sufficiently deep in the gel is of a power-law form with a universal
exponent. The volume fraction dependence also exhibits such scaling but with a nonuniversal exponent. The theory has
also been applied to thermal gels composed of colloids with sticky brush layers. Generalization of the approach to
suspensions of nonspherical colloidal molecules has been initiated. Distinctive changes in the location of ideal glass and
gel boundaries, barriers and yield stresses with particle shape are found. This work was done in collaboration with
Y.L.Chen. V.Kobelev, E.J.Saltzman and G.Yatsenko.
300. Rheology and microstructure of a concentrated, near hard-sphere, colloidal

suspensions using 1-2 plane flow-SANS
Dennis P. Kalman1 , Lionel Porcar 2 and Norman J. Wagner 1 , (1)University of Delaware, Newark, DE, (2)National
Institute of Standards and Technology, Gaithersburg, MD
Colloidal suspensions of hard-spheres show significant shear thinning and shear thickening at volume fractions above
about Φ=0.20; these suspensions show progressively more shear thinning and shear thickening with increasing volume

fraction. Shear thickening is known to occur via the formation of load bearing hydroclusters from theory, simulations,
flow-SANS experiments, and indirect rheological measurements, but there are no previous SANS measurements of the
structural rearrangements that accompany shear thinning or thickening directly in the plane of shear (the 1-2 or flow-
gradient plane). Here, we study model suspensions of near hard-sphere silica particles, approximately 100nm in
diameter in a near contrast-matching Newtonian solvent mixture of deuterated ethylene glycol and polyethylene glycol
via rheo-SANS in the radial and tangential direction (1-3 and 2-3 shear planes) and flow-SANS down the gap (in the
1-2 plane). Volume fractions of Φ=0.52 and 0.40 are examined in the 1-2 plane. Significant anisotropic structure is
evident around the peak in the structure factor in the shear thickened state, which is compared with theory and
simulations for the structure of the hydroclustered state. The microstructure results are compared to the measured
rheology to develop structure-property relations for colloidal suspensions.
301. Rheology of two dimensional weakly aggregated suspensions

Sven Reynaert, Paula Moldenaers and Jan Vermant, Katholieke Universiteit, Leuven, Belgium
Two-dimensional suspensions are interesting both for a fundamental study of suspension dynamics and mechanics, as
well as for the applications in the stabililization of high interface systems such as foams and emulsions. Control over
the suspension structure of a planar particle monolayer can be achieved by destabilizing an initially crystalline
monolayer of colloidal particles. This requires adequate combinations of salt and surfactant in order to tailor the
interaction potential. A magnetic rod interfacial stress rheometer is used to characterize the dynamic rheological
behaviour of particle monolayers with a controlled aggregate structure. The linear viscoelastic properties and some non-
linear rheological features will be shown. Also the compressional rheology is characterised using a Langmuir trough. It
will be shown that interfaces with both high elastic shear and compressional moduli can be obtained. As all
microstructural information can be readily accessed, direct comparison between structural and mechanical properties is
possible, providing mechanistic insight in the yielding and flow behaviour of these systems. The role of controlled
surface rheology in emulsion and foam formulation will be briefly addressed.
302. Keynote: Orientational transitions in supensions of ellipsoidal non-spherical particles

in sheared viscoelastic liquids
Jan Vermant, D. Gunes and J. Mewis, Katholieke Universiteit, Leuven, Belgium
TBA
303. Influence of process variables on the rheological properties of highly concentrated

water-in-oil emulsions
Oscar A. Alvarez 1 , Lionel Choplin 2 , Veronique Sadtler 2 , Philippe Marchal 2 and Marie-José Stébé3 , (1)Universidad de
los Andes, Bogotá, Colombia, (2)Laboratoire GEMICO, ENSIC - INPL, Nancy, France, (3)Equipe Physico-chimie des
colloïdes UMR SRSMC N°7565 Nancy Université/CNRS Faculté des Sciences BP 239, Nancy, France
Concentrated emulsions are mixtures of two immiscible liquids (water and oil, generally), in which the volume fraction
(Fv) of the dispersed phase is higher than 0.74. If Fv is higher than 0.90, these emulsions are defined as highly
concentrated emulsions.
Semi-batch process is the main protocol used to obtain this kind of products. It consists of two steps, the first one is
aqueous phase incorporation into the surfactant-oil mixture phase under given mixing conditions, and the second one is
the homogenization step in the same equipment (with possible modifications in the mixing conditions).
We studied process variables influence on rheological characteristics of highly concentrated water-in-oil emulsions.The
studied mixing variables were: aqueous phase mass flow rate (Qw) and agitation speed (N) during the incorporation
step, and homogenization speed (N') and homogenization time (th) in the second step. The system under study is
composed of n-dodecane as oily phase, deionized water as aqueous phase and sorbitan monooleate (Span 80) as
emulsifying agent. The rheological behavior of highly concentrated water-in-oil emulsions was evaluated, one hour after
their preparation at room temperature, through mechanical spectrometry in the linear viscoelastic domain.
Results show a relationship between the rheological characteristics of highly concentrated water-in-oil emulsions

(elastic modulus (G')) and energy consumption during emulsification process (E). This relationship can be described by
GaE0.6 . In addition, we observed that energy consumption in homogenization step was higher that in incorporation
step.
304. Applications of Ultra Small Angle Neutron Scattering (USANS) to the Coatings Industry
Alan I. Nakatani 1 , Antony VanDyk 1 , Lionel Porcar 2 and John G. Barker 2 , (1)Rohm and Haas Company, Spring
House, PA, (2)National Institute of Standards and Technology, Gaithersburg, MD
Commercial coatings formulations are complex mixtures of inorganic pigments, dispersants, colorants, rheology
modifiers, and polymeric binders. The ability to understand and control the interplay of interactions between these
various components is critical to obtaining a high quality coating. Many published studies have been conducted on
model polymer latex systems or model pigments and the relationship to commercial materials is often difficult to assess.
The size scale of many of the commercially used latices and pigments is too large for the angular scattering range
covered by traditional small angle neutron scattering instrumentation and the opacity of the samples prevents optical
scattering measurements at the concentrations of interest. Ultra Small Angle Neutron Scattering (USANS) provides an
angular range uniquely suited for studies on materials of interest to the coatings industry. In this presentation, we have
used the contrast matching formalism on two different sample systems of interest. The first system is a mixture of
pigment (TiO 2 ) and polymeric dispersants. The second system is a mixture of a polymer latex and pigment. For each
system samples were prepared where each component was independently contrast matched by preparing samples in
the appropriate ratio of H 2 O to D 2 O. The studies were performed as a function of shear rate to investigate the impact
of shear on each of the components in these samples. The results provide new insight into the underlying structures in
these samples which could not be measured directly by other techniques.
305. A study of the Nanostructure and Material Properties in beta-Hairpin Peptide Hydrogels
by SANS
Rohan A. Hule 1 , Radhika P. Nagarkar 1 , Boualem Hammouda 2 , Joel P. Schneider 1 and Darrin Pochan 1 , (1)University
of Delaware, Newark, DE, (2)National Institute of Standards and Technology, Gaithersburg, MD
Hydrogels have been established as promising biomaterials for applications such as tissue engineering, controlled
release of drugs and cell encapsulation. De novo designed beta hairpin peptides, capable of undergoing intramolecular
folding and consequent intermolecular self assembly and hydrogel formation, were investigated containing asymmetric
beta strand arms surrounding a turn sequence. The stimuli responsive self assembly of the hydrogels occurs via a
strand interdigitation mechanism, resulting in a fibrillar nanostructure. Fibril dimensions as measured by TEM and AFM
corroborate the interdigitated assembly. Bulk material properties studied using oscillatory rheology vary significantly for
the different morphologies. Hydrogels consisting of laminated fibrils exhibited enhanced moduli over non-twisting or
twisting fibrils and yielded at lower strain values. A lag in the G' increase during the initial period in time sweeps hints
at slower assembly kinetics that can be related to higher number of monomers involved in the interdigitated assembly.
SANS provides direct evidence of different fibril morphologies in terms of higher scattering intensities and lower
correlation lengths for laminating fibrils vs. twisting or non-twisting structures. Inter and intramolecular associations
during the self assembly process can also be related to Porod exponents indicative of mass fractals at high Q values.
The formation of fibrils as a result of the self-assembly can be precisely tracked by changes in the Porod exponents
and correlation lengths. Differences in the peptide registry that drive hydrogel nanostructure and properties can be
potentially utilized in specific biomaterial applications.
306. Polymer brushes in restricted geometries

Dennis Mulder and Tonya Kuhl, University of California, Davis, Davis, CA
The structure and dynamics of polymer brushes have been the subject of considerable theoretical and experimental
activity. Experimental measurements of the steric forces between grafted brushes and the structure of a single brush at
the solid-solution interface are in good agreement with theoretical predictions. Yet, the structure that brush layers adopt
during compression has remained elusive. We report experimental density distribution measurements of two polymer
brushes as a function of compression. We find a significant increase in brush concentration at the interface as the
layers are compressed in contrast to the smoothly increasing concentration that has been predicted. The

interpenetration of the brushes has also been determined. These results demonstrate that high-density brushes
collapse under confinement and explain why polymer brushes under good solvent conditions are so effective in
decreasing the friction between surfaces.
307. Structural Origins for the Superior Toughness of Double-Network Hydrogels

Taiki Tominaga1 , Vijay R. Tirumala 2 , Eric K. Lin 2 , Jian Ping Gong1 , Hidemitsu Furukawa 1 , Yoshihito Osada 1 and
Wen-li Wu 2 , (1)Hokkaido University, Sapporo, Japan, (2)National Institute of Standards and Technology, Gaithersburg,
MD
Double network hydrogels (DN-gels) are the toughest of crosslinked polymer networks which contain 90% water by
volume. The fracture toughness of a highly swollen but brittle polyelectrolyte network increases by an order-of-
magnitude from the in situ polymerization of neutral, linear chains. The order-of-magnitude increase in fracture
toughness is intriguing and has not been previously observed in other conventional interpenetrating polymer networks.
Here, we present insights into the structure and dynamics of DN-gels studied using recent neutron scattering
measurements. The scattering from individual components within the DN-gels was obtained by using a deuterium-
labeled monomer in conjunction with contrast-matched water. The highlights of our results are: (i) The two components
are not isolated and instead form a stable associative complex in water, and (ii) Compositional fluctuations, probably
associated with complex formation, correlated over large length scales (≈ 1.5 um) stabilize the structure of DN-gels
under deformation. The possible role of the observed complexation in the toughening mechanism will be discussed
based on the scattering data and other supporting measurements.
308. Thin polymer film structure using resonant soft X-ray scattering and reflectometry
Cynthia F. Welch 1 , Rex P. Hjelm 1 , Joseph T. Mang 1 , Marilyn E. Hawley1 , Debra A. Wrobleski 1 , E. Bruce Orler1 and
Jeffrey B. Kortright 2 , (1)Los Alamos National Laboratory, Los Alamos, NM, (2)Lawrence Berkeley National Laboratory,
Berkeley, CA
Thin films of carbon-containing materials are found in a pervasive number of applications, ranging from well-established
industrial binders and coatings to novel biomedical and optoelectronic devices based on recent advances in
nanotechnology. Phase separation through self-assembly gives these films their desirable properties; thus, determining
the film structure and understanding its formation are key to unravelling the structure-property relationships. However,
determining the morphology of thin, carbon-based films via traditional x-ray and neutron scattering techniques is often
difficult due to weak contrast between phases and small scattering volumes. Consequently, standard scattering
techniques often require either heavy atom, for x-rays, or deuterium labelling, for neutrons, to locate the various
chemical constituents in the structure. Here we develop soft x-ray scattering and reflectometry techniques that allow us
to analyze the morphology of thin polymer films whose phase-separated domains are distinguishable without resorting
to chemical modification or isotopic labelling. With these techniques, we achieve significant, x-ray energy-dependent
contrast between carbon atoms in different chemical environments using soft x-ray resonance at the carbon edge. We
demonstrate the use of this contrast mechanism on the phase-separated structure of a model thin polymer film. While
the realization of these methods represents a significant advance in our ability to probe the morphology of thin polymer
films, we expect that they will also find extensive use in the analysis of other thin, carbon-containing films often found in
biological systems and new nanocomposite devices.
309. On the determination of liquid mixture free energies from light scattering data
David S. Ross1 , Carl V. Lutzer 1 , Seth Fraden 2 and George M. Thurston 1 , (1)Rochester Institute of Technology,

Rochester, NY, (2)Brandeis University, Waltham, MA
We are developing a method that uses static light scattering as a non-invasive means for determining intensive free
energies of n-component liquid mixtures, by solving a second-order nonlinear partial differential equation appropriate for
single isotropic liquid phases. Forward light scattering efficiency data permit integration of this equation without
choosing parametric free energy models in advance. With prior information about phase boundary locations, the method
also accommodates phase separation. We address statistical and practical issues relevant for applying the method to
experimental data.
310. Relationship between “strain-hardening” and the structure of fibrin clots

Lionel Porcar, National Institute of Standards and Technology, Gaithersburg, MD and Danilo C. Pozzo, University of
Maryland / NIST, Gaithersburg, MD
Bio-polymer networks have mechanical properties that can be remarkably different from those of most synthetic
materials. One such property is the strain-hardening response that is exhibited by most biological tissues. Strain-
hardening allows tissues to be soft and malleable during small perturbations while being hard and stiff when they are
deformed beyond a certain limit, thus allowing them to maintain their structural integrity under large loads. Despite their
manifest importance, basic questions related to the structure of these biopolymer networks, such as how they deform
under stress, still remain unanswered. We have used “artificial” blood clots (fibrin networks) as a model system to
investigate the structure of these bio-networks under stress deformation throughout the strain-hardening regime. By
combining simultaneously rheology and Small Angle Neutron Scattering measurements (Rheo-SANS) we were able to
correlate the internal structural changes occurring in the material to the macroscopic mechanical response. Our results
will be discussed with respect to two recent theoretical models that have been proposed to explain strain-hardening.
311. Advance in structural complexity of block copolymer assembly via kinetics control
Darrin Pochan, University of Delaware, Newark, DE
Self-assembly of molecules is an attractive materials construction strategy due to its simplicity in application. By
considering peptidic or charged synthetic polymer molecules in the bottom-up materials self-assembly design process,
one can take advantage of inherently biomolecular attributes; intramolecular folding events, secondary structure, and
electrostatic interactions; in addition to more traditional self-assembling molecular attributes such as amphiphilicty, to
define hierarchical material structure and consequent properties. Synthetic block copolymers with charged corona
blocks can be assembled in dilute solution containing multivalent organic counterions to produce micelle structures such
as toroids. These ring-like micelles are similar to the toroidal bundling of charged semiflexible biopolymers like DNA in
the presence of multivalent counterions. Micelle structure can be tuned between toroids, cylinders, and disks simply by
using different concentrations or molecular volumes of organic counterion. Not only can novel micelle geometries be
constructed by taking advantage of charged corona-multivalent counterion complexations, but also completely new
assembly strategies have been observed that can create complex, one-dimensional nanostructures through
manipulation of charged, amphiphilic block copolymer kinetics in solution. One result of this new assembly strategy is
forced spherical micelle aggregation along a preferred direction leading to formation of cylindrical nanostructures with
alternating stripes of block copolymer chemistry perpendicular to the primary cylinder axis. The resulting cylinders were
used to template gold nanoparticle assembly in a periodic fashion. The second example is the construction of cylindrical
micelles with multicompartment cores of phase separated block chemistries.
312. Characterization of self-assembled nanostructures with internal phase separation from

triblock copolymers of PAA-b-PMA-b-PS
Kelly D. Hales and Darrin J. Pochan, University of Delaware, Newark, DE
The characterization and understanding of the structure of polymer nanoparticles and bulk-like phase behavior of
amphiphilic triblock copolymers of poly(acrylic acid)-b-poly(methyl acrylate)-b-polystyrene in water/tetrahydrofuran
(THF) solvent mixtures is strongly dependent on block composition as well as solvent composition. The block
copolymers were dissolved in THF in the presence of an organic counterion. Upon the slow addition of water, a variety
of structures were observed including phase-separated nanoparticles, bulk-like lamellar phase separation, spherical,
cylindrical, and disk-like micelles, as well as toroidal assemblies. The specific structure formed was dependent on the

architecture of the triblock copolymer, the amount of counterion present, and the water to THF volume ratio. This work
focuses on the structure of polymer nanoparticles and networks formed in low water content systems. The size of the
nanoparticles and whether separated nanoparticles vs. an interconnected network was formed can be controlled via
solvent composition. Importantly, both the nanoparticles and network phases contain their own inherent nanostructure
due to local phase separation of the block copolymers. Cryo-transmission electron microscopy, traditional transmission
electron microscopy, and neutron scattering were used to examine these samples.
313. Dynamics of amphiphilic block copolymer micelles

Raoul Zana, Carlos Marques and Albert Johner, Institut C. Sadron (CNRS), Strasbourg, 67000, France
The Pluronics ® (polyethyleneoxide-polypropyleneoxide-polyethyleneoxide, PEO-PPO-PEO) are the only amphiphilic

block copolymers for which results for the kinetics of the copolymer exchange between micelles have been reported for
several copolymers. The rate constants k + and k - for the copolymer entry/exit into/from micelles have been extracted
from these results for 8 copolymers. Contrary to what is observed for conventional surfactants, k + is smaller/much
smaller than for a diffusion-controlled process. Both k + and k - decrease significantly with increasing number of PO
units, n PO, but vary relatively little with the number of EO units, n EO, in the copolymer. The plot of log k - vs t4/3 n PO2/3
(t is a factor correcting for temperature) is linear. This behavior suggests that the PO block is somewhat folded in the
free (unimer) state, with less contact with water than in the fully extended conformation. This behavior explains why, for
other amphiphilic block copolymers, the reported values of k - show remarkably little dependence on the copolymer
architecture. An extrapolation of the Pluronics ® results on the basis of Aniansson's expression for k - suggests that for
copolymers with a more hydrophobic block (i.e., polybutyleneoxide or polystyrene) the exchange process may be too
slow for being detected on the laboratory time scale. The folding of the hydrophobic block in the unimer state precludes
the determination of the free energy increment for the transfer of a hydrophobic unit from water to micelle from the cmc
dependence on the hydrophobic block polymerization degree. The micelle formation/breakdown of Pluronics ® micelles
appears to occur via fragmentation/coagulation reactions.
314. Self-assembly of amphiphilic proteins with redox cofactors

Vidya Karunakaran, Paul A. O'Brien, Viraj Parekh, P. Leslie Dutton and Bohdana M. Discher, University of
Pennsylvania, Philadelphia, PA
Redox-active nanoscale materials such as porphyrin binding proteins are of immense interest because of their potential
use as catalysts in light-energy harvesting processes or as bioelectronic devices. To realize this potential, we have
designed simple, robust peptides (maquettes) that assemble into four-helix bundles. The maquettes presented here
possess overall amphiphilic character that enables their complex multi-component assembly in detergents,
phospholipids vesicles or at air-liquid interfaces. To enable electron transfer within the protein and subsequently across
a membrane, we have incorporated multiple binding sites for redox-active cofactors. We have tested how the position of
the binding site with respect to the membrane affects the assembly, affinity, and redox properties. Results reported
here include AP maquettes with up to 6 binding sites for protoporphyrins.
315. Hierarchical Self-assembly Based on the Metal-bisligand Coordination Complexes and

a Block Copolymer
Yun Yan, Nicolaas A. M. Besseling, Arie de Keizer and Martien A. Cohen Stuart, Wageningen University, Wageningen,
Netherlands
Metal-bisligand coordination complexes are self-assembled supramolecules1. The water solvable metal-bisligand
coordination complexes with negative charges on coordination centre can be regarded as negatively charged
polyelectrolytes. This polyanions are found to form hierarchical self-assemblies with polyneutral-polycations block
copolymer2. In this research, we report (1): Formation of spherical and worm-like micelles in poly(2-vinyl-N-methyl-
pyridium iodide)-polyethylene oxide (P2MVP41-PEO204) /Zn-L2EO4 coordination complexes. The latter is formed by
mixing 1,11-bis(2,6-dicarbonate potassium-4-yloxy)-3,6,9-trioxaundecane, L2EO4, with zinc nitrate. (2) Formation of
coacervate fibbers in the mixture of Zn-L2EO4 and A-B-A type polyaminoacid block copolymer, where A represents
neutral block while B represents positively charged block. This new class of self-assemblies are very interesting

because of the existence of metal ions in the coacervate core, which enable carriage of metal ions with water soluble
nano vehicles, and also shed lights on other practical fields.
Figure 1. Cryo-TEM images of coacervate core micelles formed in the PMVP41-PEO204/ Zn-L2EO4 mixed system at f-
= 0.5.
References: 1. Vermonden, T.; Van Steenbergen, M. J.; Besseling, N. A. M.; Marcelis, A. T. M.; Hennink, W. E.;
Sudhölter, E. J. R.; Cohen Stuart, M. A. J. Am. Chem. Soc. 2004, 126, 15802-15808. 2. Yan, Y.; Besseling, N. A. M.;
de Keizer, A.; Marcelis, A. T. M.; Drechsler, M.; Cohen Stuart, M. A. Angew. Chem. Int. Ed. 2007, 46,
316. Rational design of peptide assemblies for bio-separations

Raymond S. Tu, Vikas Jain and Angela Jimenez, The City College of The City University of New York, New York, NY
Our goal is to develop a novel technology for robust and sequence specific DNA separation. The approach is based on
the formation of a self-assembly composed of de novo designed amphiphilic peptides, where the specific binding
results in secondary structure enhancement and self-assembled phase transformations. Peptides can be rationally
designed with native configurational fluctuations, and this entropically favored state is only broken on binding to form a
well-ordered state. This process has been coined fishing because the fluctuating linear chain is facilitating the capture
and catalysis of target molecules. A common misconception that is prominent in our teaching of molecular biology is the
paradigm that protein sequence (primary structure) defines a uniquely folded protein structure (tertiary structure) that, in
turn, directly relates to the presentation of an active binding site. This paradigm has been frequently used to define the
thermodynamics and kinetics of biological processes. Yet the model underestimates nature's versatility. This work
describes the development of peptide-motifs where peptides can actively respond to specific sequences of DNA,
resulting in enhanced amphiphilicity and self-assembly. The engineering of these natively disordered proteins is
accomplished by judiciously manipulating the topography of the folding energy landscape to control actively assembly
as a function of binding.
317. Engineering self-assembly between biological materials
Suzanne M. Barber1 , Philip J. Costanzo2 , Jaroslaw Majewski 3 , Chad E. Miller 3 , Vishal Trivedi 4 , Walter Stockinger 4 ,
Timothy E. Patten 5 , Axel Nohturfft4 and Tonya L. Kuhl 1 , (1)University of California Davis, Davis, CA, (2)Army Research
Laboratory, Silver Springs, MD, (3)Los Alamos National Laboratory, Los Alamos, NM, (4)Harvard University, Cambridge,
MA, (5)UC Davis, Davis, CA
Rarely in Nature are single molecule interactions used for cell adhesion. Rather, several different types of molecules or
structures interact in concert to build effective adhesion. To study how these multivalent adhesive interactions are
utilized by biological systems, we are working to develop a tailorable, self-assembled biosensor that can probe the
range of interactions from the single molecule level to the ensemble average of multiple interactions. We selectively
self-assemble functionalized polymer linkers with complementary terminal groups onto patterned nanoparticles to probe
ligand-receptor interactions on the surface of the membrane. However, multivalent interactions, resulting from ligand-
receptor pairs, must partner with the membrane properties to result in fusion. Therefore in parallel, we are studying the
composition and behavior of cell membranes, both in vitro and in vivo. In particular, we study intracellular vesicles
produced from particles phagocytosed by J774 cells. By studying the phase behavior, composition and interfacial
behavior of phagosomal extracts, we aim to devise an improved model cell membrane system. We propose that by
developing a more sophisticated model of a cell membrane, a wider range of techniques may be effectively used to
study critical biological processes, such as adhesion and fusion.

318. Interfacial Solubilization Mechanisms in the Micellar Solubilization of Oils from

Monodisperse Droplets
Suwimon Ariyaprakai and Prof. Stephanie R. Dungan, University of California, Davis, CA
The mechanism by which hydrophobic solutes such as oils move from emulsion droplets into surfactant aggregates
such as micelles continues to be debated. Controlling roles of micelle adsorption, micelle pinch-off, molecular diffusion
or of rapid micelle uptake have been proposed by various research groups. In this study, nearly monodisperse alkane-
in-water emulsion droplets were mixed with aqueous micellar solutions, allowing solubilization to proceed. Because
these emulsions were nearly monodisperse, we were able for the first time to observe, using static light scattering, the
progressive decrease in average droplet size due to solubilization, and to analyze the rate of this decrease using a
population balance approach to calculate the mass transfer coefficient. We studied the effect of oil chain length,
surfactant type and concentration, and the aqueous phase viscosity on the mass transfer kinetics. The influence of
viscosity and of surfactant concentration, in particular, provide insight into the role of molecular diffusive processes
relative to interfacial mechanisms. Understanding solubilization mechanisms is important in a host of natural and
industrial processes, including nutrient absorption and release of pharmaceutical agents.
319. Particle Stability in Semidilute and Concentrated Polymer Solutions

David L. Green and Nupur Dutta, University of Virginia, Charlottesville, VA
Engineered composites are often formulated by grafting polymer brushes to the surfaces of nanoparticles to disperse
them into polymer solutions and melts. In these suspensions it is well established that nanoparticles can exhibit a wide
variety of phase behaviors through depletion flocculation at low-to-moderate free polymer concentrations. However, few
studies fundamentally elucidate the fate of polymer-grafted particles in concentrated polymer solutions and melts.
Researchers who have studied these systems predict that ungrafted and grafted nanoparticles, once destabilized by
depletion flocculation, should restabilize in concentrated polymer solutions. In contradiction, we will show the results of
recent light scattering experiments on polydimethylsiloxane (PDMS)-grafted silica nanospheres in PDMS/cyclohexane
mixtures which indicate that at high free polymer volume fractions (0.5 – 1.0 v/v) the interfacial wetting of the grafted
brush is needed to stabilize the nanoparticles against aggregation. We correlate this behavior to wetting phase
diagrams that predict the regions of stability and instability for the PDMS-g-silica nanoparticles. Overall, these studies
represent new ways of quantifying the factors that control the dispersion of polymer-grafted nanoparticles in
concentrated polymer solutions and melts – systems that are ubiquitous in formulating engineered composites.
320. Effects of interfacial dynamics on bulk flow patterns: drop deformation in an

extentional flow
Andres Gonzalez-Mancera, Mustapha Jamal and Charles D. Eggleton, University of Maryland, Baltimore County,
Baltimore, MD
We consider a multiphase system in which a liquid drop is suspended in a distinct fluid. Surface-active molecules
adsorb to the interface and are often use to stabilize the drop and to reduce surface tension. We also consider
liposomes which are self-enclosed structures composed of curved lipid bilayer membranes located at the interface
between an internal liquid and a suspending liquid. Lipid bilayer membranes are predominantly made from amphiphilic
molecules, a special class of surface-active molecules.
When the suspending liquid is set in motion, viscous stresses dynamically alter the tension distribution at the interface.
Our study focuses on understanding the role that interfacial dynamics play on the transfer of energy between the
interface and the bulk fluids. We simulate the deformation of a particle in an axisymmetric extensional flow and
subsequent relaxation using the boundary integral method.
We model the interface of a surfactant laden drop using the Frumkin surface equation of state and consider equilibrium
surfactant concentrations ranging from zero to a highly packed monolayer. The lipid bilayer membrane is modeled using
an elastic two-dimensional continuous isotropic material with a varying elastic material property that depends on local
area changes. The elastic model was derived considering the mechanical behavior of a highly concentrated surfactant
monolayer. We analyze flow field properties such as streamlines, stress field and energy dissipation and identify
characteristic flow patterns as a function of interfacial properties.

321. Remotely powered distributed microfluidic pumps and mixers based on miniature
diodes
Suk Tai Chang 1 , Vesselin N. Paunov 2 , Dimiter N. Petsev3 and Orlin D. Velev 1 , (1)North Carolina State University,
Raleigh, NC, (2)University of Hull, Hull, United Kingdom, (3)University of New Mexico, Albuquerque, NM
We demonstrated earlier how miniature semiconductor diodes could self-propel by harvesting electric energy from
external AC fields and converting it to mechanical propulsion on the microscale. Here we report how this mechanism
can be used in new types of microfluidic devices. Miniature diodes embedded into microfluidic channel walls could act
as distributed pumps or mixers powered by a global external field. The millimeter-sized diodes generate DC fields
across their electrodes as a result of rectification of the external AC field. The resulting localized electroosmotic flux on
the surface of diodes evokes an overall flow in the microfluidic channel in the direction of either the cathode or the
anode depending on their surface charge. The flow velocity linearly increases with applied voltage, but does not
depend on the frequency of the field, which could eliminate problems with vortices in areas of non-uniform field that
often occur in other AC electrohydrodynamic pumps. The combined application of AC and DC fields in our microfluidic
chip allows efficient separation of particles with small differences in their charges or size. This localized-electroosmotic
flow between the diodes in the channel wall could also be used in efficient controllable microfluidic mixers. This
research may establish the foundation of new actively controlled nanofluidic-electronic chips for manipulating liquids,
solutes and analytes at the nanoscale.
322. Extending the Threads in Surfactant-Mediated Microscale Tipstreaming

Wingki Lee, Shelley L. Anna and Lynn M. Walker, Carnegie Mellon University, Pittsburgh, PA
Microfluidic flow focusing devices have been used to synthesize micrometer-scale emulsion droplets via the thread
formation mode of drop breakup. Thread formation occurs when surfactants are dissolved in one or both liquid phases.
In a particular range of surfactant concentrations and flow rates, a thin thread is drawn between two primary droplets.
As the thread elongates, it disintegrates into a stream of tiny droplets, whose sizes depend on the final thread diameter
and the physical properties of the liquids. In the present work, we investigate the role of physical parameters on thread
formation. In particular, we show that the thread length is extended when the downstream geometry is modified to
stretch the thread more rapidly. In addition, we construct a phase diagram indicating that as the viscosity ratio
decreases, the range of capillary numbers in which threads form increases and the threads become longer and thinner.
These results suggest ways of optimizing the thread formation process to form ever smaller droplets.
323. Surfactant Induced wettability alteration in fractured carbonate reservoirs

Robin Gupta and Kishore K. Mohanty, U. of Houston, Houston, TX
The conventional water flooding recovers little oil from oil-wet fractured reservoirs. Most of the water passes through
the factures and does not imbibe into the matrix due to negative capillary pressures. The goal of this work is to induce
wettability alteration on carbonate rocks such that water would be imbibed resulting in oil production. Many anionic
surfactants and a few cationic surfactants have been studied. The salinity is adjusted by varying the concentration of
sodium carbonate which also increases the pH above the PZC for carbonates preventing adsorption of anionic
surfactants on surface. Interfacial tension (IFT) of the order of 10-2 mN/m are observed for anionic surfactants (of the
order 1 mN/m for cationic) at optimal salinity. Contact angle studies have been conducted on initially oil-wet calcite
plates. Surfactants have been identified which alter the water-oil contact angle to below 90„a. Limited studies with an
AFM indicate the removal of adsorbed organics by surfactants. The screened surfactants are used to imbibe the initially
oil-wet carbonate cores. The oil recovery is monitored with time. A numerical simulator is developed to understand the
process by analyzing in-situ distribution of IFT, flow, capillary pressure, relative permeability and surfactant
concentration. The surfactant molecules diffuse from fractures into the matrix and change wettability and IFT. This leads

to reduction in capillary pressure and aqueous phase invades from bottom of the core pushing oil out from the top. The
change in wettability results in an increase in oil relative permeability which increases oil recovery rate.
324. Dynamic Wetting of Boger Fluids
Yuli Wei 1 , G. Seevaratnam 1 , S. Garoff 1 , E. Rame2 and Lynn M. Walker 1 , (1)Carnegie Mellon University, Pittsburgh,
PA, (2)National Center for Space Exploration Research, Cleveland, OH
The impact of fluid elasticity on the dynamic wetting of polymer solutions is important because many polymer solutions
in technological use exhibit non-Newtonian behaviors in the high shear environment of the wedge-like flow near a
moving contact line. Our former study showed that shear thinning induced by a semi-flexible high molecular weight
polymer reduces the viscous bending near a moving contact line as compared to a Newtonian fluid having the same
zero-shear viscosity. This results in a dramatic reduction of the dependence of the effective dynamic contact angle on
contact line speed. In this talk, we discuss dynamic wetting of Boger fluids which exhibit elasticity dominated rheology
with minimal shear thinning. These fluids are prepared by dissolving a dilute concentration of high molecular weight
polymer in a “solvent” of the oligomer of the polymer. We demonstrate that elasticity in these fluids increases curvature
near the contact line but that the enhancement arises mostly from the weakly non-Newtonian behavior already present
in the oligimeric solvent.
. Understanding and exploiting the surface chemistry of single walled carbon nanotubes
Michael S. Strano, University of Illinois Urbana-Champaign, Urbana, IL
Recent advances in the spectroscopy of single walled carbon nanotubes have significantly enhanced our ability to
understand and control their surface chemistry, both covalently and non-covalently. We have used this insight to study
how this chemistry controls intermolecular interactions for several applications. Molecular detection using near-infrared
light between 0.9 and 1.3 eV has important biomedical applications because of greater tissue penetration and reduced
auto-fluorescent background in thick tissue or whole-blood media. We have pioneered the use of carbon nanotubes as
tunable near-infrared fluorescent sensors that are highly photo-stable In one system1, the transition of DNA secondary
structure from an analogous B to Z conformation modulates the dielectric environment of the single-walled carbon
nanotube (SWNT) around which it is adsorbed. The SWNT band-gap fluorescence undergoes a red shift when an
encapsulating 30-nucleotide oligomer is exposed to counter ions that screen the charged backbone. We demonstrate
the detection of the mercuric ions in whole blood, tissue, and from within living mammalian cells using this technology.
Similar results are obtained for DNA hybridization and the detection of single nucleotide polymorphism. We also report
the synthesis and successful testing of near-infrared ?-D-glucose sensors2 that utilize a different mechanism: a
photoluminescence modulation via charge transfer. The results demonstrate new opportunities for nanoparticle optical
sensors that operate in strongly absorbing media of relevance to medicine or biology.
Another problem we have focused on is how the electronic structure of a carbon nanotube influences its chemical
reactivity. For example, rate constants for electron transfer reactions involving single walled carbon nanotubes should
vary with their chirality vector (n,m), a measure of the helical ‘twisting' of the graphene lattice in the nanotube. To date,
the functional form of this relationship has proven elusive. We have performed completely automated reactions of single
walled carbon nanotubes (SWNT) with 4-hydroxybenzene diazonium salt under various experimental conditions, and
analyzed their influence on the reaction selectivity using UV-vis-nIR absorption spectroscopy and a previously
published spectral deconvolution procedure. The selectivity of the reagent to metallic SWNT over semiconducting
SWNT was greater at low salt concentrations (73%) and lower at high salt concentrations (54%). The activity of
diazonium was increased upon illumination; however, similar rate constants for the SWNT (relative to the (11,5)
nanotube) were computed for the light and dark reactions, indicating that the type of diazonium intermediate affects the
extent of reaction and not the rate. The steady state data has been modeled using an adsorption-reaction scheme, and
an electron transfer theory is developed to yield the first structure-reactivity relationship for SWNT.
325. Designing Novel Biosensors from the Nanoscale Up

Amanda J. Haes, University of Iowa, Iowa City, IA
Miniature optical sensors that specifically identify low concentrations of biological and environmental substances are in
high demand. Currently, there is no optical sensor that provides identification of the aforementioned species without

amplification techniques and at naturally occurring concentrations. Recently, it has been demonstrated that triangular
silver nanoparticles have remarkable optical properties and that their enhanced sensitivity to small changes in their
local environment can be used to develop a new class of optical sensors using localized surface plasmon resonance
(LSPR) spectroscopy and optimized surface chemistry. The examination of both model and non-model biological
assays will be presented. It will be demonstrated that the LSPR nanosensor rivals the sensitivity and selectivity of and
provides a low-cost alternative to commercially available sensors.
326. Keynote: Nonequilibrium statistical mechanics, proteins, and nucleic acids

Jan Liphardt, University of California - Berkeley, Berkeley, CA
Tools such as counter-propagating optical tweezers are allowing researchers to manipulate single proteins and nucleic
acids with ever higher spatial and temporal resolution. However, our ability to interpret the data collected from single-
molecule experiments is still only rudimentary since many take place very far from equilibrium. Fortunately, several
theoretical results from nonequilibrium thermodynamics that were long-held to be untestable curiosities make it possible
to extract thermodynamic parameters from nonequilibirum experiments. The aim of my talk is to provide an overview of
research at the intersection of nonequilibrium statistical mechanics and single molecule biophysics. I will conclude with
a survey of open problems in the field.
327. Photo-control of the form-dynamics-function relationship of enzymes

Shao-Chun Wang, Andrea C. Hamill and C. Ted Lee Jr., USC, Los Angeles, CA
We have recently developed a novel method to reversibly control protein conformation with simple light illumination.
This method relies on the interaction of proteins with photoresponsive “azoTAB” surfactants that can be switched from
the photo-active to a photo-passive state with exposure to visible or UV light, respectively. The active surfactant binds
to and unfolds proteins, while the passive surfactant dissociates from proteins inducing refolding. To examine the
partially-folded structures that result, we have utilized small-angle neutron scattering (SANS) along with shape-
reconstruction algorithms. Briefly, shape reconstruction involves optimizing the positions of the “scattering centers”
within the protein to best fit the SANS data. With azoTAB under visible light, lysozyme unfolding is localized to a
swelling of the hinge region connecting the alpha and beta domains, while UV illumination refolds lysozyme to a native-
like conformation. To investigate the effects of hinge swelling on protein dynamics, we have performed neutron spin
echo (NSE) experiments. NSE can access relaxational dynamics over time scales from 0.01–100 ns and length scales
from 10–150 Å, appropriate for the study of domain motions within proteins. Interestingly, NSE detects internal motions
within lysozyme in the presence of active surfactant (visible light), while converting the surfactant to the passive form
with UV light results in a “dormant” protein in the nanosecond/nanometer regime, similar to native lysozyme. Notably,
these internal motions are accompanied by a 7x “superactivity” of the enzyme versus the native state. AzoTAB induces
unique allosteric control of enzyme activity through hinge swelling and enhancing enzyme flexibility.
328. Probing SDS-PAGE protein separations using small angle neutron scattering
Danilo C. Pozzo, University of Maryland / NIST, Gaithersburg, MD
Sodium dodecyl sulfate polyacrylamide electrophoresis (SDS-PAGE) is the most widely used method to carry out
analytical separations of small poly-peptides and proteins. Despite its recognized importance, our understanding of the
transport of surfactant denatured proteins during electrophoresis is based greatly on assumptions of protein
conformation inside the gel and on macroscopic measurements of their mobility. We have recently designed and built a
new cell that allows us to perform small angle neutron scattering (SANS) measurements during the process of
electrophoresis. Contrast-variation SANS is used to provide, for the first time, a structural picture of the conformation of
protein-surfactant complexes during this separation process. Our recent SANS observations are discussed and related
to transport models (Ogston model and reptation model) that have been proposed to occur during SDS-PAGE.
329. Therapeutic Proteins Encapsulated in PEG-based Polymersomes

David A. Christian, Diana M. Bowen and Dennis E. Discher, University of Pennsylvania, Philadelphia, PA
Therapeutic proteins are generally potent but their effect in vivo is short-lived. The extension of this therapeutic

timescale has motivated recent work on protein encapsulation in drug delivery devices (i.e. liposomes, microparticles,
hydrogels) or modification by polyethylene glycol (PEG). We are investigating the ability of PEG-based block copolymer
vesicles - or polymersomes - to encapsulate such proteins for controlled release, and in the process studying the
interactions between block copolymers and complex, aggregating proteins. We are using recombinant human insulin as
one therapeutic protein for encapsulation and tuned release. Initial results indicate that the encapsulation of fluorescein-
labeled insulin in polymersomes is possible. Insulin-loaded polymersomes can then be processed to a 100nm diameter
and separated from unencapsulated insulin. These insulin-loaded nano-polymersomes are shown to be stable for
months at 4„aC as well as in whole blood in vitro. However, insulin is a complex protein that is readily capable of
aggregating to form dimers, hexamers, and higher molecular weight aggregates. This aggregation results from exposure
to agitation, high temperature, and hydrophobic interfaces such as the air-water interface. Because high molecular
weight PEG molecules have been shown to have little interaction with proteins or even to stabilize proteins in such
adverse conditions, it is thought that the 100% PEGylated surface of the polymersome membrane will have minimal
interaction with the proteins - making the aqueous lumen of the polymersome a stable environment for encapsulated
proteins. We intend to further examine the effect of polymersome encapsulation on the structure of insulin as a model
protein therapeutic.
330. Targeted particulate binding to cellulose surfaces mediated by bifunctional fusion

proteins
Gautam Pangu1 , Eric Johnston1 , Jordan Petkov2 , Neil Parry 2 and Daniel Hammer1 , (1)University of Pennsylvania,
Philadelphia, PA, (2)Unilever R&D, Bebington, United Kingdom
The targeted deposition and binding of particulates to cellulose mediated by a molecular family of heterobifunctional
fusion proteins is studied in this work. The fusion protein consists of a domain that binds to a particle either directly or
through a model red dye, and a domain that binds to cellulose. The strength of adhesion of a single particle to a
cellulose fiber is measured by using micropipette aspiration as a function of its adhesive specificity, surface density and
contact time. In addition, the dynamics of adhesion of the functionalized particles to cellulose-coated glass slide under
controlled hydrodynamic flow at various shear rates is explored using flow chamber assays for two scenarios:
detachment of bound particles, and attachment of particles in suspension. Highly specific adhesion is observed in both
studies. The force of adhesion was ~ 2 nN for the fully functionalized particles with the frequency of adhesion > 90% in
micropipette aspiration assay, while average force required to detach a bound particle was ~ 125 pN in flow chamber
assay. The adhesive dynamics simulations of particle binding to cellulose coated substrate indicate that the
experimentally observed response of bound particles to the application of shear force can be simulated by combining
probabilistic nature of receptor-ligand binding with heterogeneity in receptor density observed across particle population.
331. Influence of adsorbed fibrinogen on non-Specific micron-scale adhesion

Surachate Kalasin and Maria Santore, University of Massachusetts,, Amherst, MA
Cell adhesion in biology is attributed to a handful of specific ligand-receptor interactions, or common motifs such as
RGD. Conversely, bio-technical situations such as the interactions between the body and implanted materials, assay
devices contacting biological fluids, and even biomarine fouling will be largely influenced by nonspecific interactions.
Indeed, some of the biological cell adhesive behavior may also be influenced by long range nonspecific interactions
before ligand-receptor binding comes to bear. To that end, we ask the question: how much adsorbed protein is
sufficient to produce adhesion at an interface which is otherwise substantially non-adhesive? Here we adsorbed
different amounts of fibrinogen (from 0.05 to 5 mg/m2) on a model surface which is non-adhesive or minimally-
adhesive: silica. When a series of these surfaces are exposed to flowing suspensions, we find that even though the net
long range electrostatic field is negative, small amounts of fibrinogen, less than 0.5 mg/m2, are sufficient to give
adhesion, either through hydrophobic interactions or through the interaction of positive regions of the protein with the
approaching negative surface. We further observe that the adhesion “turns on” sharply at a distinct threshold,
reminiscent of surface fluctuation studies with a purely electrostatic model. Hence this work not only answers the
question “How much of a sticky protein can be tolerated before bioadhesion becomes a problem?”, it also demonstrates
the role of fluctuations in protein-driven non-specific adhesion.
332. Keynote: Drug Delivery and Imaging Using Nanoparticles Produced by Block-
copolymer Directed Flash NanoPrecipitation

Robert K. Prud'homme, Walid Saad, Ying Liu, Marian Gindy and Margarita Herrera-Alonso, Princeton University,
Princeton, NJ
Nanoparticle formulations of hydrophobic drugs present unique opportunities for treatment of solid tumor cancers, for
delivery of drugs by aerosol administration. The common requirements of these applications are precise control of
particle size and surface functionality. We present our new process --Flash NanoPrecipitation – a controlled
precipitation process that produces stable nanoparticles at high concentrations using amphiphilic diblock copolymers to
direct self-assembly. Uniform particles with tunable sizes from 50-500 nm can be prepared in an economical and
scalable manner. The key to the process is the control of time scales for micromixing, polymer self-assembly, and
particle nucleation and growth. The diffusion-limited assembly enables particles of complex composition to be formed.
The PEG protective layer creates long-circulating particles and the inclusion of PEG chains with terminal ligands allows
drug targeting. Examples of particle formation for controlled delivery of multiple drugs from nanoparticles will be
presented. This enables the simultaneous, controlled release of multiple drug “cocktails” from nanoparticles for the
treatment of cancers and HIV. The incorporation of gold or magnetite nanoparticles or fluorophores with drugs into a
single nanoparticle enables simultaneous delivery and medical imaging.
333. Structure of “flexible” liposome formulations as probed by SANS
Oluwatosin A. Ogunsola1 , Margaret E.K. Kraeling2 , Matthew B. Dowling 1 , Robert L. Bronaugh 2 and Srinivasa R.
Raghavan 1 , (1)University of Maryland, College Park, MD, (2)Food and Drug Administration, College Park, MD
Recently, there has been much interest in creating liposomes that can penetrate skin and thereby deliver their
encapsulated contents for therapeutic (e.g., a drug or vaccine) or cosmetic purposes. Several studies have shown that
so-called “flexible” liposomes or transfersomesTM are indeed capable of penetrating skin. These liposomes are created
by mixing lipids with small amounts of a denaturing agent such as Tween 80 or an alcohol. The flexibility of these
liposomes has been quantified by permeability measurements, while their skin penetration has been evaluated by
confocal microscopy. In this study, we use small-angle neutron scattering (SANS) to further probe the structure in
formulations that are supposed to consist of flexible liposomes. Our studies suggest that the above solutions may
actually contain a combination of liposomes and micelles. In other words, the effect of adding detergent is not just to
make the liposomes flexible, but also to micellize a fraction of the lipids. To our knowledge, this aspect has not been
highlighted in the literature thus far. Our findings suggest a different hypothesis for the skin-penetrating action of these
liposome formulations. We test this hypothesis further by examining the penetrating ability of new liposome-micelle
mixtures into hairless guinea pig skin using confocal microscopy.
334. Using Atomic Force Microscopy to investigate the interactions between living cells and
particles covered with RGD-containing proteins and the role of integrin binding
Hiroyuki Shinto, Yuki Aso and Ko Higashitani, Kyoto University, Kyoto, Japan
The integrins are transmembrane adhesion molecules and act as cell-adhesion receptors that form contacts with
extracellular matrix (ECM). They interact with one of many ECM components often by recognizing the tripeptide
arginine-glycine-aspartic acid (RGD) in the substrate (e.g., laminin, fibronectin, or vitronectin).
In the present study, we have measured the interaction forces between living malignant melanoma B16F10 cells and
three types of polystyrene latex (PSL) spheres, using the Atomic Force Microscopy (AFM) with the colloid probe
method: (i) bare PSL (bare/PSL) spheres; (ii) carboxyl-coated PSL (COOH/PSL) spheres; (iii) RGD-coated PSL
(RGD/PSL) spheres, which were modified by RGD-containing proteins, namely ProNectin ® F Plus. The adhesion forces
of these PSL spheres with the surface of B16F10 cells give the order of (bare/PSL) < (COOH/PSL) < (RGD/PSL) in
magnitude. This strong adhesion of the RGD/PSL sphere to the cell surface is considered to originate from the integrin-
RGD binding.
Also, we have measured the cell-particle adhesion forces in a culture medium including RGD tripeptides, which inhibit
the adhesive function of the cell integrins by binding with them. The adhesion of COOH/PSL and RGD/PSL spheres
became weaker with increasing the concentration of the dosed inhibitors, while that of bare/PSL sphere remained
almost constant. These results indicate that the integrins play an important role in cell-particle adhesion, depending on
the surface chemistry of particles. The possible mechanism of cell-particle adhesion will be given in our talk.

335. Deposition of biocomposite coatings from live cells and large particles by convective-
sedimentation assembly
Lindsey B. Jerrim and Orlin D. Velev, North Carolina State University, Raleigh, NC
We developed a method for depositing live cells and large particles in uniform, close-packed monolayers. It is based on
convective assembly at high volume fractions in the presence of sedimentation ("convective-sedimentation" assembly),
and allows rapid deposition of uniform, close-packed coatings of yeast cells onto a glass plate (see figure). A
computational model was developed to calculate the thickness profile of a coating by breaking the deposition
mechanism into three discrete components: convection, evaporation, and sedimentation. The use of this model, in
conjunction with parametric experiments, determined that both increasing the forward angle of the device and
decreasing the angle between the slides in the device increase the uniformity of the coatings deposited. In the next
step of this work, the convective-sedimentation assembly was used to deposit composite coatings of live cells and large
latex particles as prototypes of self-cleaning materials. The latex particles form a protective, porous cover over the
yeast cells, which cluster around the bottom parts of the microspheres. When exposed to growth media, the cells
proliferate and form a layer over the latex particles. When this coating is exposed to fluid flow, the overlaying cell layer
is sloughed off, along with any debris that collects on the layer of cells. The cells remaining with the latex particles in
the coating will then continue to proliferate, thereby regenerating the coating.
336. Multi-Compartment Carriers for Enhanced Drug Delivery

Guohui Wu, university of california, santa barbara, santa barbara, CA, Rachel Freund, Santa Barbara City College,
Santa Barbara, CA and Joseph Anthony Zasadzinski, University of California, Santa Barbara, CA
Vesosomes, a multi-compartment structure consisting of drug-loaded liposomes encapsulated within another bilayer, is
a promising drug carrier with improved drug retention and stability compared with unilamellar liposomes. The vesosome
preparation takes advantage of the interdigitated phase of saturated lipids, which causes lipid bilayers to form flat, open
sheets at low temperature, that close to form large unilamellar vesicles at higher temperatures. During this closure, the
interdigitated sheets encapsulate other lipid vesicles or colloidal particles to form and thereby become the outer
membrane of the vesosome. However, vesosomes exterior shells made from a single lipid component, such as
dipalmitoylphosphatidylcholine (DPPC), has an average diameter of 1.3 µm, too large for optimal intravenous use. The
addition of poloxamer 188 (P188) at low concentrations preserves the interdigitated phase transition and can effectively
decrease the vesosome diameter. Freeze-fracture TEM and light scattering were used to evaluate the size distribution
and polydispersity of the vesosomes formed; poloxamer led to a decrease in the average diameter to about 0.6 µm.
The polymer may also provide an extra steric layer protection of vesosomes against flocculation or recognition by the
immune system. Applying osmotic pressure by diluting the vesosomes with buffer of increased salt concentration can
further decrease the vesosome diameter.
337. Impact of surfactant in solid oral dosage forms for small molecules
Craig A. McKelvey, Merck & Co., Inc., West Point, PA
Surfactant is used in oral dosage forms as a solubilizer and/or wetting agent. Applications including liquid filled
capsules, conventional dry tablets, and less conventional dry amorphous formulations employ surfactant for different
purposes. This talk will discuss the impact of surfactant in these dosage forms, including (1) partial binary and ternary
phase behavior of common pharmaceutical liquid filled capsule formulation components (corn oil, Polysorbate 80,
fractionated mono-,di-, and triglycerides, water etc.), (2) the synergistic effect of a bile salt on microemulsification
efficiency, and (3) the impact of surfactant during the dissolution and subsequent recrystallization of an insoluble drug
in a conventional dosage form.

338. Interfacial Colloidal Sedimentation Equilibrium Microstructures

Michael A. Bevan and Richar E. Beckham, Texas A&M University, College Station, TX
To intelligently design, control, and optimize self-assembly of three-dimensional colloidal structures on substrates (e.g.
photonic crystals), it is necessary to understand how interactions between colloids, surfaces, and external fields lead to
various interfacial microstructures. In this talk, we present confocal microscopy measurements and statistical mechanical
analyses of the sedimentation equilibrium of inhomogeneous colloidal fluids coexisting with crystals above macroscopic
planar surfaces. In contrast to most previous sedimentation equilibrium studies, the present work focuses on relatively
compact microstructures over 10-100 particle diameters due to the similarity of particle dimensions and the
characteristic gravitational lengthscale (mgd/kT~1). A new method is reported to obtain sedimentation equilibrium
profiles of sub-micron fluorescent silica core-shell colloids by deconvoluting intensity profiles as density distributions
without locating particle centers. This approach overcomes limitations on accurately locating very large numbers of 3D
particle centers in the presence of significant Brownian motion, but still allows real-space visualization of equilibrium
fluid and crystal phase microstructures. Inverse analyses of the resulting sedimentation equilibrium profiles using
perturbation theory (based on the local density approximation), Monte Carlo, and a new density functional theory
formulation are used to extract particle pair potentials in excellent agreement with independent measurements.
339. Dynamics and Collapses of Two-Dimensional Colloidal Lattices

Sowmitri Tarimala, Chihyuan Wu and Lenore L. Dai, Texas Tech University, Lubbock, TX
One interesting aspect of colloidal particles is the formation of colloidal crystals at the two-dimensional and three-
dimensional level. Here we report the dynamics and collapses of colloidal lattices at liquid-liquid interfaces using
Pickering emulsions as an experimental template. The colloidal particles oscillate around their equilibrium positions. The
short-time diffusion constant of single particles increases with increasing the lattice spacing; the oil phase viscosity only
has an effect on diffusion at large inter-particle distances. Strikingly, we observe that the equilibrium structure can be
disturbed when increasing the output laser intensity in a confocal laser scanning microscope which leads to the
collapse of colloidal lattices under small radiation pressure forces.
340. Spontaneous pattern formation by dip coating of colloidal suspensions on

homogeneous surfaces
Moniraj Ghosh, johns Hopkins University, Baltimore, MD, Fengqiu Fan, Saoirse Corporation, Cambridge, MA and
Kathleen J. Stebe, Johns Hopkins University, Baltimore, MD
A partially wet, energetically homogeneous plate is withdrawn vertically at velocity U from a suspension of well-wet
colloidal particles. Periodic horizontal striped assemblies form at the three phase contact line, with stripe width and
spacing depending on the withdrawal velocity U relative to a transition velocity U t . Thick stripes separated by large
spaces form for U < U t . For U > U t , thin stripes separated by small spaces form. Stripe spacing is reduced by an order
of magnitude and varies weakly with U until a maximum velocity is reached at which the stripes fail to form. A partially
wet surface can entrain a meniscus. For U < U t , the meniscus forms with a pinned contact line. As the plate moves
upward, it stretches the meniscus until it becomes too heavy to be retained by the wet, porous network provided by the
particles at the contact line. The contact line then jumps backwards to find a new equilibrium location, and the process
begins anew. For U>U t , a film of thickness h is entrained above the meniscus. For h smaller than the particle diameter
D, particles aggregate where the entrained film thickens to match up to the wetting meniscus. When an entrained
particle becomes exposed to air by evaporation, it becomes the new pinning site. h increases with U; at some velocity,
h becomes comparable to D. Particles flow into the film and deposit there in a disordered manner. A diagram
summarizing particle deposition is developed as a function of D, U and h.
341. Dipole interactions between dielectric spheres in AC electric fields
Manish Mittal1 , Eric W. Kaler 2 and Eric M. Furst2 , (1)University Of Delaware, Newark, DE, (2)University of Delaware,
Newark, DE
Micron-sized dielectric spheres aggregate to form linear chains on application of an AC electric field. The dipole-dipole

attraction is the dominant force in this process. The potential energy of a pair of polystyrene spheres has been
experimentally measured. This is done by observing the equilibrium separation between particles held in static optical
traps of known trap strength at various electric field intensities. The potential is evaluated for a range of salt
concentrations and electric field frequencies. Subsequently the kinetics of “pearl-chain” growth has also been studied
under the same conditions. The potential calculated for a pair is then used to predict the aggregation kinetics and
comparisons are made with those obtained by solving the Smoluchowski equation. This study helps in validating the
potential calculated for a pair and extending the results from pair interaction to those for an ensemble of particles.
342. Electrokinetically-driven Capture of Colloidal Particles within Media of High Ionic

Strength
Matthew R. Tomkins, Jeffery A. Wood and Aristides Docoslis, Queen's University at Kingston, Kingston, ON, Canada
Experiments and numerical simulations are combined in an attempt to elucidate the mechanism by which colloidal
particles suspended in physiologically relevant (i.e., high ionic strength) media can be electrokinetically sampled on a
surface. Results are reported for the trapping of 210 nm fluorescently labeled polystyrene spheres under the influence
of a high frequency non-uniform electric field created by planar quadrupolar microelectrodes deposited on an oxidized
silicon chip. 3D computer modeling is subsequently used to yield the spatial profiles of electric field intensity,
temperature, fluid velocity and force balance on the particles. The results suggest that the experimentally observed
rapid particle trapping is achieved by the synergistic action of dielectrophoresis and electrothermal fluid flow.
Specifically, electrothermal fluid flow was found responsible for the transport of the particles from the bulk of a
suspension to the surface, where dielectrophoretic forces, which become significant only at very small length scales
from the surface, cause their stable capture. The calculations show that the time scales associated with the transport
and capture of particles when a non-uniform AC field is used are smaller by at least one order of magnitude when
compared with those corresponding to a diffusion-limited system. This study can provide valuable insights in the design
and operation of biosensors for rapid and in-situ detection of pathogens from small sample volumes, or the
development of point-of-care diagnostic devices and micro-total analysis systems (micro-TAS) that operate on AC
electrokinetic principles.
343. Aggregation: how does a doublet of spheres interact with other particles?
ABSTRACT WITHDRAWN
The dynamics of aggregation in colloidal systems are often described in terms of collision efficiencies: the ratio of actual
aggregation to that caused by only the external forces on the individual particles. A standard way to calculate these
efficiencies is to consider the effects of hydrodynamics, Brownian motion, and other colloid-scale forces on the
interaction of two spheres. However, a particle formed from two aggregated spheres is far from spherical, and the
accuracy of this approximation remains open.
In this paper we use an "exact" method to investigate the interaction between an aggregated doublet of spheres and a
third sphere, under the action of hydrodynamic forces. We show how this interaction depends on the orientation of the
doublet, compare the overall mobility of the system with that predicted more quickly by the Stokesian Dynamics
approximation, and give some engineering approximations for the radius which should be chosen for the new sphere
representing the doublet, in order to make best use of the spherical approximation.
This is work carried out in part by Anushi Weliwita, a summer project student from Sri Lanka.
344. Ionically self-assembled thin films for second-order nonlinear optics

Akhilesh Garg, Cemil Durak, Richey M. Davis and Randy Heflin, Virginia Polytechnic Institute and State University,
Blacksburg, VA
Organic materials exhibiting second-order non-linear optical (NLO) properties are a key to the development of advanced
electro-optic modulators used in fiber-optic communications system. This research concerns a layer-by-layer technique
used to fabricate films with useful second order NLO properties. A polycation - poly(allylamine) hydrochloride (PAH) -
and a polyanion, poly{1-[4-(3-carboxy-4-hydroxyphenylazo)-benzenesulfonamido]-1,2ethandiyl} (PCBS) are self-
assembled on a substrate by alternately adsorbing the two polymers. We study the film deposition process using a

Quartz Crystal Microbalance (QCM), ellipsometry, and absorbance measurements.
The deposition of multiple layers of PAH and PCBS adsorption were studied at different concentrations using a silicon
dioxide-coated substrate in a QCM. The results show a linear decrease in frequency with increasing number of
adsorbed layer signifying a homogeneous growth of the self-assembled films. Data obtained from QCM were compared
with thickness measurements from ellipsometric data and absorbance measurements to estimate the water content in
these films. These findings will help us to understand this self-assembly at the molecular level in order to make a
practical electro-optic modulation device.
345. Effects of ion size and charge on the electrical double layer formation in nanopores
Chia-Hung Hou 1 , Patricia L. Taboada-Serrano 2 , Sotira Yiacoumi 1 and Costas Tsouris3 , (1)Georgia Institute of
Technology, Atlanta, GA, (2)Georgia Institute of Technology, Oak Ridge, TN, (3)Oak Ridge National Laboratory, Oak
Ridge, TN
Electrical double layer (EDL) formation in nanoporous materials is important to many physicochemical processes of
practical significance, including energy storage in super-capacitors and water purification. The effects of ion size and
charge of electrolytes confined in charged nanopores are simulated here by Monte Carlo techniques, including
Canonical Monte Carlo and Grand Canonical Monte Carlo. Simulation results show that multivalent and monovalent
ions present different characteristics under an electrostatic field in nanopores. When the pore size approaches to the
dimension of ionic species, EDL overlapping occurs, which limits participation of ions in EDL formation. The distribution
of ionic species is also very sensitive to the ion size. Furthermore, charge inversion may occur under certain conditions
of high electrolyte concentration and high surface charge. This phenomenon is more evident in the presence of
multivalent counterions of a larger diameter. Three competitive factors can explain the fundamental mechanisms behind
the EDL behavior: (i) ion displacement due to ion-excluded volume, (ii) asymmetry in ion charge, and (iii) occurrence of
EDL overlapping. Besides the modeling work, electrochemical characteristics are revealed by cyclic voltammetry,
demonstrating that the relationship between the pore size and ion size can determine the EDL capacitance of
nanoporous electrodes. This study concludes that the consideration of ion size, in both experimental and theoretical
studies, is essential to our understanding of the EDL behavior of nanoporous materials, as well as to applications of
practical significance.
346. Synthesis of Gas-Hydrate Aggregates for Applications in Energy Systems
Patricia L. Taboada-Serrano 1 , Phillip Szymcek2 , Shannon Ulrich 2 , Megan E. Madden2 , Tommy J. Phelps2 and
Costas Tsouris2 , (1)Georgia Institute of Technology, Oak Ridge, TN, (2)Oak Ridge National Laboratory, Oak Ridge, TN
Gas hydrates are solid crystalline structures in which water cages enclose gas molecules in a unit volume equivalent to
at least a hundred unit volumes of gas under the same conditions. Naturally occurring gas hydrates can be found in
ocean sediments or the permafrost, and their existence constitutes an attractive future source of energy. Industrially,
gas hydrates offer promising means for safe storage and transport of large volumes of gas, as well as produced water
purification at the wellhead during natural gas production operations. Additionally, the utilization of gas hydrates is being
explored as a feasible method for direct carbon sequestration. In this work, we report on the investigation of strategies
for the synthesis of gas hydrate aggregates intended for applications as mentioned above. Gas hydrate aggregates of
varying degree of consistency are synthesized in a two-phase, micro-emulsion injector reactor. Degrees of
cohesiveness desired for specific applications can be controlled by the choice of guest gas and its composition in the

hydrocarbon phase, and by the regulation of such operating parameters as pressure, temperature, reactant ratios and
degree of emulsification. Results on hydrate synthesis dealing with ocean carbon sequestration and coal-bed methane
produced water treatment at the wellhead are discussed.
347. Influence of Synthesis Technique on Electrokinetic Properties of Fullerene (C60 )

Nanoparticles in Aqueous Solutions
Kai Loon Chen and Menachem Elimelech, Yale University, New Haven, CT
Buckminsterfullerene C 60 is an emerging nanomaterial that has attracted interest for its diversity of potential
applications. Since fullerene C 60 is only soluble in some organic solvents and is almost insoluble in water, recent
efforts have been made to synthesize fullerene nanoparticles suspended in water suitable for use in aqueous and
biological systems. Currently, there are two techniques employed to synthesize these nanoparticles. One technique
involves first dissolving fullerene in an organic solvent before ultrasonicating the mixture in water to remove the organic
solvent. Another technique simply requires the prolonged stirring of fullerene in water. Past studies have shown that
fullerene nanoparticles synthesized through both techniques exhibit a negative electrophoretic mobility, the source of
which is still unclear. In this study, we compare the electrokinetic properties and stability ratios of fullerene nanoparticles
synthesized through both techniques with the objective of understanding the source of their surface charge.
Electrophoretic mobility measurements showed that both nanoparticles remained negatively charged over the pH range
of 2–12, and that the electrophoretic mobility became less negative towards the lower pH. The aggregation kinetics of
these nanoparticles were derived through time-resolved dynamic light scattering over a range of sodium and calcium
chloride concentrations. The nanoparticles synthesized through prolonged stirring proved to be more stable to
aggregation than the other, implying that the synthesis technique plays an important influence over their surface
characteristics. Spectroscopic study will be conducted to detect the formation of charged functional groups on the
nanoparticles through the synthesis procedures.
348. The Effect of Filler-Polymer Interfacial Interactions on the Mechanical and Rheological
Performance of Automotive Topcoats
Dariush Hosseinpour 1 , James T. Guthrie2 and John C Berg 1 , (1)University of Washington, Seattle, WA, (2)University
of Leeds, Leeds, United Kingdom
Abstract:
The nature of interactions in assembled coatings containing an alumina filler that has been coated with different
chemical agents was investigated. The continuous medium was an automotive acrylic-melamine topcoat. The alumina
particle was incorporated into the polymer solution with the aid of wetting and dispersing agent over a range of particle
loading levels up to a particle volume concentration (pvc) of 50%. The approach taken involved ultimate tensile strength
evaluations and rheology studies. In general, it was found that there is a strong correlation between the ultimate tensile
properties and both the alumina loading level and the nature of the surface treatment given to the alumina particles.
Functionalization of the alumina with agents, to give apolar characteristics resulted in deterioration of the composite
tensile strength. Alumina particles with polar surface treatments gave an interaction with the matrix that improved the
mechanical performance of the system. This improvement was attributed to the role of the Lewis acid–base
interactions. The rheological studies and subsequent calculations show that, at the dispersion stage, the apparent
thickness of adsorbed polymer layer varied with the nature of the surface of the alumina. The adsorbed layer had an
intermediate thickness for the dispersions containing the polar alumina. This thickness for the systems containing
apolar alumina and untreated alumina was the greatest and the least, respectively.
349. Estimation of Hamaker coefficients for PEM fuel cell supported catalysts
Ram Subbaraman, Thomas Zawodzinski, Jr. and J. Adin Mann, Case Western Reserve University, Cleveland, OH
Supported Platinum electrocatalysts are used in Polymer electrolyte membrane fuel cells (PEMFC) to catalyze the
hydrogen oxidation and oxygen reduction reactions. The high surface to volume ratios of supported catalysts maximizes
the area of catalytic surfaces available for reactions. A proper distribution of platinum nanoparticles on the carbon
support minimizes the loss in activity due to agglomeration of the nanoparticles. Since colloidal interaction forces drive

the deposition process, it is imperative to understand the interactions between the support and the catalyst
nanoparticles. This interaction is used as the basis of our modeling of electrode structure using a hierarchical scheme of
successively more complex structures. The free energy of interaction we measure is scaled by the Hamaker coefficients
for the materials. We estimate these coefficients from optical spectra using Lifshitz theory; optical spectra for the carbon
support and catalyst particles are measured. The Hamaker coefficients we compute are used in computer simulations
of the formation of particle ensembles using a stochastic model reported earlier that takes into account near neighbor
interactions. The sensitivity to the values of the Hamaker coefficient on the processes of nanoparticle aggregation,
dispersion on the surface and loading of catalysts will be discussed. Kinetic Monte Carlo calculations are performed to
obtain nanoparticle cluster structure with and without the effect of the support interaction. We will discuss the
implications of the strength of the various interactions on the expected durability of fuel cell electrocatalyst structures.
350. Numerical simulation of nanocrystal formation in solution by burst nucleation and

diffusional growth
D.T. Robb and V. Privman, Clarkson University, Potsdam, NY
The mechanism of "burst nucleation" of crystals from a supersaturated solution, as first put forward by LaMer and
Dinegar (J. Amer. Chem. Soc. 72, 4847 (1950)), has been widely used in explaining the chemical synthesis of both
mono- and poly-crystalline colloidal particles from solution. However, to our knowledge, the proposed kinetics of the
burst nucleation mechanism have not been fully verified. Here we report the results of numerical simulations of a model
of the burst nucleation process, in which instant rethermalization of sub-critical embryos and irreversible diffusive growth
of super-critical clusters is assumed. We present approximate analytical results for the long-time behavior of the
cluster-size distribution in the model, and discuss the applicability of the model and numerical results to experimental
colloidal systems.
351. The Balanced Nucleation and Growth Model for Controlled Crystal Nucleation and Size
Distribution – I. The Model
Ingo Leubner, Crystallization Consulting, Penfield, NY
The Balanced Nucleation and Growth (BNG) Model was first proposed and experimentally supported in 1980(1-4). The
BNG model has correctly predicted previously unknown nucleation behaviors.
The present derivation of the BNG model is based on the classical concepts of Becker and Doering, but replaces the
kinetic nucleation rate with the introduction of crystal growth processes during the nucleation phase.
The BNG model predicts the experimental result that many crystallization processes lead to a limited number of crystals
during a nucleation period which is followed by growth only. Further, the model predicts the crystal formation during the
nucleation phase, the crystal size distribution, maximum crystal size, number of crystals, nucleation rate and time.
Model variables are the molar reactant addition rate during the nucleation phase, nucleation efficiency, critical nucleus
size,and maximum crystal growth rate. These are related to experimental parameters. Without growth, the crystal
number is proportional to addition rate and nucleation occurs continuously during the time of reactant addition.
The BNG model was originally derived for balanced double-jet batch precipitation, and later extended and
experimentally confirmed for controlled double-jet continuous crystallizations. (5)
1. Leubner, I. H., et al, Photogr. Sci. Eng., 24:268 (1980); 2.Leubner, I. H., J. Phys. Chem., 91:6069 - 6073 (1987; 3.
Leubner, I. H., J. Disp. Sci. Technol., 22 :125 – 138 (2001); 4. Leubner, I. H., J. Disp. Sci. Technol., 23:577 – 590
(2002); 5. Leubner, I. H., J. Imaging Sci. Technol., 42:357(1998)
352. The osmotic motor

John F. Brady and Ubaldo Cordova-Figueroa, California Institute of Technology, Pasadena, CA
We propose a model for self-propulsion of a colloidal particle – the osmotic motor – immersed in a dispersion of
colloidal ‘bath' particles. The osmotic motor is propelled by a chemical reaction that consumes bath particles over a
portion of its surface. The non-equilibrium microstructure of bath particles induced by the surface reaction creates an

‘osmotic pressure' imbalance on the motor's surface causing it to move to regions of lower bath particle concentration.
The osmotic motor's behavior is calculated for two scenarios: one in which the motor is held fixed and a second where
it is free to move. The departure of the bath particle concentration from equilibrium is characterized by the Damköhler
number Da: the ratio between the surface reaction velocity and the diffusion velocity. The computed microstructure is
employed to calculate the driving force of the motor, from which the self-induced osmotic velocity is determined via
application of Stokes drag law. For small departures from equilibrium (Da << 1), the self-propulsion is determined by
the reaction velocity. In the large Da limit the surface reaction dominates over diffusion and the osmotic velocity cannot
be greater than the speed of bath particles that are about to react. The implications of these features for different bath
particle volume fractions and particle sizes are discussed. Theoretical predictions are compared with Brownian
Dynamics simulations.
353. Diffusion in charge-stabilized colloidal suspensions: Theory, simulation and

experiment
Gerhard Naegele1 , Adolfo J. Banchio2 , Adam Patkowski 3 and Jacek Gapinski 3 , (1)Research Centre Juelich, Juelich,
Germany, (2)Universidad Nacional de Cordoba, Cordoba, Argentina, (3)A. Mickiewicz University, Poznan, Poland
We report on a joint experimental-theoretical study of diffusion processes in dense suspensions of charge-stabilized

colloidal spheres. Numerous transport properties have been calculated by means of a recently developed accelerated
Stokesian dynamics simulation tool, and using methods of many-body theory adapted to colloidal soft matter systems.
The simulation and theoretical methods describe quantitatively our static and dynamic synchrotron radiation scattering
experiments on colloidal particles, globular proteins and DNA fragments. Salient results of this study comprise the
absence of screening of hydrodynamic flow in salt-free suspensions, and a hydrodynamic explanation for the
unexpected non-monotonic concentration dependence of self-diffusion in suspensions of moderately charged particles.
354. Colloidal traffic through static and dynamic optical lattices

Gabriel C. Spalding, Illinois Wesleyan University, Bloomington, IL
Twenty years ago Arthur Ashkin, Steve Chu, and co-workers published the first paper using the single-beam optical
gradient trap, now known as Optical Tweezers. Recently, in the near field, we have successfully demonstrated an
approach that allows optical forces alone to assemble thousands of microparticles over macroscopic areas. Separately,
the addition of simple holographic techniques has extended the basic capabilities of optical tweezing, making it a more
viable tool for the assembly of micro-systems and the organization of specimens into user-defined structures. Our early
efforts at filling a 3D lattice of optical traps led to an appreciation for the dynamics of injected microparticle streams,
which yield a surprisingly successful method of sorting or re-routing within microfludic environments. Here, we present
real-space studies of Brownian hard sphere transport though externally defined potential energy landscapes.
355. Direct visualization of rod dynamics in three dimensions using confocal microscopy
Deshpremy Mukhija and Michael J. Solomon, University of Michigan, Ann Arbor, MI
The dynamics of suspensions of anisometric colloids are of both fundamental and technological interest because of their
effect on liquid crystal phase transitions, rod-jamming and the transport of rigid, anisotropic bacteria, viruses and
polymers. Here, we develop and test an experimental method to investigate the dynamics of rod particles by measuring
their rotation and translation in three dimensions. The method relies on solvent viscosification to retard dynamics to
scales that are compatible with 3D confocal laser scanning microscopy. We demonstrate the performance of the
method by tracking the Brownian motion of fluorescent poly (methyl methacrylate) rods (aspect ratio, L/D = 3.1 and 7)
grafted with poly (dimethylsiloxane). The rods are dispersed at dilute concentration in a solvent mixture of viscosity
2000 cp. Rod translational and rotational diffusivities are extracted from the measured translational mean square
displacement and time correlation functions of the rod director, respectively. The orientational dynamics of the rods are
characterized relative to both their azimuthal and polar angles. Experimental values obtained agree well with theory. As
an example of the future utility of this method, we investigate the rotational dynamics of depletion induced colloidal rod-
gels.
356. Shear-induced migration of suspensions in 3D microfluidic geometries

Changbao Gao and James F. Gilchrist, Lehigh University, Bethlehem, PA
We investigated shear-induced migration of 1 micron Brownian particles in 1D, 2D, 3D steady microfluidic flows
generated in straight, herringbone, and staggered herringbone channels respectively. The transverse flows induced by
recessed herringbone structures in the top of the channels interplay with particle migration to the low shear regions of
the pressure-driven flow. Using high-speed confocal laser scanning microscopy, we were able to image directly flowing
particles inside the channels. Moreover, we located the 3D positions for each particle and obtained 2D concentration
and 2D velocity profiles to better understand of the effects from the underlying flow topology, colloidal hydrodynamics,
and Reynolds and Péclet number on particle migration.
357. Dynamics of suspensions of pH-responsive hydrogel colloids

Jae Kyu Cho, L. Andrew Lyon and Victor Breedveld, Georgia Institute of Technology, Atlanta, GA
Colloidal hydrogel particles have attracted interest as building blocks for chemical sensors, photonic crystals and as
drug delivery vehicles. In addition, they are interesting model systems to study the phase behavior of colloidal
dispersions with soft interaction potentials. The most commonly used pNIPAm hydrogels are temperature sensitive,
showing a swelling-deswelling transition around 30 degrees Celcius; by including acrylic acid copolymer, one can obtain
pNIPAm-co-AAc hydrogels that are also pH responsive.
For this work, we have investigated the dynamics of swelling and deswelling of these stimuli-responsive colloids in both
dilute and concentrated suspensions via particle tracking video-microscopy in a transparent microdialysis cell. The
device allows us to change the solvent composition (e.g. pH) in a controlled manner while simultaneously tracking the
motion of hydrogel particles.
In dilute suspensions, we have studied the swelling-deswelling response of hydrogels of different sizes and varying AAc
contents to elucidate the kinetics of the microstructural rearrangements of the hydrogel. In concentrated suspensions,
the pH-induced particle expansion causes transitions between fluid, glassy and crystalline phases. Data will be
presented on the dynamics of the observed phase behavior, in particular crystal growth and jamming.
358. Microfluidic Assembly and Packing of Colloidal Granules
Robert F. Shepherd1 , Jacinta C. Conrad1 , Summer K. Rhodes1 , Darren R. Link2 , David A. Weitz 3 , Manuel Marquez 4
and Jennifer A. Lewis 1 , (1)University of Illinois, Urbana-Champaign, Urbana, IL, (2)RainDance Technologies, Inc.,
Guilford, CT, (3)Harvard University, Cambridge, MA, (4)Phillip Morris USA, Richmond, VA
The microfluidic assembly and packing of colloid-filled hydrogel drops and dried granules of varying shape and
composition is investigated. Drops are formed by shearing a concentrated colloidal microsphere-acrylamide suspension
in a continuous oil phase using a sheath-flow or a double emulsion capillary device. Silica microspheres are
synthesized with different fluorescent cores to allow direct visualization of the process. Homogenous and Janus
(hemispherically distinct) spheres and disks are produced by confining the assembled drops in microchannels of
prescribed geometry. To preserve their drop structure, photopolymerization of an acrylamide-based hydrogel solution is
carried out immediately after drop-breakup. Representative drops and dried granules are imaged using fluorescence
and scanning electron microscopy to probe their structural evolution during assembly and drying, while micro-CT is
used to probe granular packing. Our approach opens up new opportunities for precision engineering of colloidal granule
size, shape, and composition.
359. A Generalized Hertzian Model for the Cracking of Thin Latex Films Saturated With Fluid
William B. Russel and Ning Wu, Princeton University, Princeton, NJ
The concentration of a thin film of a stable colloidal dispersion increases as water evaporates until the particles
eventually reach a random or ordered close packing. Further water evaporation generates a negative capillary pressure
that puts the film in tension. If the process temperature is below the glass transition temperature of the elastic particles,
the latex film beyond a critical thickness will eventually crack. We develop a generalized model to understand this
question of cracking. We first construct a constitutive equation relating the stress to the strain with the assumption of
Hertzian contact between colloidal particles. Then, employing a thin film approximation, we are able to reduce the

three-dimensional problem into two dimensions and calculate the relaxation of stress fields upon opening of a crack.
Based on the well-known Griffith's energy criterion (by equating the recovery of elastic energy to surface energy), the
theory predicts critical capillary pressures necessary for opening of a single infinite crack, a finite isolated crack, parallel
cracks, and intersecting cracks, respectively. The accompanying crack spacings are also predicted and they decrease
with increasing capillary pressures. Coupling the critical capillary pressure for cracking with the maximum capillary
pressure sustainable with the air-water interface at the surface of the film then yields a critical film thickness below
which cracking will not occur. Finally, the comparison between our theoretical predictions and experimental results will
be discussed briefly.
360. Rheological probes of the relaxation dynamics of densely packed drops and bubbles
Hans M. Wyss1 , Johan Mattsson2 , Kunimasa Miyazaki 3 , David R. Reichman 3 and David A. Weitz 1 , (1)Harvard
University, Cambridge, MA, (2)Chalmers University of Technology, Göteborg, Sweden, (3)Columbia University, New
York, NY
Foams and compressed emulsions exhibit a fascinating mechanial behavior; while they consist entirely of fluids, their
macroscopic rheological behavior is elastic-like within the time scales accessible to oscillatory rheology. They show the
viscoelastic behavior typical for soft glassy materials, which suggests that a slow structural relaxation should dominate
their rheology at low frequencies. In this talk we will present experimental results on these systems and discuss
differences to the behavior of suspensions of hard particles. We combine linear and nonlinear viscoelastic
measurements by performing constant-rate sweeps, keeping the strain rate constant as the oscillation frequency is
varied. The viscoelastic response of these systems at different extents of oscillatory strain rate supports the validity of
Strain-Rate Frequency Superposition (SRFS) [*] for these systems; the shape of the structural relaxation remains
unchanged within a wide range of applied strain rates. However, the same techniques also allow us to detect a
secondary relaxation process that appears to be intimately linked to the main structural relaxation itself, with a time
scale that shows the same strain rate dependent scaling behavior. We present a simple model description that
qualitatively accounts for the observed behavior.
[*] see /cond-mat/0608151
361. Yield stress and thixotropy: on the difficulty of measuring yield stresses
The yield stress of many yield stress fluids has turned out to be difficult to determine experimentally. This has led to
various discussions in the literature about those experimental difficulties, and the usefulness and pertinence of the
concept of yield stress fluids. We argue here that most of the difficulties disappear when taking the thixotropy of yield
stress fluids into account, and will demonstrate an experimental protocol that allows reproducible data to be obtained
for the critical stress necessary for flow of these fluids. As a bonus, we will show that the interplay of yield stress and
thixotropy allows one to account for the ubiquitous shear localization observed in these materials. However, due to the
thixotropy the yield stress is no longer a material property, since it depends on the (shear) history of the sample.
362. DWS-based micro-rheology on vesicle depletion gels

Matthew L. Lynch and Tom Kodger, Procter & Gamble Company, Cincinnati, OH
Traditional DWS-based micro-rheology measures the high-frequency moduli of viscoelastic fluids by tracking the motion
of particle tracers. We extended this concept to vesicle depletion gels where the viscoelasticity arises not only from the
interstitial viscoelastic fluid but also from the microstructure of the dispersion. Importantly, DWS measurements allow the
direct measure of vesicle motion (bypassing the need for tracers) with essentially no applied stress. There is a broad
agreement between the magnitude of the moduli measured with oscillatory rheology and DWS-based micro-rheology
demonstrating the general application of this combined technique for studying particle gels. This approach is being
used to study collapse rates, aging and delayed collapse of these gels.
363. Nonlinear microrheology of a wormlike micelle solution using ferromagnetic nanowire

probes

Nathan Cappallo, Clayton Lapointe, Robert L. Leheny and Daniel H. Reich, Johns Hopkins University, Baltimore, MD
We describe the application of high-aspect-ratio ferromagnetic nanowires as microrheological probes of wormlike

micelle solutions composed of equimolar cetylpyridinium chloride/sodium salicylate (CPCl/NaSal). Employing high-speed
video microscopy to track the rotation of suspended nanowires in response to external magnetic fields we access both
the linear and nonlinear rheology of the fluid. The linear viscosity at low rotation rates is strongly temperature
dependent as expected from macroscopic rheometry. At high rotation rates the viscosity exhibits pronounced shear
thinning that is surprisingly independent of temperature. The onset of the nonlinear response is characterized by a
shear thickening that has no apparent counterpart in the macroscopic rheometry. Measurements involving step changes
in rotation rate reveal that, once the fluid has been prepared into a shear-induced state, it exhibits nonlinear behavior
far within the expected linear regime. Further, the shear-thinned fluid generates an out-of-plane torque on the wire
whose magnitude varies as a power law with the rotation rate, with a power-law exponent of approximately 0.4. From
time-resolved measurements tracking the motion of the wire in response to this torque we extract an effective viscosity
for drag perpendicular to the nonlinear shear flow. This viscosity reveals insight into the anisotropic behavior of the
shear induced state.
364. Active Laser Tweezer Microrheology of a Colloidal Suspension

Indira Gopal and Eric M. Furst, University of Delaware, Newark, DE
We investigate the behavior of a colloidal suspension using active, oscillatory microrheology. The experimental system
is an aqueous suspension of index matched fluorinated ethylene propylene (FEP) particles embedded with either 2 um
silica or 3 um polystyrene probe particles. The probes are trapped and oscillated using laser tweezers at frequencies of
5-1000 Hz and at amplitudes of 25-400 nm. The oscillation amplitude and phase of the probe are measured using a
photo diode and lock-in amplifier, which are used to compute the frequency dependent microviscosity of the
suspension. Frequency thinning is observed at all concentrations and is most significant for volume fractions above 0.3.
The results are in quantitative agreement with both previous measurements of the suspension microviscosity [1] and
recently developed theory [2].
[1] Meyer, A., et al., Journal of Rheology. 50(1), 77-92, (2006). [2] Khair, A. S., and J. F. Brady, Journal of Rheology.
49(6), 1449-1481, (2005).
365. Apparent Microrheology of Oil-Water Interfaces by Single Particle Tracking

Jian Wu and Lenore L. Dai, Texas Tech University, Lubbock, TX
We investigate the dynamics of charged microparticles at polydimethylsiloxane (oil) - water interfaces using Pickering
emulsions as an experimental template. The mobility of the charged particles depends largely on the viscoelastic
properties of the oil phase and the wettability of the solid particles. More importantly, we have explored the potential of
developing one-particle microrheology at liquid-liquid interfaces. The complex, loss, and storage moduli of oil-water
interfaces as a function of frequency measured from microrheology are compared with those of bulk oils measured from
a conventional rheometer and developed bulk microrheology. The nature of the tracer particles plays an important role
in one-particle microrheology at liquid-liquid interfaces, especially when the oil phase is viscoelastic.
366. Dissolution of concentrated surfactant systems: convection and microstructural

effects
Marco Caggioni, Christopher Stoltz and Pat Spicer, Procter and Gamble Company, West Chester, OH
We utilize a combination of millifluidic and particle tracking microrheology experiments to study dissolution dynamics in
concentrated surfactant systems. Previous work conducted demonstrated the diffusion-limited nature of this process
and highlighted the need for a better understanding of mesophase formation and convective effects on dissolution
dynamics [1,2]. Our experiments enable us to measure diffusivity in the different meshophases formed during
dissolution by combining results obtained with different boundary conditions. The use of millifluidic devices allows us to
investigate the role of convection on dissolution dynamics while microrheology provides information on the evolution of
local viscoelastic properties.

1 Lim, J. C., Miller, C. A., "Dynamic Behavior and Detergency in Systems Containing Nonionic Surfactants and Mixtures
of Polar and Nonpolar Oils," Langmuir, 7, 2021-7 (1991).
2 Chen, B.-H., Miller, C. A., Walsh, J. M., Warren, P. B., Ruddock, J. N., Garrett, P. R., Argoul, F., Leger, C.,
"Dissolution Rates of Pure Nonionic Surfactants," Langmuir, 16, 5276-83 (2000).
367. Co-assembly of Alkylated DNA Oligomers and Nonionic Surfactants

Shane T. Grosser, Jeffrey M. Savard and James W. Schneider, Carnegie Mellon University, Pittsburgh, PA
Electrokinetic separation of DNA oligomers is a fundamental procedure in bioanalytical chemistry. While length
resolution is typically achieved by the use of polymer gels as sieving matrices, a faster alternative is to end-label
oligomers with uncharged objects so that the charge-to-mass ratio varies with oligomer length. With this goal in mind,
we have been exploring the use of nonionic micelles as end-labels for DNA in capillary electophoresis. DNA oligomers
of interest are end-alkylated (either covalently or by hybridization of an alkylated probe) to provide for interaction with
micelles. Unlike covalently attached polymers or proteins, nonionic micelles transiently attach to alkylated DNA by a co-
assembly mechanism, and this provides important advantages in bioanalytical applications. One is that the mobility of
the alkylated DNA can be tuned to prevent co-migration of oligomers. Using open-channel capillary electrophoresis in
the presence of Triton X-100, we demonstrate that DNA mobility is a very strong function of the attached alkane length
in the range of C12 to C18. A phase partitioning model is presented that fully accounts for the effect of alkane length,
DNA oligomer length, micelle size, and micelle concentration on the observed mobility. The model can be used to
measure the length of alkylated DNA, and model parameters can be predicted by thermodynamics of the co-assembly
process. Bi-alkylated DNA oligomers have also been synthesized. The combined effect of micelles at each end on is
found to be additive for long oligomers, but is attenuated for short ones due to hydrodynamic communication between
the micelles.
368. Reversible heteroaggregation of lipid vesicles using DNA as biomolecular combination

locks
Paul A. Beales and T. Kyle Vanderlick, Princeton University, Princeton, NJ
Besides being model systems for studying biological processes in cell membranes, lipid vesicles offer promise as
containers for use in technological applications. Gaining control of the interactions between vesicles of different
populations will enable vesicles with different chemical contents to be brought together into higher order structures for
manipulation: potentially their cargo could be mixed in small volumes by inducing fusion events between the vesicles in
such conglomerates. We use single-stranded DNA (ssDNA) anchored to the vesicle membrane to bind to vesicles of a
second population with the complementary ssDNA anchored to their membranes. The vesicles self-assemble into
superstructures of bound vesicles directed by the specificity of the interaction between complementary ssDNA strands.
We find three regimes of aggregation behaviour: no aggregation, stable aggregates and aggregates that grow until
flocculates are visible in solution. The rate of aggregation is determined by the vesicle collision rate and the probability
of hybridisation of complementary ssDNA strands during a collision. Vesicle binding is found to be reversible by heating
above a melting temperature for the DNA duplex. The thermal stability of the DNA duplex is found to be greatly
enhanced when anchored to the vesicles compared with the stability in free solution. This is caused by the enhanced
local concentration and reduced conformational entropy of the DNA due to being anchored to the lipid vesicles.
369. Numerical study on the self-assembling of DNA-dendrimers

Julio Largo, University of Rome La Sapienza, Roma, Italy, Francis W. Starr, Wesleyan University, Middletown, CT and
Francesco Sciortino, Universita' di Roma La Sapienza, Roma, Italy
The synthesis of nanoparticle building blocks functionalized with specifically designed oligonucleotides [1] has opened
new possibilities for the assembly of networked materials. The DNA-type interactions offer selectivity and sensitivity that
will play an important role in the self-assembly of these particles. These properties allow us to control the inter-particle
interactions that will lead to the construction of the desired supra-molecular structures. We present a molecular
dynamics simulation study of a simple DNA-dendrimer model designed [2] to capture the basic characteristics of the
biological interactions. Exploring a large set of state points [3], we follow the progressive formation of a percolating
large-scale network whose connectivity can be described by random percolation theory. We identify the relative regions

of network formation and kinetic arrest versus phase separation. The location of the two-phase region can be
interpreted in the same framework as reduced valency models. This correspondence provides guidelines for designing
stable, equilibrium self-assembled low-density networks. Finally, we demonstrate a relation between bonding and
dynamics, by showing that the temperature dependence of the diffusion constant is controlled by the number of fully
un-bonded dendrimers.
The design of an effective inter-particle potential for this family of dendrimers is discussed. The results obtained with
this effective potential are compared with the results of the full-system.
[1] Mirkin C A, Letsinger R L, Mucic R C and Storhoff J J Nature 382 607–9 (2006)
[2] Starr F.W. and Sciortino F.,J. Phys.: Condens. Matter 18 L347–L353 (2006).
[3] Largo J., Starr F.W. and Sciortino F. Langmuir (2007).
370. Phase behavior and surface anchoring of an isomeric monolayer at a nemtic liquid
crystal/aqueous interface
Andrew D. Price and Daniel K. Schwartz, University of Colorado, Boulder, Boulder, CO
In the absence of an external field, the long-range alignment of a nematic liquid crystal (NLC) layer depends on surface
anchoring by the bounding surfaces. A dynamic surface composed of an adsorbed amphiphilic monolayer at the
nematic/aqueous interface anchors the nematic in both a temperature and surface pressure-dependent manner in
response to the molecular organization of the monolayer. When composed of the azobenzene derivative 8Az3COOH
anchoring is also shown to significantly depend on the isomeric (cis-trans) composition of the monolayer. Long-range
alignment of the NLC layer is characterized by both the birefringence and director azimuth. Exhibited are isotropic 2D
vapor and liquid phases, primarily dependent on surface pressure, and condensed mesophase domains with defined
director azimuths at temperatures below 8-10 o C. Isomeric mixtures additionally exhibit a smectic C-like phase that
anchors the NLC with varying degrees of birefringence and no set director azimuth. The phase diagram of an
8Az3COOH monolayer adsorbed at a nematic/aqueous interface is plotted as a function of the control parameters
(temperature, surface concentration, and irradiation).
371. Single-molecule studies of surfactant adsorption, desorption, and surface diffusion

Daniel K. Schwartz, Andrei Honciuc and Adam Harant, University of Colorado, Boulder, Boulder, CO
We report single-molecule observations of surfactant adsorption, desorption, and surface diffusion at the solid/solution
interface using total internal reflection fluorescence microscopy (TIRFM). Typical surfactants used include carboxylic and
phosphatidic acids; substrates include fused silica and single crystal sapphire. The observation of individual adsorption
and desorption events permits the calculation of molecular "on rates" and "off rates" as a function of concentration, and
their comparison to the net adsorption rate as measured by laterally-averaging techniques. The surface residence time
distribution is also determined, and is consistent with first-order desorption kinetics. Surface trajectories of individual
molecules are analyzed as a function of surface crowding, and analyzed with respect to two-dimensional Brownian
motion. Typical surface diffusivities are in the range 0.01-0.1 square microns/second. Some interesting anomalies from
ideal Brownian behavior are observed at long diffusion times.
372. Structural Transition of Polyelectrolyte Brush at the Air/Water Interface

Hideki Matsuoka, Ploysai Kaewsaiha, Yoshiko Suetomi and Tasuku Yamada, Kyoto University, Kyoto, Japan
The nanostructure and its transition of polyelectrolyte brushes in the amphiphilic diblock copolymer monolayers on the
water surface were investigated by X-ray and neutron reflectivity techniques. The critical brush density (cbd), where the
transition between carpet-only/carpet+brush structures occurs, was quantitatively determined and its dependencies on
the hydrophilic chain length and salt concentration were examined. The cbd for polymethacrylic acid (PMA) brush
decreased with increasing PMA chain length. The cbd for polystyrenesulfonate (PSS) showed no chain length
dependence but increased beyond the critical salt concentration. The cbd for polyacrylic acid (PAA) showed no chain
length and no salt concentration dependencies. Hence the brush formation mechanism is suggested to be different from

each other for these three polyelectrolyte brushes. The salt effect on PSS brush and small ion transportation from/to
the PSS brush layer were also discussed. Ref. P.Kaewsaiha, K.Matsumoto, H.Matsuoka, Langmuir, 23(1), 20-24
(2007).
373. Self-assembly of multilayer structures at the air-water and silicon-water interfaces
Mauro Moglianetti1 , Simon Titmuss 1 , S.P. Armes 2 and Robert K. Thomas1 , (1)Oxford University, Oxford, United
Kingdom, (2)University of Sheffield, Sheffield, United Kingdom
The self-assembly of multilayer structures has been observed for two different polymer/surfactant systems at the air-
water and at silicon-water interfaces through neutron reflectivity measurements.
At the air-water interface, poly(dimethyl aminoethylmethacrylate) (poly(DMAEMA)) and sodium dodecyl sulphate (SDS)
form multilayer structures at different surfactant concentrations at high and low pH. The use of different isotopic
compositions, in particular a perdeuterated polymer in combination with both hydrogenated and perdeuterated
surfactant, have allowed a complete characterization of the distribution of the polymer and surfactant across the
multilayer structure.
At the silicon-water interface, a high charge density polyelectrolyte incorporating poly(ethylene oxide) side chains
(poly(PEOyMEMA:METACx)) forms a multilayer structure at a bulk concentration of SDS that is below the CMC. The
position of the characteristic Bragg peak in the reflectivity profile, suggests the presence of surface micelles. The use of
multiple isotopic compositions allows us to propose a multilayer structure in which layers that are predominantly
composed of SDS micelles and water alternate with layers that are predominantly polymer and water. The micellar
layers do include some polymer, which suggests that a cooperative binding mechanism is responsible for the multilayer
structure.
374. Underwater Contact Angle Hysteresis of Superhydrophobic Polymer Surfaces

H. Yildirim Erbil, Gebze Institute of Technology, Kocaeli, Turkey
Surfaces that would decrease marine biofouling attract considerable theoretical and practical interest in the last decade.
Recently, it was demonstrated that engineered topographically corrugated surfaces are capable of reducing biofouling
because the fouling organisms that are larger than the primary length scale of the surface texture would exhibit reduced
adhesion strength as there would be fewer attachment points. However, when roughness and chemical heterogeneity is
introduced to a surface, then usually a large contact angle hysteresis, (H = θ adv - θ rec) is found showing the
deviation from the ideal flat and homogeneous surfaces. There are reports that H of the substrate has some effect on
biofouling and coatings having the lowest H show the best biorelease properties. In all of these publications, H and the
critical surface tension (γc) values of substrates were measured under air. Relating these values to the underwater
biofouling process is an indirect method and unjustified because low-energy surfaces in air tend to form high-energy
interface in aqueous solutions, and vice versa. Thus, there is a need to determine (Hunderwater) values for better
correlation to bioadhesion. Underwater contact angle measurement can be done by applying the two-liquids contact
angle method and its combination with the one-liquid method have been discussed. In this work, we show the
determination of underwater contact angle hysteresis of rough, hydrophobic polymer surfaces using two-liquids and air
bubble in water methods and discuss its possible implications on biofouling.
375. Lotus Inspired Superhydrophobic Coating using a Simple Single-step Sol-gel

Approach
Eric D. Branson1 , C. Jeffery Brinker 1 , Frank B. van Swol 1 and Seema Singh 2 , (1)Sandia National Labs / University of
New Mexico, Albuquerque, NM, (2)Sandia National Laboratories, Albuquerque, NM
Over the last decade there has been a growing interest in creating superhydrophobic (SH) surfaces stimulated by a
wide range of potential applications. Superhydrophobicity is loosely defined as contact angles of water exceeding 150º.
It has been suggested that contamination, corrosion, oxidation, current conduction and flow resistance can all be
reduced on superhydrophobic surfaces. Wenzel and Cassie - Baxter have established equations relating surface
roughness and contact angle. Both natural and synthetic SH materials show that both micro and nano scale roughness
are needed to achieve superhydrophobicity. Using our simple silica based aerogel procedure, SH films with contact

angles greater than 165º have been achieved with minimal roughness (~ 40nm). Using AFM, NMR, and scattering
(GISAXS/light), we are correlating pore size and surface roughness to superhydrophobicity. Furthermore we have
developed a procedure to optically control wetting of our SH surfaces. Exposure to UV light causes the macroscopic
contact angle to vary continuously from about 165º to 0º depending on exposure time. The result is a UV dose-
dependent decrease in contact angle. Spatial patterning is achieved by UV exposure through a mask as with
conventional lithography. This treatment changes the surface energy without affecting the surface structure. Vapor
phase exposure to a trimethylsilane restores the contact angle to nearly its original value. We present our simple single
step procedure for creating optically transparent SH coatings with minimal surface roughness and show the optimum
conditions needed for droplet rolling while also including some potential applications of these coatings.
376. Retention forces of a liquid slug in a rough capillary with symmetric or asymmetric
features
C. W. Extrand, Entegris, Chaska, MN
On surfaces with asymmetric or “saw tooth” features, liquid slugs or drops tend to move preferentially in one direction.
In these systems, capillarity manifests itself as a retention force that holds back the movement of liquids against
externally applied forces, such as gravity or pressure. In this theoretical study, the imbalance of capillary forces that
leads to directionally-biased wetting is examined. Capillary tubes with symmetric and asymmetric saw tooth features
were used to estimate the ratios of retention forces in opposing directions. Our analysis suggests that the difference
between the retention force in one direction versus the other can be maximized by increasing feature asymmetry and
minimizing inherent hysteresis (liquid-solid adhesion) of the materials of construction. This work has implications for
small channels or surfaces of fluid handling components found in microfluidic devices and fuel cells.
377. DNA Multi-Ring Formation Via Evaporation Process

Lu Zhang, Siddharth Maheshwari, Hsueh-Chia Chang and Y. Elaine Zhu, University of Notre Dame, Notre Dame, IN
The evaporation of a droplet often leads to the formation of a ‘coffee ring' pattern due to the outward evaporative flux
which carries the nonvolatile solute to the edge of the contact line. In this talk, we present an interesting observation of
multi-ring formation of DNA stain and elucidate the mechanism responsible for this unique multi-ring pattern formation
upon drying DNA droplets. A high-speed fluorescence microscope is used to visualize the structure and dynamics of the
multi-ring formation, which results from a pinning-depinning dynamics in contact line. At high concentrations, we
observe viscous figuring as a result of the stagnation flow, which is responsible for the formation of periodic multi-rings.
At lower concentration, we observe film rupture accompanied by contact-angle changes in a saw-tooth pattern, which
suggests rapid contact-line receding and results in the formation of aperiodic rings. We further examine the effects of
DNA concentration, droplet size and evaporation temperature on the spontaneous emergence of multi-ring patterns.
378. Phase separation in mixed Langmuir monolayers of n-pentadecanoic acid and

perfluoroundecanoic acid
Siwar Trabelsi and Daniel.K Schwartz, university of Colorado, Boulder, CO
Micro-phase separation in mixed Langmuir monolayers of n-pentadecanoic acid and perfluoroundecanoic acid is
observed due to chemical dissimilarity between the hydrogenated and fluorinated alkyl chains. We studied the influence
of various experimental parameters - including mixing ratio, n-alkyl chain length and temperature - on the morphology
of the mixed monolayer using Brewster angle microscopy and atomic force microscopy. In addition, we characterized
the role played by a third line-active molecular component, i.e. "linactant". A linactant molecule plays an analogous role
to that played by a surfactant in 3D. Linactants tested include partially-fluorinated molecules and two-tailed molecules.
We observe that the presence of linactant at very low concentrations systematically reduces characteristic domain
sizes, consistent with a decrease in line tension. A quantitative characterization of the fundamental line activity of the
linactant is performed by measuring line tension isotherms in the mixed monolayer. The measurement involves the
observation of relaxation dynamics of the domains, initially deformed from their equilibrium shape by surface shear.
379. Effect of wetting and interfacial properties on crystallization pattern of saturated salt
solutions during drying

Noushine Shahidzadeh-Bonn, Salima Rafai and Gerard Wegdam, Universiteit van Amsterdam, Amsterdam,
Netherlands
Salt weathering is an important cause of damage in building materials (stones, bricks, etc..) and threatens our cultural
heritage (statues, fresco, monuments..). However, there is still a lack of fundamental understanding of the difference in
crystallization damage between different salts such as sodium sulfate and sodium chloride. We study, using direct
imaging and optical microscopy, the growth of salt patterns during evaporation of saturated salt solutions on flat
surfaces with well controlled wetting properties. The results show the importance of wetting properties of the wall and
the presence or absence of a liquid film on the place where crystallization takes place (preference for liquid/air,
solid/liquid interfaces or solid/liquid/air contact line) and the crystallization pattern. These results were completed by the
experimental studies of crystal growth in capillary tubes with different geometries (circular and square cross section) as
simple model systems for a single pore within a porous medium. For the square capillary tube, the presence of thick
liquid films in the corners strongly affects the drying rate, ion transport and the onset of crystallization. Consequently,
the crystallization patterns are found to be very different even for a single salt in the two types of capillaries.
380. Determination of the basal and edge surface free energies of talc using the acid-base
theory
Jinhong Zhang and Roe-Hoan Yoon, Virginia Tech, Blacksburg, VA
The thin-layer wicking technique was employed to determine the contact angles (q) of different liquids on powdered talc
samples. The measured contact angles were then used to calculate the surface free energy (g S ) of a talc sample,
including its dispersion (g S d ), acidic (g S + ), basic (g S -), and acid-base (g S AB) free energy components, using the van
Oss-Chaudhury-Good (OCG) equation. By conducting the measurements at two different particle sizes, it was also
possible to determine the free energies of the edge and basal surfaces of the layer-structured mineral. The results
show that the basal surfaces are basic and the edges surfaces are acidic. By determining the surface free energies
before and after treating a talc sample with a polymer, it was possible to determine if the reagent adsorbs preferentially
on the basal or edge surfaces of the mineral and with what possible mode of orientation. The method developed in the
present work can also determine the particle size at which fracture begins to occur along the edge surfaces of the
mineral.
*Corresponding author: Tel. (540)231-7056; e-mail: ryoon@vt.edu
1Present address: Department of Mining and Geological Engineering The University of Arizona,Tucson,Arizona 85721
381. Surfactant effects on the activity and structure of the human adenosine A2a G-protein
coupled receptor
Michelle A. O'Malley and Anne Skaja Robinson, University of Delaware, Newark, DE
G-protein coupled receptors (GPCRs) represent the largest group of integral membrane proteins, accounting for over
50% of all pharmaceuticals targets. However, GPCRs prove difficult to study due to problems with their expression,
purification, and stability outside of the membrane environment. GPCRs, as with all membrane proteins, require
surfactants to stabilize their conformation outside the plasma membrane. High-level expression and purification of the
human adenosine A2a (hA2aR) receptor in a heterologous yeast system has enabled the characterization of this
receptor through biophysical techniques. Here, we assess the ability of different surfactants to stabilize the human
adenosine A2a (A2aR) receptor, as measured through ligand binding and biophysical methods. After solubilization from
the yeast membrane in n-dodecyl-beta-D-maltoside, different surfactants including maltosides, thiomaltosides, and
glucosides were exchanged and the effects of this exchange on the protein detergent complex (PDC) were carefully
monitored. The addition of a mammalian cholesterol analog (CHS) to the PDC is found to be crucial to the maintenance
of proper structure of A2aR. This interaction may hold the 7-alpha helical domains of the GPCR more rigid, in an active
conformation within the micelle. Furthermore, surfactants which share common structure and differ only by one carbon
length show marked differences in the ability to stabilize hA2aR. We will further explore the effects of surfactant type,
chain length, and other parameters on the activity of purified A2aR and on the protein detergent complex.
382. Diffusing Colloidal Probes of Calcium Mediated Cadherin Interactions

W. Neil Everett and Michael A. Bevan, Texas A&M University, College Station, TX
The ability to measure kT- and nanometer-scale potentials of mean force between proteins provides a fundamental
basis to understand many problems in biology and medicine. Yet, the current state-of-the-art in measuring protein
interactions is generally limited to mechano-chemical measurements of binding pair off-rates or spectroscopic
interrogation of ensemble dissociation constants. In this talk, we describe the use of freely diffusing colloids as probes
of thermally accessible, equilibrium interactions between cadherin fragments (cell-cell adhesion protein superfamily)
covalently attached and oriented on lipid bilayers supported on colloid and wall surfaces. In particular, two separate
methods involving diffusing colloidal probes are employed to measure the Ca2+ dependence of homophilic cadherin
interactions. In the first method, video microscopy is used to measure particle pair distribution functions from which
particle pair potentials are obtained via inverse Monte Carlo analyses. In the second method, integrated evanescent
wave scattering and video microscopy are used to simultaneously measure single and ensemble particle-wall
interactions to yield both equilibrium potentials and association dynamics. All measurements are performed in
physiological ionic strength buffers with varying [Ca 2+ ] to obtain information on short-range, protein-protein potentials.
The use of different particles sizes and supported lipid bilayers is exploited in this work to provide flexible control over
protein surface density, lateral mobility, and number of parallel association events. Ongoing work is extending these
approaches to sensitively interrogate heterophilic cadherin interactions using homophilic interactions from the present
work as a baseline.
383. Interactions Between Nucleoporins and Karyopherins Using a Quartz Crystal

Microbalance with Dissipation Monitoring with Relevance to Transport Across the Nuclear
Pore Complex
Amit K. Dutta 1 , Jacklyn Novatt 2 , Tijana Jovanovic2 , Antoine Bouchoux1 , Anna S. McKenney 2 , Mike P. Rout 2 , Brian T.
Chait 2 and Georges Belfort 1 , (1)Rensselaer Polytechnic Institute, Troy, NY, (2)The Rockefeller University, New York,
NY
The Nuclear Pore Complex (NPC) is the sole mediator of exchange between the nucleus and the cytoplasm in all
eukaryotic cells. While small molecules pass through the NPCs unchallenged, large macromolecules are excluded
unless chaperoned across by transport factors collectively termed Karyopherins (Kaps). The translocation of the
complexes of Kaps and their cargo proteins occurs through the specific affinity and binding between Kaps and
particular nuclear pore complex proteins (nucleoporins) called FG-Nups, that share a degenerate multiple-repeated
“Phe-Gly” motif. Our approach has been to form self-assembled monolayers (SAMs) of the FG-Nups bound directly
onto a gold surface via a cysteine-tag. The SAMs obtained were characterized using a quartz crystal microbalance with
dissipation monitoring (QCM-D) by observing the change in frequency and dissipation during adsorption. Kaps were
adsorbed onto an FG-NUP SAM to study the binding between FG-Nups and Kaps. A change in the slope of the
frequency versus dissipation plot confirmed the binding between FG-Nup and Kap. The relative floppiness of these
proteins was estimated from the specific dissipation during adsorption of these proteins onto gold. These results help
elucidate the binding mechanisms involved during the transport of large proteins through the NPC.
384. Sphingomyelinase-induced aggregation of low density lipoprotein

Michael J. Walters and Steven P. Wrenn, Drexel University, Philadelphia, PA
Cardiovascular disease (CVD) is the leading cause of human death in the US. Despite decades of intensive research,
the formation of atherosclerotic lesions is not fully understood. Aggregation of low density lipoprotein (LDL) is believed
to enhance the initiation of atherosclerosis. We are interested in sphingomyelinase (Smase)-induced aggregation of
LDL - as it relates to uptake by macrophages – which we demonstrated previously abides by colloidal principles of
mass action. Here we address the relative rates (kinetics of enzyme hydrolysis versus particle aggregation dynamics) to
suppress time as an independent variable and view LDL aggregation in ceramide space. Ceramide formation was
measured as a function of time for enzyme concentrations in the range 0-0.24 units Smase/mL at a fixed substrate
concentration 0.33 mg LDL/mL. LDL aggregate sizes were measured (dynamic light scattering, method of cumulants) as
a function of time for the same enzyme concentrations. Trends are shown between ceramide concentrations and
resulting aggregate sizes, giving more information on the relationships between these two values both during and after
completion of the enzymatic reaction and the aggregation process. We will present our results and discuss the findings
from a colloidal perspective. This work demonstrates the role that colloidal science can play in better understanding

human disease.
385. Engineering αL I Domain using Yeast Display to Modulate Adhesive Behavior

Lauren R. Pepper, Eric T. Boder and Daniel A. Hammer, University of Pennsylvania, Philadelphia, PA
Activated lymphocyte function-associated antigen-1 (LFA-1, αLβ2 integrin) found on leukocytes facilitates firm adhesion
to endothelial cells by binding to intercellular adhesion molecule-1 (ICAM-1), which is upregulated on the endothelium
at sites of inflammation. Recent work shows that LFA-1 in a preactivation, low-affinity state may also be involved in the
initial tethering and rolling phase of the adhesion cascade. The ligand binding epitope of LFA-1 is contained in the
inserted (I) domain, and a conformational change in this region during activation increases ligand affinity. We have
displayed wild-type I domain on the surface of yeast and validated expression using I domain specific antibodies and
flow cytometry. Surface display of I domain supports yeast rolling on ICAM-1-coated surfaces under shear flow. I
domain mutants were also expressed, and soluble ICAM-1 binding studies validated that these mutants have a range
of affinities for the ligand. Expression of the locked open, high-affinity I domain mutant supports firm adhesion of yeast
under shear flow, while yeast displaying intermediate-affinity I domain mutants exhibit a range of rolling phenotypes.
Rolling behavior for these mutants fails to correlate with ligand binding affinity. These results indicate that unstressed
binding affinity is not the only molecular property that determines adhesive behavior under shear flow. Work to validate
this observation on a larger scale is underway utilizing I domain mutant libraries to characterize the molecular structure-
function relationship via directed evolution. Understanding of adhesive behavior of particles on ICAM-1 surfaces will
facilitate further engineering of LFA-1 I domain for inflammatory targeting applications.
386. The structure, stability, and curvature of protein-coated lipid bilayer interfaces
Margaret Horton 1 , Christian Reich 1 , Suliana Manley2 , Bert Nickel 1 , Alice P. Gast 3 and Joachim O. Rädler 1 ,
(1)Ludwig-Maximilians-Universität, Munich, Germany, (2)National Institutes of Health, Washington, DC, (3)Lehigh
University, Bethlehem, PA
Proteins bound to lipid bilayer membranes provide a physical model for macromolecular complexes on cellular
membranes, and a template for immobilizing molecules at biocompatible surfaces. We study the proteins streptavidin
and avidin self-assembled on the surfaces of supported lipid bilayers (SLBs) and fluid lipid bilayer vesicles. Proteins
bind to the lipid bilayers through biotin-functionalized lipids, and streptavidin interacts laterally to form two-dimensional
protein crystals. We systematically vary the relative amounts of streptavidin and avidin at the lipid bilayer surface to
investigate how crystalline proteins influence the structure, fluidity and curvature of lipid bilayers. Our experimental
approach combines fluorescence microscopy and X-ray reflectivity, allowing us to determine the molecular structure of
the protein/lipid interface, and the influence of microscopic protein crystals on the physical properties of the interface.
Using synchrotron X-ray reflectivity, we measure the dimensions of the bound protein layer, as well as the thin hydrated
layer separating the proteins from the lipid bilayer. We compare the stability of our protein-coated lipid bilayer interfaces
to previous studies of protein-coated lipid monolayers. With fluorescence microscopy, we demonstrate how proteins
confer stability to lipid bilayers subjected to mechanical stress and slightly decrease lipid diffusion constants. The
experimental framework that we present can be extended to study more complex protein-lipid interactions at a single
lipid bilayer interface.
387. Steric stabilization of magnetite nanoparticles with charged, water-soluble triblock

copolymers with polyether end groups
Richey Davis, Qian Zhang and Judy Riffle, Virginia Tech, Blacksburg, VA
Novel triblock copolymers consisting of end blocks of polyethylene oxide (PEO) and a center block consisting of
urethane and carboxylic acid groups have been shown to sterically stabilize magnetite nanoparticles that have potential
drug delivery applications.(1) For these applications, it is essential to control the state of dispersion of the magnetite
nanoparticles, especially with a coating of a biocompatible polymer such as PEO which can inhibit protein binding.
These block copolymers adsorb on particles of magnetite, Fe3O4 approximately 10 nm in diameter via the carboxylic
acid-containing center block. This leads to the formation of a PEO brush layer that sterically stabilizes the particles in
an aqueous buffer solution for periods of weeks. Critical parameters that were measured included particle size with the
adsorbed triblock stabilizer, the number of polymer chains/unit area bound to the particles, and the zeta potential of the
particles. The hydrodynamic diameter of the polymer-magnetite complexes can be predicted using the Density

Distribution model by Vagberg, et.al., that was based on the blob model for star polymers. The observed colloid stability
can be related to the interparticle pair potential that governs particle dispersion by the modified Deryaguin-Landau-
Verwey-Overbeek (DLVO) theory in which the steric pair interaction is modeled with a theory developed by Likos et al.,
based on interactions between star polymers.
(1)L. A. Harris, J. D. Goff, A. Y. Carmichael, J. S. Riffle, J. J. Harburn, T. G. St. Pierre, M. Saunders, Magnetite
Nanoparticle Dispersions Stabilized with Triblock Copolymers, Chemistry of Materials, 15, 1367-1377 (2003).
388. Multicolor Quantum Dot Encoded Polystyrene Beads for Use in an Ultra-miniaturized
Microarray Platform
Shyam V. Vaidya, Charles Maldarelli, M. Lane Gilchrist and Alexander Couzis, City College and the Graduate Center
of the City University of New York, New York, NY
Focus of this paper is the development of optically barcoded polymer beads for use in high throughput multiplexed
screening applications such as protein microarrays. Luminescent semiconductor nanocrystals (or quantum dots (QDs))
with different emission wavelengths (colors), and encapsulated in different compositions in polystyrene (PS) beads are
used to define an optical barcode. The encapsulation is undertaken by copolymerizing the PS beads with the QDs
using a spraying suspension polymerization procedure. A mechanism is detailed by which these QDs are incorporated
in the bead matrix allowing for a controlled distribution of colors and compositions. QD embedded PS beads of
approximately 50 microns in diameter are obtained. Confocal laser scanning microscopy (CLSM) and fluorometry
results for the PS beads embedded with three color CdSe/ZnS core-shell QDs in varying concentrations are reported.
Distinguishable optical barcodes derived from the spectral scans of these QD loaded PS beads are reported. These
optically bar-coded PS beads arrayed in a square grid of microwells on a substrate will play host for biological
receptors such as cell surface membrane proteins, whose interactions with target molecules in analyte solutions would
be detected in high-throughput screening of drug molecules or pathogens.
389. Phospholipid membranes and ultrasound
Mona Pong 1 , Sumet Umchid 1 , Peter Lewin1 , Jerzy Litniewski 2 , Andrzej Nowicki2 and Steven P. Wrenn 1 , (1)Drexel
University, Philadelphia, PA, (2)Polish Academy of Sciences, Poland
“Stealth” liposomes containing poly(ethylene glycol) (PEG) are good candidates for drug delivery due to their
biocompatibility. Additionally, interest in using ultrasound energy in intracellular drug delivery has been growing rapidly.
Combining the technology of ultrasound and the science of lipids will lead to advancements in the field of targeted drug
delivery. Development and treatment optimization of such non-diagnostic applications of ultrasound requires a
fundamental understanding of interactions between the acoustic wave and phospholipid membranes, be they cell
membranes or liposome bilayers. This work investigates the changes in membrane permeation (leakage mimicking
drug release) in vitro during exposure to ultrasound applied in two frequency ranges: “conventional” (1 MHz and 1.6
MHz) therapeutic ultrasound range and low (20 kHz) frequency range. Phospholipids vesicles were used as controllable
biological membrane models. Membrane properties were modified by changes in vesicle dimensions and incorporation
of PEGylated lipids. The results of this work might be helpful to optimize acoustic field and membrane parameters for
gene or drug delivery.
390. Diffusive transport in nanostructured hollow colloidal capsules

James K. Ferri and Rufaro Mukogo, Lafayette College, Easton, PA
Novel diffusion controlled delivery vehicles are among a host of recent developments in the micro and nano-
encapsulation active ingredients in nutrition and biomedicine. Recently a technique for the synthesis of hollow
biocompatible nanocapsules using layer-by-layer adsorption of oppositely charged polyelectrolytes was introduced.
Here a method is presented to characterize the transport properties in these nanostructured materials and develop
structure-property relationships between the membrane thickness, composition (i.e. chemical constituency), and
synthesis conditions on the transport coefficients of the resulting nanocapsules. These variables are related to the
transport properties via the mesh size of the polyelectrolyte membrane. Solute transport in the capsule membrane is
measured via fluorescence recovery after photobleaching (FRAP). Coupled conservation equations are written in the
nanomembrane and the capsule interior. The diffusion coefficient in capsule interior, D1, is measured by PFG-NMR.

Data are presented for capsules synthesized from the polyanion poly-sodium 4-styrene sulfonate (PSS) and polycation
poly-allylamine hydrochloride (PAH) that are 30nm and 50nm thick. For these capsules, unsteady transport of 66kDa
TRITC-Dextran, which has a hydrodynamic radius of about 10 nm in solution, is measured. It is demonstrated that
transport in both the capsule wall and interior must be considered, and that the value for D2, the transport coefficient in
the capsule wall, is bounded between 1x10-15 m2/s and 1x10-14 m2/s.
391. Targeting integrins with surface-bound ligands: Specifity & affinity of binding
interactions
Mark H. Lee, Marla McConnell, David Boettiger and Russell J. Composto, University of Pennsylvania, Philadelphia, PA
Text Not Available.
392. Lipid Based Liquid Filled Capsule Formulations as Enabling Technology for Rapid
Development of Poorly Soluble Compounds
Eleni Dokou 1 , Michael Lowinger1 , Craig A. McKelvey 1 , Andrey Peresypkin 2 , Anand Balakrishnan 1 and W. Peter
Wuelfing 1 , (1)Merck & Co, Inc., West Point, PA, (2)Merck & Co, Inc., Rahway, NJ
As the number of hydrophobic drug development candidates in the pharmaceutical pipeline increases, it is particularly
challenging to deliver effective formulations for poorly soluble compounds. Lipid based Liquid Filled Capsule
Formulations, and in particular Self-Emulsifying (or Self-Microemulsifying) Drug Delivery Systems (SEDDS/SMEDDS)
have been used to enhance the bioavailability of poorly soluble compounds.
These systems typically contain an oil (lipid), surfactants and in some cases a co-solvent. Upon dispersion in an
aqueous environment similar to that encountered in the gastrointestinal tract, these systems emulsify under conditions
of mild agitation. The primary mechanism of action that leads to higher bioavailability for these formulations is
solubilization of the drug (by means of emulsion formation, micellar solubilization or via cosolvency), thus avoiding slow
dissolution from the crystalline state, which is frequently the rate limiting step for the absorption of hydrophobic drugs.
This leads to overall higher bioavailability, and often reduces variability in absorption.
This presentation will discuss some of the key features of lipid based formulations, considerations for material selection
(oils, surfactants, etc.), and the in vitro tools used for formulation characterization, such as phase behavior studies and
emulsification tests. Furthermore, comparisons of the in vitro screening tools, such as dispersibility and the in vivo
performance of self emulsifying drug delivery systems will be discussed. Examples will be provided to illustrate the
effective use of lipid based liquid formulations to support the successful development of challenging poorly water soluble
compounds.
393. Modulating Lipid Self-Assembly in Skin Microstructures with Implications to the

Enhanced Transdermal Delivery of Biomacromolecules
Vijay T. John, Grace Tan, Peng Xu, Louise B. Lawson, Jibao He, John D. Clements and Lucia C. Freytag, Tulane
University, New Orleans, LA
We describe methods of modulating skin lipid conformation especially through hydration, to enhance penetration of
vaccine antigens. Hydration of porcine skin tissue for a period of 4-8 hours causes a 3-4-fold expansion in the stratum
corneum. Significant structural alterations are observed, such as swollen corneocytes, separation of lipid bilayers in the
stratum corneum intercellular space, formation of spindle-shaped dilations, and the disruption of lipid membranes. Clear
conformational changes of intercellular lipids from lamellar bilayers to rolled-up structures resembling multilamellar
vesicles are observed in high clarity. Confocal microscopy studies show distinct enhancement in penetration of a large
biomacromolecule, fluorescein isothiocyanate-bovine serum albumin (FITC-BSA) through the skin when hydrated for 4
hours or greater. The fluorescent protein permeates the dermis region of highly hydrated skin, whereas in native skin, it
mainly accumulates at the surface of the skin. When the highly hydrated skin is exposed to the environment for an
hour, the skin is restored to its former compact structure. The results point towards the development of novel patch
technologies for vaccine delivery.

394. Investigating Molecular Interactions between Drug and Polymer Molecules in Solid
Amorphous Dispersions
Michael Lowinger, Hsien-Hsin Tung, C. A. McKelvey, Zhen Liu and Wei Xu, Merck & Co, Inc., West Point, PA
In an era of increasing need to develop drug candidates with tightening timelines and resources, the pharmaceutical
industry is facing an ever more challenging pipeline with >50% poorly water soluble chemical entities. Solid dispersion
formulations, an emerging field addressing some of these issues, enable the rapid development of poorly water soluble
compounds by placing the drug in a physically stabilized amorphous state capable of increasing its apparent solubility.
A solid dispersion necessitates the inclusion of a drug molecule and supersaturation-enhancing polymer in a stable,
homogeneous solid mixture produced by melt extrusion, solvent evaporation, or analogous processes. Predictive
thermodynamic models, such as Flory-Huggins, aid in the selection of a suitable polymer or mixture of polymers having
favorable interactions with the drug candidate. Inclusion of surfactants often enhances the compatibility of hydrophobic
drug with hydrophilic polymer, providing improved bioavailability over the binary system alone. By exploring the
molecular level interactions between drug and polymer candidates, we can understand the influence of structure on in
vivo performance.
395. Nano- and micro-particle two-dimensional self-assembled structures in a wedge film

Alex D. Nikolov and Darsh T. Wasan, Illinois Institute of Technology, Chicago, IL
Suspensions of nanometer to micrometer sized particles are spread over solid surfaces to develop nano- and micro-
sized structured materials with desirable structural and optical properties. A wedge film is formed by placing a droplet of
an aqueous suspension of latex particles on a smooth solid surface. The drop dries and the evaporation flux drives the
latex particles into the wedge film. The particle structuring phenomenon in the wedge film was directly observed using
reflected light microinterferometry. Both the contact angle dynamics and the particle trajectories inside the wedge film
were monitored. A sensitive infrared camera is used to monitor the temperature gradient over the droplet surface. The
evaporation flux creates the temperature gradient over the drop surface, thereby inducing the Marangoni flow. The
Marangoni flow drives particles outward from the central part of the region of the drop into the drop periphery. The
effect of surfactants on the particle flow was investigated. Under the confinement effect of the wedge film, the flow
assembles the particles into a 2-D array structure. The experimental results were rationalized in terms of a theoretical
model.
396. Microemulsions: From Science to Applications

Thomas Sottmann and Reinhard Strey, University of Cologne, Cologne, Germany
Although thermodynamically stable mixtures of at least a hydrophilic -, a hydrophobic - and an amphiphilic component,
i.e. microemulsions, gain an increasing interest in technical applications, their manifold use failed up to now. One
reason is the poor transfer of the scientific results to application. In this contribution examples will be given where this
transfer (almost) succeeded. It will be shown that the ultra-low interfacial tension in microemulsions can be used for the
efficient degreasing of animal skins. Using microemulsions as reaction media it is found that the large specific internal
interface leads to a drastic enhancement of epoxidation rates. In another application microemulsions are used for clean
combustion in motors, like e.g. diesel engines. It is known for a long time that the presence of liquid water in the
compressed, hot combustible air-fuel mixture reduces the emission of pollutants like soot and nitrogen oxides. Often
water-fuel emulsions are injected. Emulsions are thermodynamically unstable and therefore tend to separate.
Microemulsions, on the contrary, do not separate because they are thermodynamically stable. We made
microemulsions of water and diesel and tested these in truck engines. Soot was reduced by more than 90 % in steady
state operation and about 97 % in dynamic (i.e. accelerating) operation. Nitrogen oxides were 40 to 70 % lower
compared to the reference diesel. In certain modes of operation fuel consumption was reduced. Explanations and
implications of these favourable findings will be discussed.
397. Phase diagram approach to emulsion evaporation

Stig E. Friberg, University of Virginia, Cahrlottesville, VA

The evaporation from emulsions is of vital importance for a large number of industrial and technical applications and
has, hence, been studied extensively with the recent contributions from University of Hull as leading. The fundamental
treatment has evaluated different factors, which influence the evaporation rate for emulsions with sufficiently small
surfactant content to retain the 2-phase structure during the evaporation. However, a large number of emulsions have
sufficiently high concentrations of surfactant for phase changes to occur within a limited time after the evaporation is
initiated. For such systems the phase diagram approach provides a unique opportunity to describe not only the
evaporation path and the variation of amount of the compounds in the process, but, more essentially, the changes in
the number and amount of different phases. The lecture will introduce this approach and give an example describing a
typical emulsion system.
398. Antioxidant Distributions between Oil, Water and Interfacial Regions in Model Food
Emulsions
Krishnan Gunaseelan1 , Laurence S. Romsted 1 and Carlos Bravo-Días2 , (1)Rutgers University, Piscataway, NJ,
(2)Universidad de Vigo, 36200 Vigo-Pontevedra, Spain
We developed a new method for estimating antioxidant (AO) distributions in emulsions based on pseudophase models
for chemical reactivity in micelles and microemulsions. AO distributions are expressed in terms of two partition
constants between oil-interface (PO I ) and water-interface (PW I ) regions within the emulsions. To estimate values of
PO I and PW I requires two independent data sets described by mathematical relations (models) that are dependent on
these parameters and solving two equations in two unknowns. One data set is obtained from the observed rate
constant (k obs) measured electrochemically for reaction of the AO with an arenediazonium ion with increasing nonionic
surfactant in a stirred tributyrin-water emulsion. The other data set is obtained by measuring the distribution constant of
the AO between tributyrin and water in the absence of emulsifier by UV-Visible spectrometry. The distribution of t-butyl
hydroquinone (TBHQ) was determined in a simple model food emulsion - hexaethyleneglycol monododecyl ether
(C12 E6 )/water/tributyrin at 25 °C. From the PO I and PW I values, we estimate that about 65% of TBHQ is located in the
interfacial region at about 2% of C 12 E6 with significant percentage of TBHQ in the tributyrin region. The distribution
constant (K) of TBHQ between water and tributyrin in the absence of C 12 E6 is 0.015.
399. Supercritical carbon dioxide - microemulsions as precursors for nanofoams: Study of

microstructure
Lorenz G. A. Kramer 1 , Thomas Sottmann1 , Peter Lindner 2 , Ralf Schweins2 and Reinhard Strey 1 , (1)University of
Cologne, Cologne, Germany, (2)Institut Laue – Langevin, Grenoble CEDEX 9, France
For the production of nanofoams, which have very small heat conductivity and special optical properties, Strey et al
developed the new procedure: Principle Of Supercritical Microemulsion Expansion (POSME). The principle is based on
the formulation of supercritical microemulsions containing nano-sized spherical micelles swollen by a supercritical fluid.
In this study we used the non-toxic and non-flammable carbon dioxide. Staying above the critical parameters, Tc = 31°
C and p c = 72 bar, allows to continuously expand the CO 2 -swollen micelles in a supercritical state. This work examines
whether the well-known properties of microemulsions at atmospheric pressure are also found at increased pressure. We
studied the temperature dependent phase behaviour of systems of the type H 2 O/NaCl - CO 2 - technical non-ionic
surfactant at a pressure of p = 220 bar. For the first time the typical phase inversion of a non-ionic surfactant system
from a CO 2 - in - water to a water - in - CO 2 microemulsion is found. It turned out that a hydrocarbon-type surfactant
could solubilize supercritical CO 2 only inefficiently. The addition of a perfluorinated surfactant led to an improved
efficiency and could be the key for an efficient solubilisation of supercritical CO 2 . Having determined the phase
behaviour systematically, we performed small angle neutron scattering (SANS) experiments on these scCO 2 -
microemulsions to elucidate the microstructure and their variation with pressure. To this end we built a new high
pressure cell with variable volume which is suitable for SANS experiments under pressures up to p = 250 bar. First
results are presented.
400. Study of foam film drainage in relation to self-assembled nanostructures

Plamen Tchoukov, Dimitrinka Arabadzhieva, Elena Mileva and Dotchi Exerowa, Institute of Physical Chemistry,
Bulgarian Academy of Sciences, Sofia, Bulgaria
Studies on foam films formed from aqueous surfactant solutions in broad concentration interval (below and above the
critical micelle concentration) are performed. Anionic, cationic and nonionic surfactants in presence of electrolyte are
investigated. Foam film results are juxtaposed to adsorption properties of the solutions at the same conditions. The
results show that film drainage behavior deviate significantly from the predictions of the theoretical models. Film
drainage parameters, velocity of thinning and drainage time, change sharply within a relatively narrow interval of
concentrations. A distinct correlation between the run of the film kinetic parameters and observed peculiarities in the
adsorption isotherms is established. The proposed explanation of the experimental results outlines the impact of the
existing self-assembled nanostructures on the tangential mobility of foam film surfaces. We suggest an explanation
relating the specific hydrodynamics of the film, the mass transfer of amphiphilic molecules and the presence of self-
assembled structures.
401. Surfactant phase behavior and nano-emulsion formation by low-energy methods
Jordi Nolla1 , Daniel Morales 1 , J. M. Gutierrez 2 , Jordi Esquena 1 , Maria Jose Garcia-Celma 3 and Conxita Solans1 ,
(1)Institut d' Investigacions Químiques i Ambientals de Barcelona (IIQAB). Consell Superior d' Investigacions
Científiques (CSIC)., Barcelona, Spain, (2)Universitat de Barcelona, Departament d'Enginyeria Quimica, Barcelona,
Spain, (3)Universitat de Barcelona, Departament de Farmacia i Tecnologia Farmaceutica, Barcelona, Spain
Nano-emulsions are emulsions with droplet size in the nanometer scale (typically in the range 20-200 nm). Due to the
extremely small droplet size, nano-emulsions appear transparent or translucent (resembling microemulsions) and
possess stability against sedimentation or creaming. The formation of kinetically stable liquid/liquid dispersions of such
small sizes is of great interest from fundamental and applied viewpoints. Nano-emulsions are generally prepared by
dispersion or high-energy emulsification methods. However, condensation or low-energy methods, which make use of
the phase transitions taking place during the emulsification process, are receiving an increasing attention in this
context. This communication will focus on the potential of surfactant phase behavior information for the preparation of
controlled size nano-emulsions by low-energy methods. Phase behavior studies in water/polyethoxylated nonionic
surfactant/oil systems have shown that phase transitions during the emulsification process involving lamellar liquid
crystalline and/or bicontinuous microemulsions phases are required to achieve minimum droplet size. Examples will be
given on the formation of O/W nano- emulsions with droplet sizes as low as 20 nm, low polydispersity and high kinetic
stability. In addition, the use of nano-emulsion droplets as templates for the preparation of nanoparticles will be also
described.
402. Stop-flow photolithography to create custom anisotropic colloids

Patrick S. Doyle, Dhananjay Dendukuri, Shelley Gu, Daniel Pregibon and T. Alan Hatton, Massachusetts Institute of
Technology, Cambridge, MA
Polymeric particles in custom designed geometries and with tunable chemical anisotropy are expected to enable a
variety of new technologies in diverse areas such as photonics, diagnostics and functional materials. We present a
simple, high throughput and high resolution microfluidic method to synthesize such polymeric particles. Building off
earlier work that we have done on continuous flow lithography, CFL (Dendukuri et al., Nat. Mat. 2006), we have devised
and implemented a new setup that uses pressure driven flows to synthesize particles using a technique that we call
stop-flow lithography (SFL). A flowing stream of oligomer is stopped before polymerizing an array of particles into it,
providing for much improved resolution (down to 1 micron) over particles synthesized in flow. The formed particles are
then flushed out at high flow rates before the cycle of stop-polymerize-flow is repeated. The high flow rates enable
orders-of-magnitude improvements in particle throughput over CFL. However, the deformation of the PDMS elastomer
due to the imposed pressure restricts how quickly the flow can be stopped before each polymerization event. We have
developed a simple model that captures the dependence of the time required to stop the flow, on geometric parameters
of the microchannel such as height, length and width, as well as on the externally imposed pressure. Further, we show
that SFL proves to be superior to CFL even for the synthesis of chemically anisotropic particles with sharp interfaces
between distinct sections.
403. Effect of suspended clay particles on isotropic–nematic phase transition of liquid

crystal

Zexin Zhang, University of Pennsylvania, Philadelphia, PA and Jeroen S. Van Duijneveldt, University of Bristol, Bristol,
United Kingdom
Sterically stabilized nano-platelets were prepared by treating montmorillonite clay with both a surfactant and a
polymeric stabilizer. These nano-platelets, for the first time, formed stable suspensions in a thermotropic liquid
crystal(LC), 5CB. In the isotropic state of the LC, static light scattering confirmed that the clay nano-platelets were
freely suspended, with no aggregation detected even after repeated temperature cycling. Small-angle X-ray scattering
revealed that the clay was nearly completely delaminated in the LC, with some stacks of a few clay nano-platelets
having formed. Differential scanning calorimetry of the LC/clay suspensions showed a small but non-monotonic shift of
the I-N transition temperature. This behavior is similar to that of LC confined in porous media, with an initial increase of
the transition temperature on adding clay being ascribed to the effect of surface anchoring facilitating the formation of
the nematic phase; whereas a decrease at higher clay concentrations (or equivalently, for smaller pores) is ascribed to
confinement effects frustrating the formation of the nematic phase. This interpretation is supported by polarizing light
microscopy which showed the nematic domain size becoming smaller on increasing the clay concentration.
41044 modified by 158.130.30.30 on 2-15-2007-->
404. Adhesion, self assembly and structure of actin filaments

Zvonimir Dogic and Ashok Prasad, Brandeis University, Waltham, MA
Direct measurement of the intermolecular potential between a pair of charged actin filaments is essential for
understanding their pathways of self-assembly. We have developed two methods that allow us to directly measure the
adhesion energy between a pair of filaments held together by the depletion or any other attractive interaction. The
sensitivity of our force measurement is in a picoNewton to femtoNewton range. Our data indicate that thermal
fluctuations renormalize the adhesion strength in the weak binding limit. We are able to correlate changes in the
adhesion strength with changes in the structure of actin bundle.
405. Effect of double layer polarization on particle interactions in AC electric fields

Pushkar Lele, Eric M. Furst and Eric W. Kaler, University of Delaware, Newark, DE
We studied the effect of AC electric fields on pair-wise and many-body colloidal interactions. In the absence of an
electric field, the interactions for three particles in triangular and linear configuration were in good agreement with the
predicted results from Stokesian dynamics simulations, which account for the hydrodynamic interactions between
particles. In addition, we carried out a systematic experimental characterization of pair interactions under an applied AC
electric field. The electrolyte concentration in the medium and the frequency of the electric field had a strong effect on
the particle interactions. Our results suggest that the dipole-dipole interactions are dominated by the double layer
polarization around the particles. This interaction is an order of magnitude larger than the dipole-dipole force expected
from the particle polarization, as calculated by the Claussius-Mossotti factor. These effects need to be accounted for
when considering the field-induced assembly of particles in AC electric fields
406. Hydrodynamic interactions between a silica particle and a deformable droplet – effect
of particle/droplet size ratio and bulk phase viscosity
Grant B. Webber, Rogerio Manica, Scott Edwards, Geoff Stevens, Derek Y.C. Chan, Raymond R. Dagastine and Franz
Grieser, The University of Melbourne, Melbourne, Australia
In many industrial applications such as froth flotation, foams and emulsions, the interactions between solid and

deformable interfaces, or two deformable interfaces, is of critical importance. Understanding these micro-scale
interactions is vital for the prediction and control of the macro-scale behaviour. The understanding of the dynamic
interactions when one or more surfaces is “soft”, and thus the overall interaction may be dominated by surface
deformations, is of particular interest. Recent advances within the Particulate Fluids Processing Centre has enabled the
modeling of atomic force microscope (AFM) force data collected for the static 1 and dynamic interactions 2,3 between a
solid sphere and a deformable interface, or two liquid droplets. Here we present data examining the effect of the
particle/droplet size ratio and the bulk phase solution viscosity on the interaction between silica spheres and sodium
dodecyl sulfate (SDS) stabilised tetradecane droplets. In particular, this data enables us to probe the existence, or
otherwise, of a slip boundary between the two interacting surfaces. Force-distance profiles collected from AFM
experiments are compared to theoretical profiles in which different slip lengths are incorporated.
References
(1) Dagastine, R. R.; Stevens, G. W.; Chan, D. Y. C.; Grieser, F. Journal of Colloid and Interface Science 2004,
273, 339-342.
(2) Carnie, S. L.; Chan, D. Y. C.; Lewis, C.; Manica, R.; Dagastine, R. R. Langmuir 2005, 21, 2912-2922.
(3) Dagastine, R. R.; Manica, R.; Carnie, S. L.; Chan, D. Y. C.; Stevens, G. W.; Grieser, F. Science (Washington,
DC, United States) 2006, 313, 210-213.
408. Deposition of microsphere monolayers for microlens arrays

Pisist Kumnorkaew, Yik-Khoon Ee, Nelson Tansu and James F. Gilchrist, Lehigh University, Bethlehem, PA
Colloidal silica microspheres of 0.5 and 1 micron were deposited into thin films on a glass substrate via a rapid
convective deposition method. By varying deposition rate and contact angle, the optimal operating ranges in which 2D
closed-pack of silica existed were obtained. Using a confocal laser scanning microscope, dynamic self assembly of
colloidal particles under capillary force during solvent evaporation was revealed. In addition, interaction between
substrate and colloidal particles played an important role in formation of ordered crystalline arrays. The interaction was
altered by varying pH (2-11) and salt concentration of either substrate rinsing solution or colloidal suspension. Using the
same technique, stacked layers of 1 micron silica monolayer on top of 1.1 micron polystyrene monolayers and
subsequent melting of the polystyrene to partially wet the silica microspheres were deposited on GaN layer. This
process was implemented on the top p-GaN layer of InGaN quantum wells light emitting diode (LEDs) device structure,
resulting in the formation of a microlens array for enhancing its light extraction efficiency. This approach led to ~230%
increase of the LEDs output power.
407. Long-range hydrodynamic response of particulate liquids

ABSTRACT WITHDRAWN
In viscous particulate liquids, such as colloidal suspensions and polymer solutions, the large-distance steady-state flow
due to a local disturbance is commonly described in terms of hydrodynamic screening — beyond a correlation length ξ
the response drops from that of the pure solvent, characterized by its viscosity η0 , to that of the macroscopic liquid with
viscosity η>η 0 . For cases where η>>η 0 we show that this screening picture, while being asymptotically correct, should
be refined in an essential way. The crossover between the microscopic and macroscopic behaviors occurs gradually
over a wide range of distances, ξ<r<(η/η 0 ) 1/2 ξ. In liquid-laden solids, such as colloidal glasses, gels, and liquid-filled
porous media, where η→∞, this intermediate behavior takes over the entire large-distance response. The intermediate
flow field has several unique characteristics relating to its distance dependence, concentration dependence, and

temporal buildup, which are demonstrated in several model systems.
409. The viscoelastic properties of interfacial lung surfactant films

Siegfried Steltenkamp, University of California, Santa Barbara, CA and Joseph A. Zasadzinski, University of California
Santa Barbara, Santa Barbara, CA
Lung surfactant (LS) is a complex mixture of lipids and proteins originating from the type II cells that line the alveolar
epithelial walls. LS reduces surface tension in the alveolar spaces, which minimizes the work of breathing and prevents
the alveolar collapse. A lack of functional surfactant due to premature birth leads to neonatal Respiratory Distress
Syndrome (nRDS) which is routinely treated in developed countries with animal derived replacement surfactant. One of
the essential features of good LS is to reduce the surface tension at the alveolus air-water interface to near zero.
Presently, there is no simple theory relating chemical or physical properties of a monolayer with its ability to lower
surface tension in the dynamic process of breathing. Monitoring the viscoelastic properties of interfacial films allows
hypothesizing how surface viscosity depends on lipid and protein composition, packing properties and other variables at
different states of the breathing process. Our viscometer consists of a Langmuir trough equipped with Helmholz coils
which generate a controlled magnetic force to move a magnetic needle floating on the monolayer. If the applied force is
oscillatatory, the complex shear modulus is determined from measurements of the in-phase and out-phase of the
resulting strain. If the force is constant, the shear viscosity can be extracted from the terminal velocity of the needle.
Here we present the behavior of LS monolayer concerning surface viscosity at different surface pressure, composition
and phase in order to make a prediction about the optimal composition of LS.
410. Non-Aqueous Photorheological Fluids Based on Reverse Wormlike Micelles

Aimee Ketner, Patrick W. Elder and Srinivasa R. Raghavan, University of Maryland, College Park, MD
Our lab has been investigating surfactant fluids with light-tunable rheological properties (i.e., “photorheological” or PR
fluids). We recently reported a class of PR fluids based on wormlike micelles in water (JACS 129, 1553 (2007)). In this
system, light caused a well-defined drop in viscosity due to a transition from long to short micelles. Here, we report an
increase in viscosity due to light in a non-aqueous reverse micellar fluid. It is well-known that the phospholipid, lecithin
can form reverse wormlike micelles in organic solvents like cyclohexane, upon addition of a small amount of water.
These solutions consequently have a high viscosity. However, when we add a photoresponsive stilbene compound into
the water phase the solution viscosity drops. When this sample is then irradiated with UV light, the stilbene undergoes
a photoisomerization, and we observe that the viscosity reverts to a high value. These results are evidently due to the
interplay between molecular geometry and reverse micellar structure. We will present results from a variety of
spectroscopic, analytical and scattering techniques to elucidate the molecular and microstructural mechanism for our
results.
411. Photogelling fluids: Micellar solutions whose viscosity can be increased by light
Rakesh Kumar and Srinivasa R. Raghavan, University of Maryland, College Park, MD
Fluids with photoresponsive rheological properties can be useful in a variety of applications, such as in sensors,
dampers, and valves for microfluidic or MEMS devices. Currently, such fluid formulations are available only to a few
research groups since they tend to be based on specialized photosensitive molecules (e.g. a photosensitive surfactant
or polymer). Here, we describe formulations based on a commercially available zwitterionic surfactant and a
photosensitive cinnamic acid derivative. These fluids exhibit a rapid and controllable increase in viscosity (gelling) upon
exposure to UV radiation. Initially, the fluid has a low viscosity, indicating the presence of small micelles. Upon
irradiation in the UV range, the cinnamic acid derivative undergoes a trans to cis photoisomerization. This change in
geometry alters the molecular packing of surfactant/acid complex, transforming spherical micelles into long wormlike
micelles. In turn, the solution viscosity is increased by more than five orders of magnitude. Small-angle neutron
scattering (SANS) is used to confirm the dramatic increase in micellar length.
412. A Novel Associative Polymer Network with Tunable Rheological Properties
Lin Fu1 , Xuhong Guo 2 , Stephen Lincoln 3 and Robert Prudhomme1 , (1)Princeton University, Princeton, NJ, (2)East
China University of Science and Technology, Shanghai, China, (3)University of Adelaide, Australia

Water soluble associative polymers, which are usually composed of hydrophilic backbones and hydrophobic side
chains, are widely used as rheology modifiers in coating, painting, cosmetics and pharmaceutics. In this study, a novel
associative polymer network with tunable rheological properties is developed based on cyclodextrin-hydrophobe
inclusion complex. Mixtures of two polyacrylic acid backbone polymers: cyclodextrin attached to PAA and
hydrophobically modified PAA are used. With cyclodextrin host-guest inclusion as the associative sites, this novel
polymer network is able to provide more controllable rheological properties than traditional associative polymers,
because: first, the lifetime of this host-guest association can be well controlled by the length of alkyl chain inserted into
the cyclodextrin; second, the binary nature of cyclodextrin-hydrophobe inclusion prevents hydrophobes from multiple
association. At the same time, this system can serve as a model associative polymer network for understanding
polymer association theory. Dynamic rheological properties of this mixture solution can be quantitatively controlled by
adding free cyclodextrin or sodium dodecylsulfate (SDS). Dynamic modulus could change up to several orders of
magnitude, even from gel state to sol state. The phase behavior of this mixture solution is experimentally studied by
turbidity measurement and rheological approach. The thermodynamic behavior is found to show good consistency with
associative gelation theory. Further, we studied the life time of cyclodextrin-hydrophobe interaction independently from
isothermal titration calorimeter and surface plasmon resonance study. Both thermodynamics and dynamics of this
cyclodextrin inclusion process are explored for better controlling rheological properties of this model system.
413. Particle effects on an ordered cylindrical micelle gel of block copolymer solutions
Theresa A. LaFollette and Lynn M. Walker, Carnegie Mellon University, Pittsburgh, PA
Recent efforts to template hydrophilic nanoparticles in the interstitial spaces of the thermoreversible close-packed
micellar structure seen in Pluronic block copolymers has been shown successful. Previous work focused on systems
forming cubic soft crystals of spherical micelles and is currently being extended to cylindrical micelles. The pluronic
copolymer P123 (PEO20 -PPO 70 -PEO 20 ) forms both an ordered cubic micelle gel and packed cylindrical micelle gel.
Phase transitions are determined from rheology and birefringence and verified with small-angle scattering. Proteins are
used as monodisperse nanoparticles; two different sizes of particle, bovine serum albumin (BSA) and lysozyme are
added to the P123 system forming a nanocomposite. We observe an apparent hysterisis during the transition between
the cubic and cylindrical micelle gel during heating and cooling in the nanocomposites, while no hysterisis is observed
in the neat system. BSA at 2-3 wt% disrupts the formation of the packed cylindrical micelle gel while the smaller
lysozyme does not. This indicates formation of a weaker gel and is caused by the size of the particles relative to
interstitial spaces. A mechanical protocol for studying the nanocomposites has been developed and limits for placing
particles in the nanocomposite have been established.
414. Ring shaped structure in free surface flow of non-Newtonian liquids

Nilesh H. Parmar and Mahesh S. Tirumkudulu, IIT Bombay, Mumbai, India
We report the formation of a ring like structure (donut shaped) in the flow of particular non-Newtonian liquids coating a
rotating vertical disc. Experiments were performed with a known volume of the liquid and at varying rotation rates such
that inertial and centrifugal effects were negligible. Liquid injected on to the rotating disc initially coats the surface
uniformly, which then redistributes itself such that at steady state a significant amount collected into a circular ring, off
center with the axis of rotation. The ring formation was not observed in the case of Newtonian liquids. These
experiments motivated a study on the liquid of Newtonian viscous liquids on the same geometry. A lubrication analysis
for Newtonian liquid resulted in a time evolution for the film thickness that accounted for gravity, surface tension and
viscous forces. The predicted thickness profiles are in excellent quantitative agreement with those obtained
experimentally for moderate volumes of silicone oil. Shear rate calculation for the Newtonian liquid suggests that the
shear thinning nature of the non-Newtonian liquid may be the cause for the observed ring formation.
415. Liquefaction of quicksand under stress

Asmae Khaldoun, University of Amsterdam, Amsterdam, Netherlands
Quicksand is the generic name for unstable soils reputed to trap anyone who treads on it. Popular wisdom has it that
one should not move when trapped in quicksand, as motion makes one sink in even deeper and that once trapped, it
is difficult to escape1. Here we provide an explanation for these observations by studying the most commonly
encountered form of natural quicksand. We show that a spectacular liquefaction of the material occurs when a stress is

applied to the material: the liquefaction is the reason why one sinks away, and it is more pronounced for larger
stresses. By constructing 'laboratory quicksand', we demonstrate that the liquefaction is due to the structure: quicksand
is a loose granular packing of sand particles stabilized by a clay matrix that forms a particulate gel. The stress liquefies
the clay matrix, and the granular assembly collapses, expulsing water. This results in a densely packed system that
practically impossible to dilate: it is for this reason that once trapped it is difficult to get out of quicksand. A sinking test
demonstrates that, due to buoyancy, it is impossible to drown in the quicksand.

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Abstract Book 06/25/2007 06:28 PM

1. Self assembly and immunity of microemulsion and polymer networks

2. Keynote: DFT Modeling of Novel Materials

DFT Modeling of Novel Materials

3. Mechanisms of Metal Atom Clustering and Nanofilament Formation in Vapor Deposition

4. Selective deposition of metals on patterned self-assembled monolayer surfaces: Towards

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6. The Initial Stages of Self-Organization of Silica-Alumina Gels in Zeolite Synthesis

7. The Effect of an Embedded Mid-Chain Dipole on the Properties and Characteristics of

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8. Keynote: Electrical microchips in the biocolloidal domain: On-chip assembly and

9. The zeta potential of freshly cleaved mica just after immersion

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11. Synthesis and Imaging of Plasmonic Magnetic Nanoparticles

12. Squishy particles: modulating the mechanical properties of polymer vesicles

13. Bio-polyelectrolyte deposition and stabilisation of mineral colloidal particles

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14. Keynote: Some theory of colloid transport in aquatic environments

16. On role of air-water interface and surface tension in colloid transport

17. Grain Surface-Roughness Effects on Colloidal Retention in the Vadose Zone

file:///Users/furst/Desktop/CSSS%2007/Program%20book%20MAY%2007/Abstract%20Book.webarchive Page 5 of 139

18. Adsorption of nanomaterials to air-water interfaces in porous media during primary

20. Keynote: Imaging the flow of colloidal glasses

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21. Glass-like dynamics of microgel suspensions

23. Aging and non-Gaussian dynamics in a colloidal glass

24. Microscopic structure and collapse of depletion-induced gels in vesicle-polymer

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27. Barcoded microparticles for multiplexed biomolecule analysis

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31. Polycation-Clay Composites as a Basis for Controlled Release Herbicide Formulations

32. Keynote: Self-assembly of colloids: The shapes of things to come

. DNA directed assembly of non-close-packed colloidal crystals

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DNA directed assembly of non-close-packed colloidal crystals

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36. Patchy Particles and their Assembly Properties

1) Cui, J.; Kretzschmar, I. Langmuir 2006, 22, 8281-8284.

2) A. B. Pawar, I. Kretzschmar, G. Aranovich, M. D. Donohue J. Phys. Chem., 2006, in press.

37. Dielectrophoretic assembly and electrohydrodynamic mobility of "Janus" particles in AC

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39. Morphological Transitions in dilute region of CTAB/SDS/Water system: a SAXS study

40. Fast Dynamics of Wormlike Micelles

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41. Scattering form-factors for self assembled Y-junctions

42. Analysis of Microemulsions Containing a pH-Degradable Alkyl Ethoxylate Surfactant by

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44. Keynote: Self-Assembly: Connecting academia with industrial perspectives

45. Self-assembly in anhydrous sugar glasses

46. Surfactants for carbon dioxide

47. Characterization of nanostructures of mixed surfactant aggregation using Analytical

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48. Characterization of alkyl polyglucoside microstructure and phase behavior

49. In-situ polymerization and self-assembly of cationic surfactants

50. Keynote: Surfactant Effects at Alkane-Water Interfaces: Freezing and Deformation

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51. Lateral Adhesion Balance (LAB) -- a Novel Surface Characterization Technique

52. Classification of Nano-Friction Characteristics of Silica Surfaces in Electrolyte Solutions

53. Surfactant Adsorption at the Air-Liquid and Hydrophobic Solid-Liquid Interfaces:

54. Adsorption of highly extended polymers using Optical Reflectometry

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55. Ion-specific bubble coalescence inhibition in single and mixed electrolytes