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4.

Thermoresponsive polymers

4.1 Conformational transition 4.2 Co-nonsolvency 4.3 Switchable networks 4.4 Micro- and nanogels

There is no book yet on this class of materials.

4.1 Conformational transition

apolar n polar apolar T < 32C T > 32C

aqueous solutions of poly(N-isopropyl acrylamide) (PNIPAM) become abruptly turbid at the cloud point (32C) thermoresponsive (switchable) behavior

The role of H-bonding


hydrogen bonds: below the cloud point: H-bonds with H2O (cage structure) + above the cloud point: H-bonds with adjacent side groups zipper effect

chain conformation: swollen collapsed sharp transition at the cloud point collapsed chains form large aggregates turbid solution

cloud point

lower critical solution temperature, LCST behavior

H. G. Schild, Prog. Polym. Sci. 1992. S.-Y. Lin et al., Polymer 1999. Y. Katsumoto et al., J. Phys. Chem. A32002

Quantum chemical calculations


H-bonds between N-H groups and H2O are stronger than H-bonds between N-H and N-H + number of N-H/H2O bonds increases in direction dry solid wet solid suspension above cloud point solution

NIPAM / 5 H2O

NIPAM / NIPAM

NIPAM / NIPAM / 4 H2O


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J. Dybal et al., Vibr. Spectrosc. 51, 44 (2009)

LCST behavior
LCST behavior: behavior opposite of UCST reason: specific interaction of the polymer with the solvent, e.g. H-bonding

UCST behavior: demixing at low temperatures homogeneous solution at high temperature

4.2 Cononsolvency
Mw= 160 000 g/mol polymer concentration: 0.4 mg/mL

PNIPAM in H2O: LCST behavior


dioxane

PNIPAM in organic solvents: e.g. dioxane, tetrahydrofurane (THF) or methanol: good solvent at all temperatures PNIPAM in solvent mixtures H2O/dioxane, H2O/THF, H2O methanol: cloud point goes down miscibility gap

THF

methanol

the second solvent is called co-non-solvent


Tirell et al., Macromolecules 24, 948 (1991). Hirotsu, J. Chem. Phys. 88, 427 (1988) 6

Miscibility gap observed with ~single chains


(i) (ii) (iii) (i) in pure H2O and xMeOH < 0.13 : swollen chains

(ii) 0.13 < xMeOH < 0.45: collapsed chains

(iii) xMeOH > 0.45: swollen chains chain conformation depends strongly on fraction of cononsolvent
PNIPAM, 26 x 106 g/mol dilute solution, T = 20 C cononsolvent: methanol

Wu et al. JACS 2001, 123, 1376

Interaction of water/solvent with PNIPAM

PNIPAM in H2O: H2O molecules bind to PNIPAM in long sequences hydration is cooperative phenomenon

steric reason: if one H2O binds to the polar part of the side group, space is created for next H2O molecule, it is favorable to bind to the PNIPAM monomer which is next to the first H2O
F. Tanaka et al., J. Phys.: Cond. Matter 23, 284105 (2011). 8

Interaction of water/solvent with PNIPAM

cooperative binding for both solvents competition between H-bonds PNIPAM/H2O and PNIPAM/methanol: competitive adsorption sequences of H2O/methanol along chain
F. Tanaka et al., Phys. Rev. Lett. 101, 028302 (2008). F. Winnik et al., Macromolecules 23, 2415 (1990). H. Kojima, F. Tanaka, Soft Matter 8, 3010 (2012).

4.3 Switchable networks


chemical cross-linking macroscopic volume change for very small temperature change

T. Tanaka Discover Magazine 1996 10

Switchable valves
test molecule: tryptophan (TRY)
Absorbance open

20C:

40C:

closed

swollen network permeable for TRY

collapsed network less permeable for TRY

Time (h)

strongly temperature-dependent permeability applications in microfluidics, lab on a chip,


Y.S. Park et al., Langmuir 14, 910 (1998) 11

Application in microfluidics

valve in microfluidics controlled by local heating


K.-F. Arndt, TU Dresden 12

Applications in ophthalmology
ocular diseases: age-related macular degeneration, diabetic retinopathy use anti-VEGF therapy major drawback: treatment must be repeated every 4 to 6 weeks desire: develop a relatively noninvasive delivery method which is more effective and longer lasting idea: use PNIPAM hydrogels with poly(ethylene glycol) diacrylate (PEGDA) better thermoresponsive characteristics homogeneous pores encapsulate and release protein homogeneous pore size
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RT

37C

J.J. Kang Derwent, W.F. Mieler, Trans. Am. Ophthalmol. Soc. 106, 206 (2008)

protein release rate is governed by compression of hydrogel in response to temperature pore size: the finer, the longer the release time but also stiffer (difficult to inject through needle)
protein molar mass ~ 100 kg/mol

initially fast release, then leveling off still a lot of protein in hydrogel use degradable hydrogel

injected hydrogel on rat retina no movement for 2 months no inflammation


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Kinetics of swelling of a PNIPAM gel


500 m 100 s

time course of swelling of PNIPAM gel bead in water during a temperature jump
T. Tanaka et al., Phys. Rev. Lett. 55, 2455 (1985)

R2 the smaller the gel,


the faster the switching

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4.4 Microgels faster switching


heating cooling

Macrogels easy preparation slow switching collapsed inhomogeneous structure

swollen

microgels (R = 100 nm to ~5 m) more difficult preparation faster switching crystallization, glass formation,

Y. Hirokawa et al., J. Chem. Phys. 1984 M. Shibayama et al., J. Chem. Phys. 1992

T. Hellweg et al., Coll. Surf. A 2002 M. Stieger et al., Langmuir 2004, S. Hfl et al., Polymer 2007

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Collapse of nanogels
micelle with polystyrene core and PNIPAM shell R = 16 nm t = 12 nm
20 Kernradius Mizellradius halber Abstand

fast temperature jump 30C 35C

R = 7 nm t = 3 nm thermoresponsive shell collapses

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Radien (nm)

time-resolved small-angle neutron scattering collapse takes less than 0.8 s

10

0.1

10

100

1000

Zeit (s)
J. Adelsberger, C.M.P. et al., Macromol. Rapid Commun. 33, 254 (2012) 17

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Microgels with interesting optical properties


inorganic/organic hybrid microgels with strong absorption in visible range exploit the plasmon resonance of noble metals spherical gold- nanoparticles in core of PNIPAM microgel growth conditions spherical or flower-like gold core

UV-Vis spectra full lines: 15C, swollen state dotted lines: 50C: collapsed state shift of absorption maximum change of color

R. Contreras-Cceres et al., Adv. Mater. 20, 1666 (2008)

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