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Properties and Applications of Colloidal Nonspherical
Noble Metal Nanoparticles
By Tapan K. Sau,* Andrey L. Rogach,* Frank Jäckel, Thomas A. Klar, and
Jochen Feldmann
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3. Chemical Reactivities dissolution and reaction with persulfate and were attributed to the
Researchers have recently started to explore the effects of metal structural metastability of the spheroids.[24–26] It has been
nanoparticle morphology on chemical reactivity. Nanoparticles reported that chemical reactions started at ridges, apexes, or
have several inherent features that change their chemistry particular facets during galvanic replacement reactions between
compared to their bulk counterparts or constituent atoms and silver nanoparticles and HAuCl4, depending on the morphology
molecules, since adsorption and reactivity are highly structure- of the template nanoparticles and reaction conditions.[27,28] Brus
sensitive properties. The large surface of a nanoparticle may be and co-workers reported an interesting physico-chemical con-
structurally and compositionally different from the bulk due to version of sodium-citrate-stabilized colloidal Ag nanocrystals to
surface relaxation and reconstruction, the presence of adsorbed nanoprisms.[29] According to them, irreversible ‘‘hot hole’’
layers of reaction by-products and stabilizing molecules, etc.[20,21] photo-oxidation of citrate anions adsorbed on Ag nanoparticles
Additionally, the surface structure changes as a function of size, builds up a photovoltage under visible excitation. This in turn
shape, and number of components of a particle.[3,22] The large causes the photochemical conversion of spherical 8 nm Ag seeds
particle surface area results in increased interaction with their into 70 nm single-crystal disk prisms under light irradiation.
environment. These effects may lead to a radical alteration in Recently, Tsung et al. reported selective shortening by mild
chemical reactivity. oxidative dissolution of single-crystalline gold nanorods prepared
Long ago, Jang et al. pointed out that the surface geometry using the silver-ion-assisted seed-mediated method.[30] The
influences the photochemical reaction of 1,10-phenanthroline oxidation was carried out by bubbling O2 in the presence of
adsorbed on Ag nanoparticles.[23] Anisotropic chemical reactiv- HCl and a high concentration of cetyltrimethylammonium
ities of spheroidal Au nanoparticles were reported during cyanide bromide (CTAB) maintained at certain temperatures.
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Figure 1. Self-assembly of perfect and truncated cubic Pt nanoparticles
showing the effects of particle morphology on self-assembly. A) TEM image
and B) scheme of self-assembled cubic superlattices formed by perfect
nanocubes. C) TEM image and D) scheme of self-assembled fcc super-
lattices formed by truncated nanocubes. Reproduced with permission from
ref. [16]. Copyright 2008 American Chemical Society.
Figure 2. Oxidation of Au nanorods by O2 in 1 M HCl and concentrated
cetyltrimethylammonium bromide (CTAB) at 70 8C. a) UV–vis spectra
acquired at every 1 min interval during oxidation reaction of nanorods.
Transmission electron microscopy (TEM) studies showed that Au At the beginning of the reaction, the spectra exhibit two extinction peaks, a
higher-energy transverse plasmon band (TPB) and a lower-energy longi-
nanorods decreased in length whereas the diameter remained
tudinal plasmon band (LPB), characteristic of Au nanorod suspension. The
almost constant during oxidation (Fig. 2). Upon further oxidation, TPB stays at 520 nm and decreases in intensity while the LPB blue-shifts
Au nanospheres form, which ultimately dissolve into ionic gold and decreases in intensity with time. Upon further oxidation, the LPB
species. This implies that the oxidation starts at the ends of the Au disappears, indicating the conversion of nanorods into nanospheres.
nanorods. The nanorods stay single-crystalline during oxidation, Finally, the TPB extinction peak at 520 nm vanishes, suggesting the
suggesting that twinning is not involved in the oxidative oxidation of Au nanospheres into ionic Au species. b–d) Typical TEM
images of Au nanoparticles formed at various stages of Au nanorod
shortening process. This approach allows post-synthetic control
oxidation. TEM images of as-synthesized Au nanorods with longitudinal
of the aspect ratio of Au nanorods. plasmon wavelength (LPW) ¼ 785 nm (b), of shortened Au nanorods with
LPW ¼ 595 nm (c), and of final oxidation products showing spherical Au
nanoparticles (d). e) The changes of Au nanorod lengths (~) and
diameters (!) versus LPWs. f) The relationship between LPWs and aspect
4. Catalysis ratios. The line is a linear fit. Error bars in (e) and (f) represent standard
deviations. Reproduced with permission from ref. [30]. Copyright 2006
The use of palladium and platinum particles as catalysts in
American Chemical Society.
numerous chemical reactions is well known.[31] Due to the finely
dispersed states of nanoscale systems, one can obtain large
surface areas for a given quantity of materials. Nonspherical compared the catalytic properties of spherical Pt nanoparticles
particles provide ample corners, vertices, defects, kinks, and and Pt nanowires formed in mesopores of FSM-16 (a mesoporous
steps.[1] Exposure of different crystallographic facets, together silica) respectively.[38] Pt nanowires showed substantially higher
with the increased number of edges, corners, and faces, is of activity in the hydrogenolysis of butane than spherical particles, in
critical importance in controlling the catalytic activity and spite of a smaller total surface area of Pt nanowires. This was
selectivity of metal nanoparticles. Therefore, nanoparticles of attributed to the presence of more electron-deficient sites or
different sizes and shapes are highly desirable as catalysts in fuel preferential exposure of {110} planes. The morphology of Pt
cells, waste reduction, bioprocessing, and the chemical industry. metal nanoparticles significantly affected the catalytic activity in
Effects of NMNP size on the catalytic activity are well terms of product selectivity too. Pt-Rh nanowires that were
documented.[31–34] On the contrary, knowledge about the synthesized in a similar way by co-impregnating RhCl3 with
influence of metallic nanoparticle shapes on the catalytic activity H2PtCl6 also showed similar activities. Telkar et al. observed that
has started to develop only recently. Studies on the catalytic cubic Pd nanoparticles had higher turnover frequencies
activities of platinum nanoparticles showed distinctly different compared to those of spherical particles for the hydrogenation
catalytic activities for different morphologies.[35–37] Fukuoka et al. of butyne-1,4-diol and of styrene oxide.[39] Further, cubic particles
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plasmons. Associated with the excitation of surface plasmons are shape demonstrates that nonspherical nanoparticles will exhibit
REVIEW
strongly enhanced and highly localized electromagnetic fields multiple optical extinction bands due to their anisotropy. For
(i.e., local field enhancement). Surface plasmon can either be particles with shapes more complex than spherical or spheroid,
propagating, for instance at planar bulk metal surfaces, or numerical methods, such as the discrete dipole approximation
localized as in the case of NMNPs. In both cases, the (DDA), the T-matrix method, finite-difference time-domain
electromagnetic field is spatially confined at the interface; i.e., (FDTD) simulations, finite element calculations, the modified
it can be described by evanescent waves in the direction long wavelength approximation (MLWA), the multiple multipole
perpendicular to the interface. The optical properties of colloidal
method, and spectral representation, are used for the calculations
NMNPs in the UV–vis–NIR spectral range are mainly determined
of spectral characteristics.[53,58,63–73] Kuwata et al. have suggested
by localized surface plasmons that give rise to so-called localized
an empirical extension of the quasistatic (analytical) approach to
surface plasmon resonances—LSPRs observable in their extinc-
tion, i.e. absorption and scattering, spectra.[2,52,53] The electro- particles of arbitrary shapes, which can quantitatively predict
magnetic fields are not evenly distributed around nonspherical resonant light scattering from metal nanoparticles of arbitrary
NMNPs, which gives rise to shape-dependent LSPR spectra. Ag shape, whose sizes are too large for the Rayleigh approximation to
and Au nanoparticles are of particular interest in the context of be applicable.[74]
LSPR.
The optical features of the LSPR (e.g., peak absorption,
linewidth) depend on the size, shape, composition of the NMNP,
its surface charge, surface-adsorbed species, interparticle inter- 5.1. LSPR of Rod-Shaped Nanoparticles
actions, and the refractive index of the surrounding medium.[54]
LSPR is particularly pronounced if the imaginary part of the Nonspherical NMNPs offer the possibility of tuning the optical
dielectric constant is small and the real part of the dielectric properties over a broad spectral range. LSPR of gold nanorods are
constant equals twice the negative of the dielectric constant of the one of the most widely studied topics in the field of nanoparticle
surroundings.[55,56] Silver and gold fulfill these criteria and are optical properties. Short gold nanorods exhibit two bands in
commonly used as plasmonic metals. On the other hand, the vis–NIR spectral range. Based on theoretical studies and
colloidal platinum or palladium exhibit only broad absorption optical polarization measurements, the band near 530 nm has
continua extending throughout the near UV and visible range. been assigned to a transverse LSPR, which is polarized across
The effect of deviation from spherical geometry on the (corresponding to electron oscillation perpendicular to) the long
properties of NMNPs is well documented through their optical axis of the nanorod, and the other one, appearing at a longer
property studies. For nonspherical nanoparticles, such as rods, wavelength, has been assigned to a longitudinal LSPR mode,
disks, and triangular prisms, the LSPRs are typically split into which is polarized along (parallel to) the long axis. The
distinctive dipole and quadrupole plasmon modes.[57–60] Optical longitudinal LSPR peak is very sensitive to the aspect ratio
properties of NMNPs can be theoretically predicted for various (length/diameter) of the nanorod and shifts to longer wavelength
shapes. The simplest form of a nonspherical shape is a spheroid. (red-shift) with increasing aspect ratio.[62,75–77] From DDA
For spheroids, a classical quasistatic approach serves well to simulations, Brioude et al. found that thinner nanorods give
describe the spectral position, width, and strength of the dipolar larger lmax shifts than thicker ones for the same difference in
plasmon resonance.[55,59] Based on classical approaches, for a their rod lengths.[77] The morphological anisotropy of gold
metal nanoparticle sufficiently small compared to the wavelength nanorods can influence the width of the absorption band.[78] Hu
of light l, there is a resonance condition associated with each axis et al. synthesized tadpole-shaped gold nanoparticles, showing a
j of a spheroid: broad peak at 583 nm with a full width at half-maximum
(FWHM) of 150 nm.[79] These authors suggest that the electron
oscillation corresponding to the plasmon absorption along the
1
" ¼ "m 1 (1) long axis is retarded on a reflective path. This is attributed to a
Lj large disparity in size from the tip of the head through the tail of
the tadpole. The tadpole-shaped nanoparticles have yet another
where e is the complex wavelength-dependent dielectric function interesting property: the tails of the tadpoles contain a higher
of the metal, Lj is the geometrical depolarization factor along the negative charge than their heads unlike the usual case of uniform
charge distribution on the surfaces of colloidal nanoparticles, as
axis j, and em is the dielectric function of the surrounding
demonstrated by electrophoresis experiments.
medium.[54,60] L1 ¼ L2 ¼ L3 ¼ 1=3 for spherical particles. For
For small metal particles with dimensions far less than the
prolate spheroidal particles (L1 ¼ L2 < L3), the dipole resonance
wavelength, the conduction electrons are all excited in-phase with
splits into two absorption bands—longitudinal and transverse the incident electromagnetic field, yielding a dipolar oscillation.
modes—where the induced dipole oscillates along and perpen- However, in larger particles, the field across the particle becomes
dicular to the long axis of the spheroid, respectively.[61] The nonuniform and multipolar excitations, such as the quadrupolar
longitudinal resonance band shifts towards longer wavelengths and octupolar, can be observed. This gives rise to multiple
(red-shift) and increases in absorption cross-section as the aspect peaks in the optical spectrum. Such multipole resonances
ratio of the spheroid increases, whereas the transverse resonance have been detected experimentally and theoretically from gold
band remains near the wavelengths of the spherical particle nanorods/nanowires and nanoshells, and silver and gold
absorption band.[55,61,62] This example of the simplest nonspherical nanoprisms.[65,72,73,80–85] The dipolar LSPR is always situated
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wavelength, which is mainly determined by the aperture angle
and the roundness of the tip.
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nanoparticle.[104,131,139] By comparing the refractive index It should be pointed out here that there are factors, such as
REVIEW
sensitivities of a number of Au nanoparticles, Chen et al. surface-induced relaxation (surface scattering) and radiative
observed an increase in the index sensitivities when Au decay (radiation damping) of LSPRs, which impose upper limits
nanoparticles become elongated or their apexes becomes to the strength of the field enhancement in metal nanoparti-
sharper.[131] Accordingly, Au nanospheres exhibit the smallest cles.[141] Surface scattering is a function of the surface-to-volume
refractive index sensitivity of 44 nm/RIU (refractive index unit), ratio; hence, it scales with 1/r where r is the typical dimension of
and branched Au nanoparticles exhibit the largest index the particle, the radius in the case of a sphere. Thus, the degree of
sensitivity of 703 nm/RIU (Table 1). These authors also found plasmon damping is largely influenced by the nanoparticle shape.
that the sensitivities of Au nanobipyramids were higher than The radiation damping can in principle be reduced by decreasing
those of the corresponding Au nanorods with increasing the particle volume. However, in the case of very small particles,
longitudinal plasmon wavelengths. This suggests that the the plasmon is damped due to surface scattering. In the latter
nanoparticle morphology is an important factor in determining case, electrons can be scattered at the particle surface, when the
the refractive index sensitivity. However, Miller and Lazarides dimensions of the particle become comparable to or smaller than
have theoretically predicted that for any gold nanoparticle of the free-electron mean free path. The surface electron scattering
moderate size in a homogeneous dielectric environment, the depends on both the particle size and shape.[145] As the radiation
refractive index sensitivity is a function of only the LSPR band damping is larger at larger size and the surface scattering is
position, and independent of particle shape, size, or composi- stronger at smaller size, there will be an optimum volume for
tion.[133] That is, the refractive index sensitivity of all arbitrarily which the highest enhancement is achieved, depending on the
shaped nanoparticles in a homogeneous dielectric environment particle shape.[141]
will be the same if they have the same plasmon band location. It In addition to radiative damping and surface scattering, there
should be pointed out here that nanoparticles are often present in are two important size-independent damping mechanisms.
an inhomogeneous dielectric environment due to asymmetric Plasmon polaritons may either decay via single-electron excita-
surface adsorption or substrate interaction. tions where electrons of the sp band are excited to empty states
in the sp band (intraband excitation), or d band electrons are
excited to empty states in the sp band (interband excitation).[54]
6. Local Field Enhancement The latter is a particularly severe damping mechanism of Cu
Plasmon resonant particles are surrounded by strongly enhanced nanoparticles and still disturbs the plasmon resonance of
and highly localized electromagnetic fields when excited at their spherical gold nanoparticles. Yet, any nanoparticle morphology
LSPR. These fields are the direct result of the polarization which shifts the plasmon resonance away from the onset of
associated with the collective electron oscillation in the metal interband excitation automatically leads to a narrowing of the
particles. The local field (Eloc) on or near the nanoparticle will be a plasmon spectra. A narrow plasmon spectrum (or equivalently,
sum of the incident field (E) and the induced field from the a long plasmon lifetime) is beneficial for all effects that rely
oscillating electrons; i.e., Eloc is usually higher than the original on a huge field enhancement. For instance, the third-order
field E.[54,140] The local field enhancement factor, f(v), is defined susceptibility of metal nanoparticles[146] and the effective SERS
by f(v) ¼ Eloc/E. Earlier electrodynamic calculations have shown cross-section[147] are proportional to the fourth power of the
that the local field enhancement factor depends on the particle inverse of the homogeneous linewidth Ghom of the plasmon
eccentricity.[68,141–144] The field enhancement at the tip of a resonance. Knowledge of the damping mechanisms is therefore
spheroid is larger than the one created by a resonant sphere of vital for a deep understanding of the performance of metal
similar dimensions.[141–144] nanostructures.
Table 1. Sizes, plasmon wavelengths, and refractive index sensitivities (RIU: refractive index unit) of variously shaped Au nanoparticles. The numbers in the
parentheses following values are standard deviations. Reproduced with permission from ref. [131]. Copyright 2008 American Chemical Society.
Au nanoparticles Length Diameter Aspect Plasmon wavelength Index sensitivity Figure of merit
[nm] [a] [nm] [b] ratio [c] [nm] [d] [nm/RIU] [e]
[a] Length for nanocubes is the edge length, and for branched nanoparticles, it is the distance from the center to the branch tip of the particle. [b] The diameter for nanobipyramid
is the central width. [c] The ratio between the length and diameter. [d] Plasmon wavelength of Au nanoparticles dispersed in aqueous solutions. For branched nanoparticles, it is
the longer plasmon wavelength; for nanorods and nanobipyramids, it is the longitudinal plasmon wavelengths. [e] For nanobranches, it is the refractive index sensitivity of the
longer-wavelength plasmon peak, and for nanorods and nanobipyramids, it is that of the longitudinal plasmon resonance peaks.
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field distribution.[155] According to their report, the tips of the Raman intensity is thereby enhanced by the square of the product
REVIEW
triangles in general do not represent regions of highest local field of the field (amplitude) enhancement factors at the excitation
enhancement. frequency nL and Stokes Raman frequency nS.[141,148,166,176] When
Experimental determinations of field enhancements have been nL and nS are near the LSPR frequency, the observed Raman
performed using two-photon photoluminescence (TPPL) from scattering intensity is approximately proportional to the fourth
gold bowtie nanoantennas, and a comparison with the TPPL power of the local electric field enhancement.[181] Even a modest
emission from smooth gold films was made.[119] The determina- local field enhancement near the metal particle leads to
tion of field enhancements from SERS appears to be more substantial electromagnetic enhancements of Raman scattering
difficult since the total Raman enhancement factors can also intensities. The chemical enhancement mechanism arises due to
include nonelectromagnetic contributions, as discussed below. specific, localized analyte–substrate interactions upon analyte
The optical local field enhancement provides the basis for adsorption. These interactions include the electronic resonance-
many applications in molecular detection, sensing, and nano- charge transfer between the molecule and metal surface, and
photonic devices. A molecule residing on or near a metal adsorption-induced changes in the analyte polarizability.[168,179]
nanoparticle may experience a light intensity far stronger than The Stokes Raman signal is proportional to the Raman
just the intensity of the incident light due to the enhanced local cross-section of the molecule s, the excitation laser intensity, I(nL),
fields.[156] This has been exploited for a variety of applications, and the number of molecules N which are involved in the
such as the above-mentioned SERS, surface-enhanced fluores- process.[166] The surface-enhanced Stokes Raman signal ISERS can
cence (SEF), SNOM, etc.[157–164] Nonspherical nanoparticles of be written as follows:
silver and gold are attractive as SERS and SEF substrates, because
the LSPR wavelengths of these particles can be tuned over a broad
range in the UV–vis–NIR region.[159,160,165] ISERS ðnS Þ ¼ N IðnL Þ jf ðnL Þj2 jf ðnS Þj2 s ads (2)
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spherical gold nanoparticles under similar conditions. These gold nanostars coated with self-assembled monolayers of 4-MBA
REVIEW
enhancement factors were two orders of magnitude larger than (Fig. 8) and estimated a total Raman enhancement factor of 107
the calculated values. This was, therefore, attributed to the for individual nanostars.[107] This wide range of enhancement
chemical enhancement contributions on the gold nanorod factors reported for rather similar structures demonstrate the
surface. Murphy and co-workers reported the effects of aspect difficulty in determining reliable estimates for total Raman
ratios of silver and gold nanorods on SERS in colloidal enhancement factors. The difficulties may include changing
solution.[186] The optical properties of these nanorods have been analyte–particle interactions if different analytes are employed,
tailored to have variable degrees of overlap of their longitudinal different experimental situations (i.e., ensemble versus single
plasmon mode with the excitation source in the absence of objects, or geometry), or potentially different amounts of analyte
interparticle plasmon coupling effects. According to these due to different initial surface functionalization, which hinders a
authors, silver and gold nanorods of an aspect ratio of 10 and precise determination of the number of molecules contributing to
1.7, respectively, show total Raman enhancement factors in the the signal. Recently, Uji-i et al. demonstrated remote excitation of
range of 103–107, when the plasmon resonance overlaps with the SERS by forming a hotspot between a silver nanoparticle and a
excitation frequency. These enhancement factor are 10–100 times silver nanowire. SERS in the hotspot region could be observed
greater than the ones of particles with aspect ratios that lack the after launching a propagating plasmon in the wire through laser
spectral overlap between their plasmon resonance and the excitation several micrometers away from the hotspot.[190]
excitation wavelength.[186] Similarly, Xia and co-workers demon- According to Xu et al., single spherical or regular crystal
strated that for a given size, the sharper cubes gave stronger shaped nanoparticles are likely inefficient as substrates for
Raman peaks than truncated ones.[98] The difference in single-molecule SERS due to their comparatively weak electro-
enhancement factor was attributed to the variation in overlap magnetic enhancement effect.[144] Strongly coupled structures,
between the particle LSPR and the laser frequency. such as dimer configurations or particles with sharp surface
Kottmann et al. studied the relation between the nonregular protrusions, may be suitable for single-molecule SERS due to
cross-sectional shape of a nanowire, its resonance spectrum, and large and spatially confined electromagnetic enhancement
the resulting field enhancement by numerical calculations.[187] effects.[144,191,192] It should be noted however, that in dimer
According to them, the maximum field and Raman enhance- structures at very small interparticle distances (<1 nm) electro-
ments depend on the cross-sectional shapes of silver nanowires, magnetic enhancements will be limited by quantum mechanical
among others. The maximum Raman enhancement should effects such as interparticle electron tunneling.[193] Though
exceed 106 for a triangular cross-section; for a square, it is about electromagnetic enhancement is likely to produce the dominant
105, whereas it is below 104 for the hexagonal, pentagonal, and contribution to single-molecule sensitivity in SERS in these cases,
circular cross-sections. Calculations of Xu et al. indicate that the an additional chemical or electronical resonant enhancement
maximum enhancement factor achievable through electromag-
netic mechanisms is on the order of 1011.[144] This can be realized
only under special circumstances, such as for strongly coupled
structures (such as dimer configurations) or at locations close to
sharp surface protrusions.[102,107,144] From the extensive literature
that reports estimates and measurements of Raman enhance-
ment factors, we limit ourselves to mentioning a few: Tian et al.
have reported that platinum nanothorns prepared by an
electrochemical method exhibit considerably higher SERS activity
than smooth spherical platinum nanoparticles possibly due to the
lightning-rod effect.[188] The SERS signal significantly decreases
with the decrease in nanothorn tip sharpness and nanothorn
density. Murphy and co-workers reported surface enhancement
factors in the range of 107–109 for 4-mercaptobenzoic acid
(4-MBA) molecules sandwiched between a smooth gold substrate
and gold nanoparticles of several different morphologies.[182]
Recently, star-shaped gold nanoparticles received increasing
attention due to the potentially large field enhancements in the
vicinity of their tips.[105] Khoury and Vo-Dinh have reported an
enhancement factor 5 103 for SERS of 4-MBA molecules on
gold nanoparticles with such sharp surface protrusions in
solution ensemble measurements.[103] Nalbant-Esenturk et al.
estimated the Raman enhancement factors of gold nanostars to Figure 8. a) Sketch of the combined dark-field scattering and Raman
exceed 105 using 2-mercaptopyridine and crystal violet as microscope used for single-particle spectroscopy. b) Scanning force micros-
analytes.[189] Rodriguez-Lorenzo et al. recently demonstrated that copy height image of an individual gold nanostar deposited on a glass
coverslip and coated with self-assembled monolayers of 4-mercaptobenzoic
a SERS signal amplification of 1010 can be achieved in junctions acid. c) Raman spectrum of a self-assembled monolayer (SAM) of
between a gold nanostar tip and a gold surface for 4-mercaptobenzoic acid on the single gold nanostar shown in (b) (60 s
1,5-naphtalenedithiol which allows zeptomolar analyte detec- integration time and 240 kW/cm2 at the sample). Reproduced with per-
tion.[108] Hrelescu et al. reported Raman scattering from single mission from ref. [107]. Copyright 2009 American Institute of Physics.
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effect has to be invoked in order to explain the SERS moment relative to the particle surface.[159,203,204] For example, the
REVIEW
enhancement factors of the order 1014 reported in the fluorescence intensity depends on whether a fluorophore is located
literature.[144,172–174,180,191] Based on DDA calculations of the near the tip of an ellipsoid (on the major axis), or along the minor
field enhancement factors for various different silver axis of the ellipsoid. The fluorophore will experience two different
particle sizes, shapes, orientations, and interparticle spacings, modes of the LSPR. Further, there is a difference whether the
Hao and Schatz also concluded that not all of the single-molecule fluorophore dipole moment is perpendicular or parallel to the
SERS enhancement factor of 1012 can be ascribed to purely particle surface. Fluorescence is either enhanced or quenched
electromagnetic effects.[58] Wokaun et al. have shown that since the molecular transition dipole is enhanced or canceled by
radiation damping limits the values of the attainable electric the corresponding image dipole induced in the metal.[203]
field intensity at the tip of small metal rods and hence limits the Depending on the aspect ratio, a radiative rate enhancement by
enhancement factors found in SERS.[141] According to them, the a factor of 103 or greater can be found for a fluorophore (transition
difference between various shapes is virtually eliminated for moment) orientation perpendicular to the surface of an
larger volumes due to radiation damping. ellipsoid.[203] Therefore, quenching or enhancement of the
fluorescence and changes of fluorescence lifetime are dependent
on the morphology of the metal particles.
Gold nanoparticles have also been observed to show weak
8. NMNPs and Fluorescence intrinsic photoemission via an interband transition mechan-
Fluorescence, the spontaneous radiative decay of electronically ism.[205] This effect can be enhanced by many orders of
excited molecules, is widely used as a signal transduction tool for magnitude in the presence of plasmon resonances.For example,
the detection of trace levels of analytes, imaging, and El-Sayed and co-workers have shown that the photoluminescence
single-molecule studies of biological systems. Metal nanoparti- quantum efficiency from gold nanorods can be enhanced by 6 to 7
cles have been found to either quench or enhance fluorescence orders of magnitude compared to bulk metal.[206] Li et al. have
intensity of a fluorophore.[156,162–164,194–196] The quenching and demonstrated that sufficiently long gold nanorods (aspect
enhancement are determined by interactions between fluoro- ratio > 13) exhibit intense fluorescence.[160] The emission
phores and metal surfaces depending on the location of the observed in gold nanorods of different aspect ratios is a function
fluorophore around the particle, the orientation of its transition of local field enhancement factors and is therefore enhanced in
dipole moment relative to the particle surface, and the the spectral vicinity of the LSPR.[160,206–208] Enhanced emission of
particle–fluorophore distance.[156,162–164,194–198] Quenching may the rod is more than 1 order of magnitude larger compared to that
occur by Förster resonant energy transfer (FRET) to the surface for the nanosphere.[207] Under pulsed laser excitation, Au
plasmon absorption of the metal particle. FRET is a dipole–dipole nanorods were observed to emit a strong TPPL, which is many
interaction mechanism in which a donor fluorophore in its times brighter than the TPPL from single dye molecules.[209,210]
excited state transfers its energy radiationless to an acceptor. The strong TPPL is thought to arise from the plasmon-enhanced
FRET has been widely used to measure the distance between sites two-photon absorption cross-section due to coupling of weak
or biomolecules due to its 1/R6 distance dependence (R is the electronic transitions in the metal to the particle plasmons.[210,211]
distance between the dipoles concerned).[199–201] When donors TPPL has been recently used as a nonlinear optical imaging
and acceptors are present in proximity with sub-wavelength mode, which will be discussed below.
metal particles, the rates of energy transfer increase at distances
up to 70 nm, which is 10-fold larger than typical Förster
distances.[199,200] 9. Applications of Nonspherical NMNPs
Enhancement occurs through the increase of the strength of
the incident light field which increases the rate of excitation, and 9.1. Analytical Applications
an increase in the radiative decay rate of the fluorophore.[194] The
resonantly enhanced local field of metal nanoparticles can NMNPs, and in particular gold nanoparticles, possess large
increase or suppress the rate of excitation. Metal particles can scattering cross-sections, high degree of biocompatibility, rich
greatly enhance local excitation intensities, since the light surface functionalization chemistry, and high photostability.
intensity is proportional to the square of the field. Another Therefore, these particles have been shown to be very useful for
important effect of metal particles is that they can modify the biomolecular manipulation, labeling, and detection.[212–214]
intrinsic radiative decay rate of a fluorophore. An appropriate Further, for several (in vivo) applications, nonspherical gold
proximity and orientation of fluorophores to metal particles nanoparticles are also advantageous because their LSPR can be
modifies the photonic mode density around the fluorophore and tuned to the NIR wavelength range, the so-called biological
will lead to a radiative rate outranging the rate of losses under window, where the absorption, scattering, and fluorescence from
favorable circumstances.[194,197] Theoretical calculations show an endogenous biological chromophores are minimal.[215]
increase of the radiative decay rate of up to two orders of Sensitivity and specificity are two critical issues in modern
magnitude for a fluorophore near a prolate silver nanoparticle, biomedical diagnosis research. Yguerabide and Yguerabide
unlike the radiative rate increase in case of a spherically or a demonstrated that single NMNP can be used as optical reporters
nonresonantly shaped nanoparticle.[202] in clinical and biological applications by using the strong elastic
The shape of a nanoparticle exerts its influence on the light scattering properties of these particles.[86,117,216] Plasmon
fluorescence of a fluorophore depending on the location of resonant particles have very high scattering cross-sections
the fluorophore around the particle and the orientation of its dipole compared to other optical labeling entities under the same
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illumination conditions. For example, the cross-section for elastic LSPR biosensor for the binding of streptavidin to biotin.[235] The
REVIEW
light scattering from an 80 nm plasmon resonant particle is lowest streptavidin concentration that was experimentally mea-
equivalent to the absorption cross-section of 500 000 individual sured was 1 nM, which was substantially lower than that detected
fluorescein molecules or >105-fold that from typical semicon- by biotinylated single gold nanospheres.[109,235,236]
ductor quantum dots.[217] The impressive signal of ultrabright Sönnichsen and Alivisatos reported that gold nanorods could
plasmon resonant particles allows them to be individually be exploited for the study of rotational motion in biomole-
identified and counted relatively easily, pushing the analyte cules.[237] Murphy and co-workers demonstrated the use of optical
detection limit to a dramatically low value. This, being aided by patterns, produced by resonant Rayleigh scattering from gold
the high photostability and absence of blinking, promises an nanorods, as markers by which local deformations of stretchable
ultrasensitive assay format based on single-target molecule polymers could be measured using image correlation techniques.
detection. NMNPs can replace or complement the colorimetric, These authors proposed that modified gold nanorods could be
fluorescent, or radioactive labels routinely used in immunoassays used for examining mechanical effects in biological tissues.[238] Li
and cellular imaging.[86,216–219] et al. suggested the use of relatively intense fluorescence of
Single or aggregated NMNPs can also act as transducers that sufficiently long gold nanorods (aspect ratio >13) as probes in
convert the changes in the interparticle distance or local refractive fluorescence-based microarray assays and optical biosensor
index into spectral shifts in their absorption and scattering development, and demonstrated the application of this concept
spectra. Thus the plasmon resonant nanoparticles have very by monitoring DNA hybridization events by measuring the
promising applications as label-free biosensors.[109,137,220–223] concomitant change in fluorescence intensity.[160] Nishizawa et al.
This sensing property uses the spectral change or the LSPR have demonstrated that hollow Au nanotubules support
brought in by the biomolecular event occurring in the vicinity of selective ion transport analogous to that observed in ion-exchange
the plasmon resonant nanoparticles. The biomolecular event can polymers, when the inside radius of the tubule is small relative to
either change the interparticle distance and thereby the coupling the thickness of the electrical double layer.[239] The metal
of surface plasmons between the particles or the local refractive nanotubule membranes can be cation-permselective, anion-
index of the nano-environment of the nanoparticle. When permselective, or nonselective, depending on the potential
the plasmon resonant particles are very close to each other, the applied to the membrane. Metal nanotubule membranes have
plasmon oscillations from adjacent particles can couple giving potential for applications as universal ion-exchange membranes,
rise to hybridized plasmon modes derived from the modes of the and in chemical separations, such as biomedical separations or
individual particles.[224–226] The occurrence of a strongly industrial gas separations.[240]
distance-dependent red-shifted mode has been utilized by NMNPs have been used for the detection of inorganic ions,
researchers to develop colorimetric sensors for the detection of organic molecules, and biomolecules. One of the major
DNA as well as insertions, deletions, and mismatches at a mechanisms of detection involves the change in the LSPR due
single-base resolution.[227–229] Similarly, Dujardin et al. reported to interaction between the particle and adsorbed analyte. Sudeep
self-assembly of oligonucleotide-functionalized short gold nanor- et al. reported selective detection of micromolar concentrations of
ods.[14] As discussed earlier in Section 5.5, the LSPR peak position cysteine and glutathione in the presence of various other a-amino
and intensity are sensitive to the local refractive index acids by exploiting the interparticle plasmon coupling in Au
surrounding the nanoparticle. The binding of biomolecular nanorods.[241] Rex et al. have demonstrated the analytical potential
targets to receptor-functionalized nanoparticles results in a of Au nanorods for monitoring Hg in water samples with
change in the local refractive index and hence spectrally shifts outstanding selectivity and sensitivity based on amalgamation
the LSPR of nanoparticles. These changes enable monitoring of without previous separation or preconcentration of the original
molecular binding in real time with high sensitivity by simple sample.[242]
spectrophotometric techniques.[109,230,231] Chen et al. have shown
that for gold nanorods the longitudinal LSPR band sensing mode
exhibits much higher sensitivity and linearity to the concentration 9.2. Photothermal Therapy
of the target biomolecules compared to that of the gold
nanospheres.[137] Marinakos et al. have also observed that the Large absorption cross-sections and the decay of plasmons into
nanorod-based sensors have advantages over gold nanosphere- electronic excitations with subsequent electron–phonon relaxa-
based sensors.[220,232,233] In addition to a significantly lower tion make metal nanoparticles very efficient heat sources. Metal
detection limit, the signal of the nanorod sensor provides the particles normally show rather poor light emitting ability.
internal self-reference due to the measurement of wavelength Therefore, they can efficiently convert the absorbed light into
shift of the plasmon bands.[220,232,233] The peak wavelength shift heat via nonradiative electron relaxation dynamics, known as
is solely determined by changes in the dielectric properties (i.e., photothermal effect, and serve as nanometric local heat
refractive indices) in the immediate vicinity of the nanoparticles, sources.[243–248] As the light absorption cross-section is greatly
and concentration change has minimal or no effect on this enhanced under plasmonic resonance conditions (the spectrum
parameter. Spectral changes induced by changes in the refractive of the heat generation rate demonstrates a typical plasmon peak at
index in the vicinity of individual gold nanorods due to target the LSPR frequency), the magnitude of generated heat will
binding have been utilized by Yu and Irudayaraj for multiplex depend on the particle size and shape, in addition to the nature of
biosensing by using the longitundinal plasmon mode of nanorods the metal and the number of nanoparticles present in the system.
of different length functionalized with different specific analyte As optical and thermal responses are closely related, metal
acceptors.[234] Recently, Nusz et al. reported a single-gold nanorod nanoparticles can be used as nanometric heat sources and probes
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vior.[229,243,249,250] For example, heat-induced changes in optical
properties (e.g., refractive index) of the surrounding inhomoge-
neous medium can be recorded in photothermal imaging.[251]
The heat generated in metal nanoparticles may also induce phase
transformations in their surrounding matrix and can be used to
release drugs from polymer capsules or to release the contents of
small containers inside living cells.[252–255] The importance of
nanoparticle shape in the photothermal effect has been
demonstrated in photothermal therapy.[256,257] In these applica-
tions, after attaching to tumor cells, the nanoparticles are
irradiated by short laser pulses and the absorbed light energy is
quickly transformed into heat. The heat generated may reach
thresholds which result in desired target damage through
thermal denaturation and coagulation or through mechanical
stress caused by microbubble formation, acoustic, and shock
wave generation.[258,259] The photothermal therapy is relatively
simple to perform and has the potential of treating tumors
embedded in vital regions without surgical resection. In order to
effectively absorb light in biological medium, the metallic
nanoparticles should show a LSPR in the biological window
(650–900 nm). LSPR of several kinds of nonspherical Ag and Au
particles, such as nanorods, nanoshells, nanocages, and
nanostars, can be tailored to this range.[107,153,260] Suitable Figure 9. Photothermal destruction of SK-BR-3 breast cancer cells (in
selection of the experimental parameters, therefore, promises vitro) treated with immunogold nanocages (45 nm size) and irradiated
highly localized and controlled destruction or treatment of the by an 810 nm laser at a power density of 1.5 W/cm2 for 5 min. A well-
targets varying from a few nanometer to tens of micrometers defined circular zone of dead cells is revealed by A) calcein AM assay, and
(such as from bacteria to (cancer) cells).[256,257,261–266] B) ethidium homodimer-1 (EthD-1) assay. In the control experiment, cells
Experimentally, it has been observed that 30–40 nm particles irradiated under the same conditions, but without immunogold nanocage
treatment maintained viability, as indicated by C) calcein fluorescence
are most effective for photothermal therapy.[267] According to
assay and D) the lack of intracellular EthD-1 uptake. Reproduced with
some calculations, silica core–gold nanoshells (core diameter: permission from ref. [274]. Copyright 2007 American Chemical Society.
50–100 nm, shell thickness: 3–8 nm) and gold nanorods (aspect
ratio ¼ {15–20 nm}/{50–70 nm}) are more efficient photothermal
labels and sensitizers than solid single gold spheres of equivalent other components that allow additional functionalities to be
volume.[268] Gold nanoparticles, especially nanorods, are emer- introduced (such as an extra segment that binds to an
ging as one of the most promising candidates for photothermal endosomolytic agent) to create a versatile synthetic gene delivery
applications since they are strong absorbers, biocompatible, easily system. Takahashi et al. have reported that Au nanorods can be
conjugated to antibodies or proteins, and have adjustable optical used as carriers for a phototriggered gene delivery, with 1064 nm
properties.[153,269] Owing to the large plasmon resonance laser irradiation triggering the release of plasmid DNA from
absorption efficiency of nanorods, the threshold energy density phosphatidylcholine-modified nanorod–DNA (PC-NR–DNA) com-
for photothermolysis can be sufficiently small.[265] Further, due to plexes via morphological transformation of Au nanorods into
their large scattering cross-section, nanorods can be used spherical nanoparticles.[277] Kitagawa et al. have reported controlled
simultaneously for imaging and photothermal therapy.[261,270–273] release of myoglobin protein from the myoglobin–gold nanorod
Gold nanoparticles of other morphologies such as nanocages and complexes by NIR (pulsed) laser irradiation.[278]
nanoshells, whose optical properties can be tuned to the vis–NIR
spectral region, have also been tested for their photothermal
therapeutic properties (Fig. 9).[266,274] Chen et al. reported that 9.3. Cellular Uptake and Imaging
immunogold nanocages had lower power density threshold of
1.5 W cm2 for selective destruction of cancer cells than those Chithrani et al. have studied the size- and shape-dependence of
reported for gold nanorods (10 W cm2) or gold nanoshells the uptake of gold nanoparticles into mammalian cells.[279] These
(35 W cm2).[257,261] However, in addition to the morphology authors found that 50 nm spheres were taken up more effectively
effect, other parameters such as the density of nanocages on each by the cells compared to both smaller and larger spheres in the
cell could also contribute to the lowering of the thermal damage 10–100 nm size range. On the other hand, uptake of lower-
threshold. aspect-ratio (1:3) nanorods was greater than that of those with
Salem et al. have demonstrated a new nonviral gene therapy higher aspect ratio (1:5). Interestingly, nanospheres were taken
approach by using multisegment metal nanorods.[275,276] up more efficiently than nanorods with dimensions in the
Differential molecular binding strategies were used to attach 10–100 nm range. However, the difference in surface chemistry
plasmids and a cell-targeting protein to spatially separated regions could be partly responsible for the difference in uptake between
of the delivery system. This approach can be extended to include spherical and rod-shaped NMNPs. Still very little is known about
Adv. Mater. 2010, 22, 1805–1825 ß 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1819
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the independent role of particle size, shape, and surface physical and chemical properties of nonspherical NMNPs, which
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1820 ß 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2010, 22, 1805–1825
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imaging for reading.[307] Due to the strongly anisotropic will be to make them multifunctional and to control their
REVIEW
plasmonic response of the nanorods only a small subpopulation properties via the local environment or external stimuli. This is
is thermally reshaped for a given laser wavelength and essential for construction of future nanodevices. Looking further
polarization. The use of five wavelengths and two polarization to future potential applications, one can expect that the NMNPs of
orientations, therefore, allowed the authors to write and read controlled morphologies will find applications as in vivo force
18 images in three layers spaced by 10 mm (Fig. 10). They sensors; morphological seeds for aligned block copolymer/
estimated that the storage density can reach 1 Tbit cm3 which inorganic nanocomposites with anisotropic properties; smart
would result in a capacity of about 1.6 Tbyte for a DVD-sized disk. catalysts (for fuel cells, waste treatment, bioprocessing, etc);
Pan et al. have studied the optical limiting properties of a number enhancers in photovoltaics and other energy conversion devices;
of metal (Cu, Co, Ni, Pd, Pt, and Ag) nanowires.[308] They have better therapeutic and imaging agents; probes for single-molecule
found that the nanowires have broadband optical limiting sensing of drugs, toxins, and environmental pollutants; and key
capability and that the optical limiting performances of some components in energy transport and novel opto-electronic
metal wires are comparable to or better than those of carbon devices.
nanotubes. Thus, metal nanowires can find
applications as cheap and efficient optical
limiters. Recently, Selhuber-Unkel et al. have
shown that gold nanorods can be used as
efficient optical handles in nanoscale experi-
ments.[309] These authors anticipate that gold
nanorods can be employed as force sensors
in future in vitro and in vivo studies as well
as force transducers in single-molecule
experiments.
Adv. Mater. 2010, 22, 1805–1825 ß 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1821
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Acknowledgements [33] T. K. Sau, A. Pal, T. Pal, J. Phys. Chem. B 2001, 105, 9266.
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