Perspective

pubs.acs.org/JPCL

Anisotropic Nanoparticles and Anisotropic Surface Chemistry

Nathan D. Burrows, Ariane M. Vartanian, Nardine S. Abadeer, Elissa M. Grzincic, Lisa M. Jacob,
Wayne Lin, Ji Li, Jordan M. Dennison, Joshua G. Hinman, and Catherine J. Murphy*
Department of Chemistry, University of Illinois at UrbanaChampaign, 600 South Matthews Avenue, Urbana, Illinois 61801, United
States
ABSTRACT: Anisotropic nanoparticles are powerful building blocks for materials
engineering. Unusual properties emerge with added anisotropyoften to an
extraordinary degreeenabling countless new applications. For bottom-up assembly,
anisotropy is crucial for programmability; isotropic particles lack directional interactions
and can self-assemble only by basic packing rules. Anisotropic particles have long
fascinated scientists, and their properties and assembly behavior have been the subjects
of many theoretical studies over the years. However, only recently has experiment
caught up with theory. We have begun to witness tremendous diversity in the synthesis
of nanoparticles with controlled anisotropy. In this Perspective, we highlight the
synthetic achievements that have galvanized the eld, presenting a comprehensive
discussion of the mechanisms and products of both seed-mediated and alternative
growth methods. We also address recent breakthroughs and challenges in regiospecic
functionalization, which is the next frontier in exploiting nanoparticle anisotropy.

improved properties in applications such as electronic

circuitry,21 optical lters and lms,2224 and sensors based on
surface-enhanced Raman scattering (SERS).25,26 Nanoparticles
can also be assembled in polymer lms27 with alignment
control through mechanical deformation28,29 or geometric
connement within block copolymers30 as well as inorganic
templates.31 Further dynamic manipulation of nanoparticle
assemblies and their alignment is possible through composites
with liquid crystals.32,33 Composite lms can be produced that
imbue chirality into the assembly and therefore the optical
properties.34

olloidal nanoparticles can be prepared in an everincreasing number of shapes and sizes, giving rise to a
host of varied physicochemical properties.17 Anisotropic
nanoparticles possess asymmetric axes, and this break in
symmetry is the origin of remarkable physical properties in
metallic, semiconducting, and polymeric materials. These
particles also provide interesting targets for regiospecic
functionalization. Together, these features make anisotropic
nanoparticles attractive subjects for fundamental and application-driven research. Gold nanorods are a classic example of
nanoparticles whose shape anisotropy results in unique optical
properties (Figure 1A).8 The isotropic counterpart to the gold
nanorod, the gold nanosphere, possesses a single localized
surface plasmon resonance (LSPR), but the two dierent axes
of rods (the longitudinal and transverse) give rise to two
distinct plasmon resonances. The location of the longitudinal
plasmon band is inuenced by the aspect ratio (length/width)
of the nanorod, making it possible to tune the LSPR.9
Discovery of shape-dependent properties of noble metal and
semiconductor nanoparticles has prompted the development of
a myriad of exotic particle shapes,1 such as stars, owers, wires,
triangles, and plates, for a host of applications including sensing,
imaging, and photothermal therapy.1015 Anisotropic particles
have been explored as near eld transducers for heat-assisted
magnetic recording for data storage.16 Electronic properties can
also emerge from structural anisotropy, as observed with carbon
nanotubes, which have garnered much attention in the past 20
years for their utility in electronics and sensing.17,18
Furthermore, the assembly of nanoparticles can result in
unique mesoscale phenomena that show emergent properties
beyond the sum of the materials disparate parts19 and can even
eect how cells respond to nanoparticles.20 The patterned
deposition of nanoparticles on various substrates can lead to
2016 American Chemical Society

Anisotropic nanoparticles possess

asymmetric axes, and this break
in symmetry is the origin of
remarkable physical properties in
metallic, semiconducting, and
polymeric materials.
Anisotropy is not limited to shape but can also arise from the
chemical composition and surface chemistry of the particle. The
most well-known chemically anisotropic colloid is the Janus
particle, a sphere whose hemispheres feature distinctly dierent
chemical compositions.37 Such diverse chemistry can aord
Janus particles amphiphilicity and novel optical and magnetic
properties, making them useful as emulsion-stabilizing
surfactants,38 catalysts,39,40 and as building blocks for selfReceived: October 3, 2015
Accepted: January 28, 2016
Published: January 28, 2016
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Perspective

Figure 1. A Venn diagram of morphological and chemical anisotropy with examples: (A) gold nanorods, (B) gold nanoparticles grown site
selectively on cadmium selenide nanoplatelets (adapted from Naskar et al),35 and (C) polymer Janus nanoparticles featuring poly(L-lactide) and
poly(styrene-co-aminoethyl methacrylate) faces (adapted from Urban et al).36

assembly.41 Figure 1C shows an example of a Janus particle, in

which one hemisphere is composed of poly(L-lactide) (PLLA)
and the other is composed of poly(styrene-co-aminoethyl
methacrylate) (PS-co-AEMA), allowing for chemical reactions
to selectively occur on one face of the particle.36 A given
nanoparticle can exhibit both shape and chemical anisotropy
(Figure 1B) by employing regiospecic surface functionalization. For example, anisotropic semiconductor nanoparticles
with site-selective attachment of gold nanoparticles on the ends
have been developed for catalyst and sensing applications.35
Figure 2 illustrates the most common and general ideas on
how to control nanoparticle shape; namely through templating,43 vaporliquidsolid extrusion,44 preferential absorption
of ligands and minimization of surface energy,45 defect/
dislocation driven growth,46 and coalescence and oriented
attachment.47 This Perspective highlights insights into the
mechanisms and kinetics of anisotropic nanoparticle growth
with an emphasis on seed-mediated growth, introduces
alternative methods to seed-mediated growth, and addresses
exciting developments and challenges in regiospecic surface
chemistry.
Anisotropic Seed-Mediated Growth. The seed-mediated growth
of anisotropic nanoparticles is a logical extension of the
principles of LaMer for the synthesis of monodisperse colloids.
The well-known LaMer diagram48 (Figure 3A) illustrates the
ideal temporal separation of nucleation (Aii) from growth (Aiii)
and describes the preparation of seed nanoparticles. It starts
with the generation of solute monomers (Ai) building in
concentration through a variety of mechanisms, including: the
decomposition of inert compounds, hydrolysis in organic or
aqueous media, a redox reaction, precipitation by poor solvents,
and the direct reaction of ions or chelates.4850 At some point,
the concentration of monomers (C) surpasses its solubility level
(Cs) and becomes supersaturated. During this prenucleation
stage (Ai), no self-initiated, stable nucleation takes place. In this
supersaturated state, clusters of monomers are continually
forming and dissolving; however, thermodynamically, as seen
through an application of the well-known Kelvin equation,
there is a energetic barrier to the formation of a new solid phase
due to a high surface area to volume ratio.51 A nucleation stage
(Aii) occurs when the monomer concentration surpasses a selfinitiated nucleation concentration (C*min), where clusters of a
sucient size are able to form, overcoming that energetic
barrier, which then favors continued nanoparticle growth over

Figure 2. General ideas on how to control nanoparticle shape. (A)

Examples of the multitude of shapes achievable for noble metal
nanoparticles. Adapted from ref 42 with permission from The Royal
Society of Chemistry, copyright 2009. (B) Assembled cowpea
chlorotic mottle virus virion templates with mineralized cores of
(NH4)10H2W12O42, unstained (left) and negatively stained (right).
Adapted from ref 43 with permission from Wiley, copyright 1999. (C)
Silicon nanowires grown by vaporliquidsolid extrusion in 1 h at 600
C in a 20% disilane and 80% He solution at a pressure of 5 104
Torr. Adapted from ref 44 with permission from Macmillan Publishers
Ltd. (Nature), copyright 2006. (D) Cartoon demonstrating the
preferential binding of the surfactant to the side Au{100} and Au{110}
faces, over the {111} faces at the ends, results in blocking the nanorod
growth at the sides and promotion of nanorod growth at the ends.
Adapted from ref 45 with permission from Elsevier, copyright 2011.
(E) Branched nanotree structures grown by screw dislocation driven
growth. Adapted from ref 46 with permission, copyright 2013. (F)
Single crystal of anatase hydrothermally grown by oriented attachment. Adapted from ref 47 with permission from Elsevier, copyright
1999.

dissolution. Both nucleation and growth occur during this

stage; however, this stage is dominated by rapid nucleation.
Nucleation continues until the monomer concentration drops
back below (Cmin
* ), signaling the end of this stage (Aii) and the
beginning of the growth stage (Aiii), where monomer is
consumed through addition to previously nucleated particles
until the monomer concentration reaches saturation (Cs).48,49
Successful preparation of monodisperse particles in the LaMer
model requires temporal separation of nucleation and growth.
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seed-mediated synthesis has led to the synthesis of low aspect

ratio (25) single-crystalline nanorods utilizing smaller, CTABstabilized seed nanoparticles (1.5 nm) with varying trace
amounts of silver nitrate to control the aspect ratio.1,62,63
Additional empirical developments in synthesis include a
seedless (in situ seed generation) synthesis,64,65 adjustment
of gold and ascorbic acid ratios for gram-scale synthesis,66
milliuidic synthesis,67 identication of a problematic trace
iodide impurity in stock reagents and its synthetic eects,6870
and addition of salicylate compounds,57,71 Gemini surfactants,72
and alternative reducing agents.73
Most anisotropic nanoparticles produced by seed-mediated
growth are kinetically controlled products. Thermodynamic
arguments for morphological control are typically invoked
through preferential adsorption of surfactant molecules on
dierent crystal facets of seed crystals. However, recent
electrochemical experiments on the adsorption of CTAB on
specic crystallographic planes of at gold demonstrate little
thermodynamic preference between crystal faces, despite
dierent levels of bromide adsorption.74,75 It is possible that
sucient dierences in the electronic state of each facet exists
and promote preferential surfactant cation adsorption.74,75
Overall, the extensive body of work on anisotropic seedmediated growth illustrates that there are many subtle avenues
of inuence over the growth kinetics that produce dramatic
eects in product morphology and yield.
The seed-mediated growth of anisotropic nanoparticles is not
limited to gold; the subtle manipulation of kinetically
controlled growth is observed in other materials as well. A
synthesis involving the heating of a polyol with a metal salt
precursor and a polymeric capping agent has been developed to
generate anisotropic metal colloids. The Xia group used this
method to produce bimetallic nanowires of silver on platinum
seeds using ethylene glycol, silver nitrate, and poly(vinylpyrrolidone).7678 Further work with this polyol synthesis has revealed numerous variables in manipulating the
anisotropic growth, including: the metal salt and capping agent
ratio,77 temperature,77 seed concentration,77 seed size distribution,77 seed crystal structure,77,78 seed material,77,78 capping
agent and its molecular weight,78 counterions and their
concentrations,7981 and iron and oxygen impurities.79 Similar
polyol-based routes to anisotropic particles have been observed
for platinum,8284 palladium,8587 gold,85,88 rhodium,89 and
numerous bimetallic systems.76,87,90
Seed-mediated growth has also been combined with
coreduction techniques to create bimetallic nanoparticles.
Notable work by the Skrabalak group with gold and palladium
resulting in two structurally distinct but kinetically related
productsoctopods and concave core@shell nanocrystals
illustrate the importance of careful kinetic control.91 Continued
research on such coreduction techniques has shown the
importance of the ratio of metal precursors,92,93 growth
solution pH,92,94 capping agent concentration,92 seed morphology,95,96 and counterions94 in controlling the morphology of
branched bimetallic nanocrystals. Most interesting in this
system is that despite dramatic changes in morphology as a
function of pH,92,94 little eect on the metal deposition rate is
observed.94
Anisotropic and heterogeneous semiconductor nanocrystals
compose yet another important class of nanomaterials aided by
seed-mediated growth techniques. As with gold, the rst seedmediated semiconductor structures were epitaxially grown,
isotropic core@shell structures.97 Advances in manipulating the

Figure 3. (A) LaMer model for monodisperse nanoparticle formation

* ,
employed in seed nanoparticle formation (Cs, solubility level; Cmin
* , maximum
minimum monomer concentration for nucleation; Cmax
monomer concentration for nucleation; Ai, prenucleation stage; Aii,
seed nucleation stage; Aiii, seed growth stage). (B) Extension of the
* , minimum monomer
LaMer model to seed mediated growth (Cseeds
concentration for nucleation on a seed; Bi, prenucleation stage; Bii,
nucleation stage on a seed nanoparticle; Biii, nanoparticle growth
stage).

Seed-mediated growth involves not only the temporal

separation of nucleation and growth, but quite frequently
their spatial separation into dierent reaction vessels. This
allows for the careful manipulation of growth kinetics and the
morphology and crystal habit of the material produced during
growth (Figure 3B). This spatial separation also allows for the
material precipitated during growth to be of a dierent
elemental composition from the seed material. Similar to the
LaMer diagram, monomers are generated by various methods;
however, ideally monomer concentration remains below the
level required for self-induced nucleation (Bi). The addition of
seed nanoparticles (Bii) allows for the nucleation of the second
material on the seed nanoparticles only, which requires a lower
solution concentration than self-induced nucleation. In practice,
however, the monomer concentration can be high enough for
self-induced in situ generation of new seeds, contributing to
increased polydispersity of the product nanoparticles. When the
seeds and growth material are the same, distinguishing between
intentionally added seeds and in situ seeds becomes impossible.
However, careful control and manipulation of the growth
conditions can avoid in situ seeds with seemingly small changes
leading to anisotropic growth of the material onto the
intentionally added seed nanoparticles (Biii).

Tiny variations in the growth

conditions are important in
determining anisotropy.
One of the rst examples of seed-mediated growth of colloids
was done by Zsigmondy for spherical gold particles.49,52 More
recently, anisotropic gold colloids have been produced via seedmediated growth,53 illustrating that tiny variations in the
growth conditions are important in determining anisotropy in
this type of growth. The earliest protocol for the seed-mediated
growth of gold nanorods employed 3.5 nm citrate-stabilized
gold nanoparticles as seeds added sequentially to three growth
solutions, each consisting of HAuCl4, cetyltrimethylammonium
bromide (CTAB), and ascorbic acid.5456 The aspect ratio of
the rods obtained can be controlled by varying the amount and
size of seeds added, organic additives and cosurfactants,57,58 and
the halide counterion.54,55,5961 The morphological yield of the
penta-twinned nanorods of high aspect ratio (>10) can also be
improved by adjusting the pH.56 Further development of this
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Perspective

morphology of semiconductor nanocrystals98 using seedmediated growth have produced heterogeneous anisotropic
nanoparticles of rod99101 and tetrapod100,101 morphologies.
Morphological control in these semiconductor systems has
been achieved by controlling the seeds crystal phase100,102 or
morphology,103 leading to very dierent nal nanoparticle
morphologies. This work has even been extended to the
synthesis of heterogeneous anisotropic structures consisting of
both semiconductors and metals.35,104,105

similar precursors, surfactants, and solvents, which are all mixed

into the same reaction vessel, and all of the contents are heated.
The elevated temperature leads to the formation of monomers,
which leads to nucleation and nanoparticle growth. Nanoparticle synthesis using the noninjection method has the
advantage of scalability over hot-injection, but the less-rapid
onset of nucleation can increase the polydispersity.114 Like in
the hot-injection method, shape anisotropy can be achieved by
choosing the surfactants such that the crystal faces grow at
dierent rates. Park et al. used the noninjection method to
made anisotropic CdSe nanoparticles with tetrapod and
matchstick shapes.114,115
The preparation of anisotropic oxide nanoparticles is dicult
using sol-gel type syntheses. Sol-gel methods usually rely on the
hydrolysis of precursor compounds into monomers that
coalesce via condensation reactions to form particles. Because
the syntheses are usually conducted at room temperature, the
resultant nanoparticles are typically amorphous116 and the
adsorption of monomers and particles is not directed but
occurs isotropically, as in the Stober method to synthesize silica
nanospheres.117 High temperature syntheses, such as hydrothermal and solvothermal methods, result in more crystalline
nanoparticles, for which kinetic shape control (such as that
used for seed-mediated growth) can lead to anisotropic
nanoparticles.118,119
Templated synthesis methods can also be used to prepare
anisotropic nanoparticles. Hard templates can be rigid
nanostructures that the desired anisotropic nanoparticles are
grown in, such as the porous membranes described by Martin
in which conductive nanocylinders were grown.120 Anisotropic
nanoparticles can also serve as hard templates on which other
materials can be grown: Obare et al. demonstrated the growth
of polystyrene and silica shells on long gold nanorods,121 and
Abadeer et al. successfully grew silica shells on short gold
nanorods.51 The hard template acts to direct the shape, even
though the materials being synthesized are isotropic. Hard
particle templates can be selectively dissolved away, yielding
hollow nanoparticles of the shell material.121 In soft template
methods, microemulsions and micelles act as the templates.
The use of soft templates often takes advantage of dierences in
the solubility of precursor and monomer compounds between
the templating droplets and the continuous phase. Although
soft templates are often spherical, Kujik et al. used a related
technique to synthesize silica nanorods.122 Cryogenic transmission electron microscopy (Cryo-TEM) images showing
silica nanorod growth over time are shown in Figure 4. To

There are many subtle avenues of

inuence over the growth
kinetics that produce dramatic
eects in product morphology
and yield.
Alternative Synthetic Techniques for Anisotropic Nanoparticles.
Besides seed-mediated growth, a number of other techniques
have been developed for the shape-controlled synthesis of
metallic and semiconducting nanoparticles. In the case of gold
nanorods, various methods, including photochemistry,106
electrochemistry107 and sonochemistry,108 have been applied
to reduce the Au3+ ions to Au0, replacing molecular reducing
agents and seeds. As in the seed-mediated growth of gold
nanorods, CTAB directed the anisotropic growth and Ag+
controlled the aspect ratio in these examples.106,107 Single
crystalline gold nanobelts have also been successfully
synthesized in the presence of -D-glucose and under
ultrasound irradiation to form reducing radicals.108
The hot-injection method has been particularly important for
synthesizing anisotropic semiconductor nanocrystals. This
method has been popular since Murray and co-workers
demonstrated the utility of the hot-injection method for the
synthesis of cadmium chalcogenide quantum dots in the early
1990s.109 To make nanoparticles using the hot-injection
method, precursors are injected into a hot solution of
surfactants in a solvent. The elevated temperature causes the
precursors to react or decompose to form the atomic or
molecular monomers that form the nanoparticles. High initial
monomer concentrations induce the nucleation of seed
particles, followed by a phase during which the leftover
monomers add onto the seeds, leading to the growth of
nanoparticles.110 By choosing surfactants and cosurfactants
judiciously, Peng et al. demonstrated hot injection methods
could be used to grow anisotropic nanoparticles.98 As
mentioned earlier, the mechanism of anisotropic nanoparticle
growth is typically governed by kinetics; anisotropic shapes are
not the most thermodynamically favorable products.110,111 Yin
and Alivisatos have suggested that the anisotropic growth of
CdSe nanorods could be due to the stabilizing eects of organic
ligands binding selectively to certain crystal faces, causing
slower growth relative to other faces.110 Peng suggested that
anisotropic growth may also be attributed to the chemical
potential of the monomers: the higher their chemical potential,
the faster the growth will be of high energy faces relative to low
energy faces.112 The dependence of particle morphology on the
concentration of the monomers lends support to this
idea.112,113 However, explaining the initial symmetry-breaking
events that lead to anisotropic growth remains a challenge.111
Closely related to the hot-injection method is the noninjection, or heat-up method.114 The noninjection method uses

Figure 4. Cryo-TEM images of silica nanorods after (A) 30, (B) 60,
and (C) 120 min of growth. Adapted from ref 122 with permission,
copyright 2011.

make these rods, the authors rst prepared a polyvinylpyrrolidone- and sodium citrate-stabilized microemulsion of water in
pentanol. When tetraethyl orthosilicate was added, the
hydrolyzed form partitioned to the aqueous phase, so the
condensation reactions to form silica occurred at the surface of
the water droplets. Because the condensation reactions took
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Perspective

rods.126129 These chemically anisotropic rods thus have

activated ends that can direct further chemistry or
interparticle interactions.

place only on one side of the water droplet, the growth of the
silica nanorods was anisotropic.
Oriented attachment is another method for growing
anisotropic particles, in which small nanocrystals serve as
building blocks that self-assemble into complicated structures.
Due to the high surface-to-volume ratio and high surface energy
of the nanocrystals, the assembly of the crystals is favored.
Because the facets energies tend to be dierent, often due to
preferential binding of ligands, the assembly can be oriented
and anisotropic architectures can be achieved. Baneld and coworkers demonstrated the successful synthesis of a 1D structure
from the attachment of TiO2 nanocrystals along the (001)
direction, where the facets have the highest surface energy.47
Similar methods have also been applied to synthesize gold
nanowires assembled from nanocrystals with a diameter of
around 2 nm.123 On the basis of a detailed electron-microscopy
study, the nanocrystals were found to align along the (111)
direction, followed by a side-smoothing diusion process to
achieve nanowires up to 1 m long.
Regiospecif ic Surface Chemistry. Nanoparticles with shape
anisotropy can be further modied to create chemical
anisotropy. Many anisotropic growth mechanisms leave
multiple exposed crystal facets on a single nanoparticle. As in
the oriented self-assembly mentioned above, the reactivities of
the exposed facets can be exploited to direct regioselective
chemistry on the surface of the particle. A basic example of
regiospecic chemistry on anisotropic nanoparticles was shown
by Banin and co-workers through the deposition of metallic
gold onto the tips of CdSe nanorods and tetrapods.104 In a
series of groundbreaking experiments, gold salt was reduced
onto CdSe nanoparticles with a clear preference for the tips
rather than the sides. This phenomenon was further expounded
upon by Kudera et al., who achieved control of PbSe growth on
one or both tips of CdS and CdSe nanorods by a simple
injection of PbSe precursors.103 In both cases, the diering
crystal facets allowed for preferential deposition of metal atoms
on the ends, rather than the sides. Transmission electron
microscopy (TEM) imaging was used to provide clear
conrmation of metal overgrowth, whereas optical absorbance
experiments provided ensemble measurements that showed a
distinct dierence in optical properties of materials with and
without deposited metal.
Although deposition of metallic salts provides an inorganic
route to postsynthetic modication, it is also desirable to assign
organic functionality to certain locations of an anisotropic
particle. Much research eort has been dedicated to controlling
the placement of functional ligands on gold nanorods, in
particular, because CTAB-stabilized gold nanorods have an
inherent, sterically driven advantage in anisotropic functionalization. Because there is a higher radius of curvature at the
nanorods ends, the arrangement of surfactant molecules is
expected to be less dense. Whereas CTAB is tightly packed at
the rods longitudinal facets, the end faces are more chemically
accessible. The rods ends are indeed more reactive to cyanide
dissolution, presumably because of the paucity of CTAB
there.124 Interestingly, this anisotropic eect seems to be
unique to CTAB-like surfactants: rods passivated by a bilayer of
phospholipids appear to have a fairly uniform, densely packed
bilayer, even at the highly curved ends, perhaps a function of
the lipids geometry.125 CTABs presumed uxionality at the
ends appears to be a fortuitous blessing because many scientists
have taken advantage of the increased accessibility to adsorb
functional thiols regioselectively to the tips of gold nano-

Chemically anisotropic rods thus

have activated ends that can
direct further chemistry or
interparticle interactions.
Self-assembly behavior, usually visualized by TEM and
ultravioletvisible (UVvis) absorption spectral changes, is
often the primary evidence for successful anisotropic
functionalization. One such example is in our group, where a
biotin-disulde molecule was synthesized and placed on the
ends of gold nanorods.130 Because of the tight CTAB packing
along the sides of the rod, the disulde was hypothesized to
adsorb only onto the tips. Further incubation with the protein
streptavidin, which can bind multiple biotin molecules, led to
favorable end-to-end assembly of the rods. In a similar fashion,
Zhen et al. showed that the tips of gold rods could be
functionalized with a thrombin-binding aptamer, and the
protein thrombin could be used to self-assemble the rods
end-to-end.131 There are many such examples of endactivated rods, but it is much more dicult to exclusively
activate the sides of the rods, which are typically coated with
CTAB, which is functionally less interesting. Xu et al. cleverly
solved this issue by deactivating the ends with nonreactive
ligands. They rst treated the CTAB rods with small amounts
of a thiolated nontarget DNA strand, which attached to the
ends and blocked them from further reaction. Then, they added
active DNA thiols, which were forced to adsorb onto the sides
of the rods, presumably penetrating the CTAB bilayer. After
incubating the rods with complementary DNA-functionalized
gold nanospheres, the authors observed by TEM that the
spheres attached almost exclusively to the sides.132 Their study
illuminates the importance of the ratio of thiol to nanorods; at
low concentrations of thiol, the ligand attaches primarily to the
ends, but high concentrations preclude any type of
regioselective functionalization.
In an experiment that exploits the enhanced reactivity of
loose regions of the CTAB bilayer and exposed parts of the
metal surface, Wang and co-workers developed methods to
selectively deposit metals such as platinum and palladium onto
the ends or sides of gold nanorods (Figure 5).133 To achieve
this, the authors rst coated either the ends or sides of the rods
with silica. Silica coating of the rods ends was realized through
preferential adsorption of tetraethyl orthosilicate (TEOS) on
the ends, whereas side coating involved an initial end-blocking
step with thiolated PEG, which forced TEOS to hydrolyze
along the rods sides. Following this, anisotropic overgrowth of
metals was performed by simply reducing metal salt on the
exposed nanorod surfaces. Successful metal overgrowth was
shown by TEM, as silica and gold atoms under an electron
beam will have clear contrast dierences; furthermore, the
optical properties of the gold nanorods were changed as the
plasmon was perturbed by the presence of deposited metals,
which was shown in the optical absorbance spectra.
In a large collection of work, Kumacheva and colleagues have
shown that even bulky, hydrophobic polymers can be axed
preferentially to gold nanorod ends. By using a thiol-terminated
polystyrene to target the ends, the authors created triblock
nanorods, the plasmonic analogue of amphiphilic block
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sensing. The use of anisotropic noble metal nanoparticles in

SERS is preferred because upon light irradiation, electromagnetic elds at tips in anisotropic particles are orders of
magnitude higher than in isotropic nanoparticles. It would be
particularly noteworthy to be able to use end-to-end dimers of
plasmonic nanorods with nanoscopic space between them for
SERS applications. This type of assembly would generate an
even more enhanced electric eld, specically at the
intersection between the tips. However, molecules of interest
would need to have access to that space to induce a highly
enhanced Raman signal. A few researchers have reported the
preparation of nanoparticle dimers,140,141 but dimers of
anisotropic nanoparticles are dicult to prepare in high yields.
More often, extended lengths of self-assembled nanorod chains
(larger than dimers) are prepared and result in variation in the
strength of the electromagnetic eld and SERS eect.142 With
better knowledge and control of anisotropic surface coatings
and anisotropic nanoparticle dimers, researchers will be able to
demonstrate even greater potential in SERS applications.

Figure 5. Routes of metal overgrowth. (A) Au nanorod capped with a

CTAB bilayer. (B) Nanorod coated with silica at the ends. (C)
Nanorod overgrown with a metal on the side surface. (D) Au nanorod
bonded with mPEG-SH at the ends. (E) Nanorod coated with silica on
the side surface. (F) Nanorod overgrown with a metal at the ends.
Reproduced from ref 133 with permission from Wiley, copyright 2013.

polymers.134 Their amphiphilic nature aorded the rods

interesting self-assembly properties and in various solvent
mixtures they formed chains, rings, bundles, or spheres. Tuning
the molecular weight of the polystyrene altered the nal
morphology of the supramolecular assemblies. In subsequent
studies, similar amphiphilic rods were treated as monomers that
could be polymerized in a step-growth-like mechanism into
supramolecular plasmonic chains.135,136 The rates and degrees
of polymerization, and the bond angles and lengths between
monomers, were characterized and controlled in an elegant
extension of the analogy. In one example of chain length
control, patchy Au/Fe3O4 nanospheres with polystyrene and
polyethylene glycol domains served as colloidal chain stoppers,
as the reactive polystyrene patch attached to the growing
chain, and the exposed polyethylene glycol halted further
hydrophobically driven polymerization.137 Clearly, amphiphilic
nanorods show promise as a way to achieve ne control in
bottom-up nanoassemblies. Theoretical studies have aimed to
generalize the design rules of these polymer-tethered rods for
further insight.138,139

AUTHOR INFORMATION

Corresponding Author

*E-mail: murphycj@illinois.edu.
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
We thank the National Science Foundation (CHE 1306596)
for funding.
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Amphiphilic nanorods show

promise as a way to achieve ne
control in bottom-up
nanoassemblies.
Future Directions. Nanoparticles of noble metals, semiconductors, and soft materials have become ubiquitous in
research studies, and their applications range across elds such
as cancer therapy, disease detection, and energy generation.
The advent of facile, reproducible, and scalable synthesis
techniques for anisotropic nanoparticles has extended these
potential applications even further. By using dierent
reactivities of crystal facets and packing of ligand layers, the
eld has gained another degree of control for the self-assembly
and application of nanoparticles. However, much more work
needs to be done in order to fully characterize and exploit this
mechanism of control. One key to better understanding such
coatings is the ability to identify and quantify the ligands on a
nanoparticle surface as a function of position, a challenge due to
the small size of nanoparticles and polydispersity often present
in as-synthesized nanoparticle dispersions.
Surface enhanced Raman spectroscopy (SERS) is a
technique that has garnered much interest for molecular
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