Journal of Colloid and Interface Science 348 (2010) 29–36

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Journal of Colloid and Interface Science

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Achieving high-purity colloidal gold nanoprisms and their application

as biosensing platforms
Zhirui Guo a, Xu Fan b, Lianke Liu a, Zhiping Bian a, Chunrong Gu a, Yu Zhang b, Ning Gu b, Di Yang a,*,
Jinan Zhang a,**
a
Institute of Cardiovascular Disease, The First Affiliated Hospital of Nanjing Medical University, Nanjing 210029, China
b
State Key Laboratory of Bioelectronics and Jiangsu Laboratory for Biomaterials and Devices, Southeast University, Nanjing 210096, China

a r t i c l e i n f o a b s t r a c t

Article history: Gold nanoprisms with average edge size of 140 nm and thickness of 8 nm were achieved in high-
Received 9 December 2009 purity (97%) by exploiting the electrostatic aggregation and shape effects through a modified seed-
Accepted 9 April 2010 mediated approach. The proposed strategy lies in the dramatically different stability and aggregation
Available online 18 May 2010
potential between the produced gold nanoprisms and spherical gold nanoparticles, which can be modu-
lated by varying the anion concentration in the reaction solution. Hence, the gold nanoprisms spontane-
Keywords: ously aggregated into precipitate whereas most of the spherical ones were still kept in the solution.
Gold
Moreover, this strategy is also flexible enough that ultra-small gold nanoprisms with average width less
Nanostructure
Electrostatic interaction
than 50 nm can be collected in good-purity. The structure and optical properties of these nanoprisms
Anisotropic shape have been studied by TEM, SAED, XRD and UV–vis–NIR spectroscopy, respectively. These high-purity col-
Biosensor loidal gold nanoprisms exhibit remarkably enhanced surface plasmon resonance (SPR) as well as strong
near-infrared absorption. Furthermore, we have also investigated their potential for biosensing based on
the sensitive changes of SPR band induced by the antibody–antigen recognition events. The experimental
results clearly suggest that gold nanoprisms can be a promising nanostructured system for plasmonic
sensor applications.
Ó 2010 Elsevier Inc. All rights reserved.

1. Introduction prisms with thickness below 100 nm are commonly categorized

Finely controlling the shape and size of metal nanostructures
has become an active area of research because the optical, electri-
cal, magnetic and catalytic properties of metal nanostructures are
strongly dependent on their shape and size [1,2]. Thanks to the ef-
forts of the worldwide research groups, multiplex shaped metal
nanostructures, including icosahedras [3], decahedrons [4], octahe-
drons [5], bipyramids [6], cubes [7], rods [8], wires [9], belts (rib-
bons) [10], and other complex shapes such as multipods [11] or
stars [12], have been synthesized during the last decade. In recent
few years, gold and silver nanoprisms (nanoplates) have attracted
great interest because of their unique optical properties known as
localized surface plasmon resonance (SPR) and promising applica-
tions in photoluminescence [13], surface-enhanced Raman scatter-
ing [14], optical coating [15] and near-infrared (NIR) light
absorbing [16]. In general, noble metal nanoprisms are a class of
two-dimensional structures with parallel top and bottom and a
nanoscale thickness. Although micrometer-sized gold or silver
* Corresponding author. Fax: +86 25 83738572.
** Corresponding author. Fax: +86 25 83738572.
E-mail addresses: diyang@njmu.edu.cn (D. Yang), jinanzh506@yahoo.com
(J. Zhang).
as nanoprisms, they have not presented the unique optical proper-
ties associated with their colloidal analogs [17]. Furthermore, the
solution of micrometer-sized prisms is prone to precipitate due
to their large size, limiting the applications in solution phase. Up
to date, a variety of synthetic strategies, such as photochemical,
thermal and biological routes, have been explored to prepare bulk
quantities of colloidal silver nanoprisms [18]. However, most of the
synthesized gold nanoprisms have edge lengths ranging from sub-
micrometer to tens of micrometer [19]. A few reports concerned
with small gold nanoprisms often generate large amounts of other
shaped structures difficult to high-efficiently separate [20]. Be-
cause gold is much more air-stable and biocompatible than silver,
the achievement of colloidal gold nanoprisms with high-purity are
quite desirable for expanding the application field which is pres-
ently unattainable by silver nanoprisms.
Recently, Ha et al. reported the synthesis of small gold nanop-
risms by a seed-mediated, cetyltrimethylammonium bromide
(CTABr)-assisted approach [21]. In their work, a proper amount
of iodide ion (I) was introduced into the reaction solution to re-
press the crystal growth along the h1 1 1i direction of gold, result-
ing in basal {1 1 1} facets bounded triangular gold nanoprisms.
However, the final reaction mixture is still accompanied with a
large fraction (55%) of spherical nanoparticles. In this paper we

0021-9797/$ - see front matter Ó 2010 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2010.04.013
30 Z. Guo et al. / Journal of Colloid and Interface Science 348 (2010) 29–36
describe our recent research on the stability and aggregation
potential between the gold nanoprisms and the spherical gold
nanoparticles produced by the above-mentioned seeding synthetic
system. It is found that colloidal gold nanoprisms with an excellent
purity (97% in number density) can be achieved from the in situ
reaction mixtures by exploiting the electrostatic aggregation effect,
without conventional centrifugation or filtration [21,22]. The pre-
sented strategy is effective while flexible enough that ultra-small
gold nanoprisms with average edge length less than 50 nm can
be obtained in good-purity. Moreover, their SPR properties is
studied and the potential as biosensing platforms using biomarker
human cardiac troponin I as a protein sensing model is
investigated. The experimental facts clearly demonstrate that gold
nanoprisms can be a promising candidate for plasmonic sensor
applications.
2. Materials and methods
2.1. Materials
Cetyltrimethylammonium bromide (CTABr)1 and Poly(styrene-
sulphonate) (PSS, Mw 70,000) were purchased from Sigma.
Tris(hydroxymethylamino)methane was received from Amresco.
HAuCl4, sodium citrate, NaBH4, L-ascorbic acid (AA), NaOH, KI,
K2CO3 and NaCl were all purchased from Shanghai Sinopharm Chem-
ical Reagent Co. Ltd. (China). All reagents were used as received
without further purification. Millipore-quality water (18.2 MX cm)
was used throughout the experiments. Tris Buffered Saline (TBS buf-
fer) was prepared by dissolving 2.42 g tris(hydroxymethylami-
no)methane and 8.8 g NaCl in 900 mL of water. The solution was
titrated with 1.00 M HCl until a constant pH value of 8.2 was ob-
tained, and then water was added to receive a 1000 mL stock solu-
tion. Human cardiac troponin I (cTnI) from human myocardium
muscle and the anti-human cTnI antibodies used in the experiment
were obtained from Research Institute of Cardiovascular Disease of
First Affiliated Hospital of Nanjing Medical University. All the glass-
ware was cleaned by aqua regia (HCl:HNO3 in a 3:1 ratio by volume)
and rinsed with water prior to the experiments.
2.2. Synthesis of gold seeds
Gold seeds were synthesized by reducing 0.4 mL of 25 mM
HAuCl4 with 1 mL of ice-cold 0.1 M NaBH4 with vigorously stirring.
The reduction was done in the presence of 1 mL of 10 mM sodium
citrate and 37.6 mL of water. Upon addition of the NaBH4, the solu-
tion turned a reddish orange color, indicating the generation of
gold nanoparticles. The resulting solution was continually stirred
for 2 min. The seed solution was allowed to stand for at least 2 h
to ensure the complete hydrolysis of unreacted NaBH4. The gold
seeds exhibited a SPR peak at 507 nm, and had an average diameter
of less than 5.0 nm (see Supporting information).
2.3. Growth and achievement of gold nanoprisms with high-purity
An initial reaction mixture of gold nanoprisms was prepared by a
one-step seed-mediated, iodide ion- and CTABr-assisted approach
with new modifications [21,22]. Typically, a 100 mL of growth solu-
tion containing 0.25 mM HAuCl4 and 0.05 M CTABr was prepared in
a 150 mL beaker. To this solution was added 55 ll of 0.1 M KI,
1
Researchers have recently reported that the iodide ion impurity concentrations in
CTABr vary from different manufacturers and the range is from less than 2.75 ppm to
840 ppm [44]. In current work, the needing [I] is greater than or equal to 50 lM.
Thus to eliminate the side effects by the iodide ion impurity in CTABr, we have chosen
Cat No: H6269 from Sigma, which contains the least iodide concentration (0.37 lM in
our reaction solution) among the CTABrs.
0.55 mL of 0.1 M AA and 0.55 mL of 0.1 M NaOH (NaOH is used to
deprotonate ascorbic acid for more effective reducibility) in turn
and the resulting solution as growth solution was stirred gently.
The orange color of the gold salt in the CTABr solution disappeared
when AA was added, due to the reduction of Au3+ to Au+. The growth
of gold nanoprisms was initiated by adding 0.1 mL of the seed solu-
tion to the growth solution. After the addition, the color of the
growth solution changed from clear to light red, and then turned
to deep claret-red over a period of 30 min. The reaction solution
was kept at 30 °C and left undisturbed during the whole aging peri-
od. There were two ways for achieving high-purity colloidal gold
nanoprisms: when the concentration of CTABr was greater than or
equal to 0.05 M, the reaction mixture was aged without disturbance
for 24 h; when the concentration of CTABr was lesser than 0.05 M,
the reaction mixture was aged for 12 h, followed by adding NaCl
until the sum of [Cl] and [Br] reached 0.2 M. After this, the reaction
mixture was aged for another 12 h. Most of gold nanoprisms
deposited on the bottom of the beaker during the aging period, and
were easily collected by pouring out the supernatant. These gold
products were redispersed to the colloidal solution for further
characterization.
2.4. Conjugation of gold nanoprisms to anti-cTnI antibodies
The high-purity nanoprisms in the CTABr solution was centri-
fuged to get rid of the extra free CTABr molecules. The nanoprism
surface was coated with PSS polyelectrolyte before antibody conju-
gation. This was done by adding 2.4 ml of 2.5 mg/mL PSS to 30 mL
nanoprism solution with an optical density of 1.0 at the long wave-
length absorption maximum. The reaction was continued for about
15 min to complete the coating process. The extra PSS in solution
was separated by centrifuging the prism solution at 3000 rpm.
The pellet was redispersed in water and titrated with 0.2 M
K2CO3 to reach a pH value of 8.2. Then the PSS capped nanoprism
solution was mixed with an excess amount of anti-cTnI antibody
(50 lg/mL) to react for 30 min. The nanoprisms conjugated with
the anti-cTnI antibodies were centrifuged twice and redispersed
into TBS buffer to form a stock solution with an optical density
of around 1.0 at the long wavelength absorption maximum (wash-
ing buffer: 1% bovine serum albumin in TBS buffer to preclude non-
specific binding).
2.5. Binding of cTnI to anti-cTnI antibody conjugated gold nanoprisms
In each experiment, 1.0 mL of anti-cTnI antibody conjugated
gold nanoprisms was added to a fixed amount (10, 50, 100, 300,
500, 700 and 1000 ng) of cTnI at room temperature under vortex
mixing. The resultant mixture was incubated for 15 min before
recording with 2802S (UNICO) spectrophotometer.
2.6. Characterization
The morphologies of the gold products were characterized by
TEM (JEM-2000EX, JEOL) operating at 120 kV. The high-resolution
TEM (HRTEM) image and the selected area electron diffraction
(SAED) pattern were recorded on a JEOL JEM-2100 transmission
electron microscope operating at 200 kV. The XRD analysis of the
gold samples was carried out by using an X-ray diffractometer
(D/Max-RA, Rigaku) with Cu Ka radiation at room temperature.
The sample was deposited onto a silicon wafer and scanned in
the 2h range of 30–90°. The Fourier transform infrared (FTIR) spec-
tra were measured on a Magna FTIR-750 (Nicolet) spectrometer
and the vacuum-dried samples were made in the form of KBr pel-
let. The UV–vis–NIR absorption spectra of the gold samples were
collected by a UNICO 2802S spectrophotometer in a wavelength
range from 300 to 1100 nm.
 Z. Guo et al. / Journal of Colloid and Interface Science 348 (2010) 29–36
3. Results and discussion
The key point of our strategy lies in the different stability and
aggregation potential between spheres and prisms. In a typical
experiment conducted in the presence of 0.05 M CTABr, the growth
of gold nanostructures has been monitored by UV–vis–NIR spec-
troscopy in real time. As shown in Fig. 1, two distinct SPR bands
emerge within 2 min after seed addition. The first one appears at
532 nm and its intensity increases with time, which indicates that
a large number of spherical gold nanoparticles are produced
accompanying the growth of nanoprisms. The second band initially
appears at 930 nm and this band red-shifts with the increase of the
intensity as the growth continues, which indicates the presence of
gold nanoprisms and the band shifts to NIR region could mirror an
increase in edge length [23]. After 10 min, the intensity of the SPR
band assigned to nanoprisms reaches its maximum and, unexpec-
tly, begins to decrease gradually. At the meantime, the SPR band of
spherical ones still keeps increasing in intensity. At the end of the
aging period, the SPR band of gold nanoprisms disappears com-
pletely and only the SPR band of spherical ones is left, which re-
veals that the generated gold nanoprisms are much less stable
than spherical ones and most of them aggregate spontaneously
into precipitation. This precipitation can be collected easily by
pouring out the supernatant. In particular, these as-obtained gold
nanoprisms are prone to form colloidal solution by redispersion
in water. As shown in Fig. 2a and b, both the spherical nanoparti-
cles in supernatant and the triangular nanoprisms in precipitate
have a relatively narrow size distribution. The average diameter
of spherical ones is 30 ± 2 nm. The nanoprisms are 140 ± 25 nm
in size along their longest edge and 8 ± 2 nm in thickness. As
counted from TEM images, the number density of the collected
nanoprisms is about 97%. Fig. 2c presents a typical HRTEM image
of a prism with its basal plane lying on the carbon-coated copper
grid. The well-resolved fringe pattern reveal the single crystalline
of the gold product, which is also confirmed by the electron diffrac-
tion pattern (Fig. 2d) and the hexagonal symmetry of the diffracted
spots suggests that the base faces of the gold nanoprism is
bounded by {1 1 1} facets [19,20]. The fringes with a lattice spacing
of 0.25 nm corresponds to the forbidden 1/3 {4 2 2} reflections
[24], which has been ascribed to the existence of stacking fault par-
allel to the {1 1 1} facets [25]. At present time, we have not yet ob-
served the stacking faults from these very thin prisms. However, in
Fig. 1. In situ UV–vis–NIR absorption spectra recording the growth process of gold
nanoprisms after seed addition.
31
the control experiment without adding I, quite a few of ellipsoids
instead of prisms were produced because of the quick growth rate
along the h1 1 1i direction of gold and we did discover the presence
of stacking faults extending across the entire ellipsoid (Fig. 2e).
Fig. 2f is the typical powder XRD pattern of the as-collected gold
nanoprisms. The overwhelmingly intensive diffraction located at
2h = 38.12° corresponds to the {1 1 1} facets of face-centered cubic
gold (JCPDS No. 4-0784), while peaks belonging to other facets are
quite weak. These observations indicate their basal {1 1 1} facets
typically lie flat on the supporting surface.
It is well-known that colloidal gold usually exhibit an intense
color because that the SPR frequency locates at the visible part of
the spectrum. Fig. 3a and b show the photographs of the resulting
spherical nanoparticle solution and the nanoprism solution,
respectively. The supernatant consisting of spherical gold nanopar-
ticles is commonly claret-red. Interestingly, the high-purity gold
nanoprism solution exhibits green in color due to the different
SPR frequency. It is also documented that the shape and the size
of gold nanostructures play important roles in determining the
number, position, and intensity of SPR modes [2,26]. As shown in
Fig. 3c and d, the supernatant mainly containing spherical gold
nanoparticles exhibits a single SPR band around 530 nm, while
the gold nanoprism solution presents two SPR bands as a result
of their high anisotropy in shape: one weak peak located at
760 nm and another strong, sharp peak centered at 1055 nm,
which can be assigned to the in-plane quadrupole resonance and
the in-plane dipole resonance, respectively [23]. The absence of
any feature of this spectrum in the range of 500–600 nm is obvious,
which implies that the amount of spherical particles is very mini-
mal, providing another piece of evidence for the high-purity of
these gold nanoprisms.
Further investigation reveals that the significant aggregation of
gold nanoprisms occurs only when the concentration of CTABr is
greater than or equal to 0.05 M. The less CTABr is employed, the
less precipitation of gold nanoprisms is observed. In a control
experiment using 0.0125 M CTABr, the produced gold nanostruc-
tures were stable enough that no aggregation was observed. The
corresponding UV–vis–NIR spectrum exhibits the weak quadru-
pole and strong dipole resonance bands, confirming the presence
of plentiful gold nanoprisms (Fig. 4a). Subsequent TEM observation
reveals that these gold nanostructures are mainly triangular
nanoprisms accompanied with spherical ones (Fig. 5a). To achieve
high-purity gold nanoprisms at a lower concentration of CTABr, we
made the effort by adding NaCl instead of CTABr to the reaction
mixture in order to increase the ionic concentration (detail de-
scribed in Section 2.3). The experimental results clearly indicate
that the aggregation and subsequent precipitation of the gold
nanoprisms takes place after introducing NaCl (Figs. 4b and 5b)
whereas the spherical ones are still kept in the solution (Fig. 4c).
What is the reason for the significantly different stability be-
tween spherical nanoparticles and nanoprisms? Generally, the sta-
bility of gold nanostructures solution by the CTABr-assisted
approach is dominated by two key factors: electrostatic repulsion
between the CTA+ bilayer along the gold surface and the steric
exclusion, both of which attribute to the cationic surfactant CTABr
[21,27–29]. Meanwhile, the anions in the reaction solution, such as
Br, would electrostatically bind to the cationic surface of the gold
nanostructures and the overall positive charge of the gold nano-
structures decreases. By partially shielding the positively charged
gold surface with Br, the electrostatic repulsion among the gold
nanostructures is decreased. Once the concentration of Br is high
enough that the decrease of the positive charges approximates a
critical point, the effect of electrostatic repulsion could be over-
come, thus inducing the gold nanostructures to reach a close dis-
tance in which aggregation might occur. Similarly, post-adding
anions (such as Cl) in the solution with a lower concentration of
32 Z. Guo et al. / Journal of Colloid and Interface Science 348 (2010) 29–36

Fig. 2. TEM images of the gold nanostructures obtained in: (a) supernatant and (b) precipitate, respectively; initial [CTABr] is 0.05 M and aging time is 24 h. The inset in panel
b shows a stack formed by gold nanoprisms standing perpendicularly to the TEM grid, which allows the precise measurement of their thickness. Scale bar = 20 nm. (c) HRTEM
image and (d) SAED pattern of a triangular gold nanoprism. The spots marked using box, circle and triangle correspond to 1/3 {4 2 2}, {2 2 0} and {4 2 2} diffractions,
respectively. (e) Gold nanoellipsoids obtained in the absence of I. The stacking faults in the ellipsoids are labeled by arrows. (f) XRD pattern taken from the as-collected gold
nanoprisms.

Fig. 3. Digital photographs of: (a) spherical gold nanoparticles in supernatant and Fig. 4. UV–vis–NIR absorption spectra of the reaction mixture before (a) and after
(b) as-collected gold nanoprisms in water, respectively. (c) and (d) show the (b) treatment by adding NaCl. (c) Spectrum of as-collected gold nanoprisms
corresponding UV–vis–NIR absorption spectra of (a) and (b), respectively. solution; initial [CTABr] is 0.0125 M.

CTABr is also able to trigger this electrostatic aggregation. On the minimal contact with any shaped particles. However, for nanop-
other hand, the shape effect of the gold nanostructures is another risms, their two-dimensional, nearly zero-curvature geometry
important factor in effecting their aggregation potential. For spher- leads to a maximal contact with each other. Thus, nanoprisms hold
ical nanoparticles, their high-curvature geometry allows to have a much higher aggregation potential than spherical ones when the
 Z. Guo et al. / Journal of Colloid and Interface Science 348 (2010) 29–36 33

Fig. 5. TEM images of: (a) reaction mixtures consist of spherical gold nanoparticles and gold triangular nanoprisms and (b) redispersed gold triangular nanoprisms. Initial
[CTABr] is 0.0125 M.

positively charged gold surfaces are largely shielded by the con-

centrated anions. As a result, the aggregation and subsequent sed-
imentation of gold nanoprisms occurs directly while keeping most
of the spherical ones in solution. Upon dispersing the precipitate of
gold nanoprisms by water, the anions binding on the cationic gold
surface would undergo a dissociation process to the solution until
diffusive equilibrium, which recovers the function of CTA+ bilayer
and allows these gold nanoprisms to form colloid again (Fig. 6).
In addition, it has been noticed that when there is no extra CTABr
in the solution, these gold nanoprisms undergo a gradual shape
reconstruction process arising from the high-energy sharp corners
of these thermodynamics-unfavored nanostructures [30]. This pro-
cess results in blunted edges of gold nanoprisms and dramatic blue
shift of their SPR band by several hundred nanometers (see Sup-
porting information). Hence it is highly recommended that the
as-collected gold nanoprisms should be stored in 5–10 mM CTABr
solution for maintaining their shape as well as optical characters.
The presented strategy is also flexible and effective for collect-
ing much smaller gold nanoprisms in good-purity. In our further
research, the growth of gold nanoprisms with the edge size of less
than 100 nm has been developed by increasing the initial amount
of seeds and I while keeping other synthetic parameters constant.
As shown in Fig. 7a, the UV–vis–NIR spectrum of the resulting reac-
tion mixture (curve1) reveals that the SPR band maximum of the

Fig. 7. (a) UV–vis–NIR absorption spectra of the reaction mixture before (curve 1)
and after (curve 2) treatment using NaCl. Curve 3 shows the spectrum obtained
from the aqueous suspension of as-collected gold nanoprisms. (b) TEM image of the
as-collected gold nanoprisms. (c) Digital photograph of the aqueous suspension of
gold nanoprisms. Initial [CTABr] is 0.05 M. The amount of iodide ion and seed is five
times of that in typical samples, respectively. The reaction mixture was kept for
12 h, followed by adding NaCl until the sum of [Cl] and [Br] reached 1.0 M. Then
the solution was aged for another 12 h before collecting the gold nanoprisms.

Fig. 6. A schematic illustration of achieving high-purity colloidal gold nanoprisms nanoprisms dramatically blue shifted to 750 nm when the addition
through a seed-mediated, iodide ion- and CTABr-assisted synthetic system. of seeds and I are five times of that in typical samples. Subsequent
34 Z. Guo et al. / Journal of Colloid and Interface Science 348 (2010) 29–36
spectroscopy observation clearly reveals that the sedimentation of
most of the gold nanoprisms after introducing sufficient NaCl
(curves 2 and 3 in Fig. 7a). TEM observation displays these as-col-
lected gold nanoprisms hold an average edge size of less than
50 nm (Fig. 7b) and their aqueous solution exhibits blue in color
due to their ultra-small size (Fig. 7c).
It has experimentally confirmed that in-plane plasmon oscilla-
tion of silver nanoprisms is extremely sensitive to environmental
or aggregative changes [31–33]. Therefore, silver nanoprisms could
be envisaged as plasmonic platforms for sensing applications.
Based on the similarity of SPR modes in shape and intensities be-
tween gold and silver nanoprisms by theoretical studies [23], it is
reasonably believed that gold nanoprisms also hold the capability
for plasmonic sensing platforms. In this research we chose human
cardiac troponin I (cTnI), a highly specific biomarker in the clinic
diagnosis of myocardial infarction [34], as a protein sensing model
based on the SPR changes of gold nanoprisms in solution. To the
best of our knowledge, there have no previous reports on using
noble metal nanoprisms as plasmonic biosensors.
Although there are several publications have demonstrated that
the washed CTABr-capped gold nanostructrues are nontoxic and
able to conjugate antibody protein directly [35,36], our experi-
ments reveal that the CTABr on the gold nanoprisms indeed cause
the denaturation and sedimentation of anti-cTnI antibodies.
Therefore, anionic polyelectrolyte PSS has been firstly coated on
the positively charged surface of gold nanoprisms by electrostatic
interaction for passivating the cytotoxicity of CTABr and keeping
optical stability. The subsequent conjugation of the antibody on
the PSS-coated gold nanoprisms takes advantage of two interac-
tions: (1) electrostatic interaction between the negative charged
PSS and the positively charged segment of the antibody; (2)
hydrophobic interaction between the aryl portion of PSS and the
hydrophobic segment of the antibody [37,38]. As shown in Fig. 8,
the in-plane dipole resonance absorption maximum has a 5 nm
red-shift after PSS coating. After the anti-cTnI antibody conjuga-
tion, there is a 10 nm red-shift of the in-plane dipole resonance
absorption maximum. No shift in the absorption maximum of
the in-plane quadrupole resonance is also observed during the
whole process, indicating that the in-plane dipole resonance of
gold nanoprisms is quite sensitive to the changes of the local
dielectric surrounding. Further evidence for CTABr-capped gold
nanoprisms coated with PSS and subsequently anti-cTnI antibody
can be seen from the gradual changes of corresponding FTIR spec-
tra (see Supporting information). Fig. 9 shows the changes in the
SPR band of the anti-cTnI antibody conjugated gold nanoprism
Fig. 8. UV–vis–NIR absorption spectra of gold nanoprisms at different stages of
surface functionalization: (a) as-collected CTABr-capped gold nanoprisms; (b) PSS-
coated gold nanoprisms and (c) anti-cTnI antibody conjugated gold nanoprisms.
Fig. 9. UV–vis–NIR absorption spectra for anti-cTnI antibody conjugated gold
nanoprims before (a) and after (b)–(h) treatment with cTnI (10, 50, 100, 300, 500,
700, 1000 ng/mL in TBS buffer), respectively. Inset is the enlarged section of the
spectra shown in the dash box.
solution after adding cTnI with increasing concentrations (10–
1000 ng/ml). It can be seen the in-plane dipole resonance band
continuously decreases in intensity with a small red-shift, which
can be assigned to the aggregation of gold nanoprisms driven by
the specific binding events between anti-cTnI antibody and cTnI.
The above experimental result is somewhat different from the
sensing based on analyte-mediated spherical gold nanoparticles
aggregation, in which the SPR peak not only gradually diminish
but also undergo an apparent red-shift process due to plasmon
coupling of particle–particle aggregates [39]. However, it is worth
mentioning that Jain et al. previously reported that the shape
anisotropy of gold nanorods can leave them to be aggregated into
two distinct orientational modes, namely end-to-end and side-by-
side, and optical experiments revealed that side-by-side linkage of
nanorods in solution exhibits a blue-shift of the longitudinal
plasmon band while end-by-end linkage gives a red-shift [40].
Recently, Sendroiu et al. also observed that the formation of ran-
dom- aggregates of gold nanorods upon DNA hybridization mainly
induce the decrease of the SPR band intensity [41]. We thus pre-
sume that adding CTnI to the anti-cTnI antibody conjugated gold
nanoprism solution could induce the nanoprisms to aggregate in
a random-orientation mode, resulting in an obvious decreasing
intensity of in-plane dipole resonance band accompanied with a
slight red-shift. Our experimental results indicate that the sensing
of cTnI is achieved with a sensitivity of ca. 50 ng/mL according to
the appearance of an obvious decrease in intensity of in-plane di-
pole resonance band, which is comparable to that of gold nanorods
used as plasmonic platform in solution [42,43]. Moreover, control
experiments indicate that no SPR changes have been observed
when the anti-cTnI antibody conjugated gold nanoprism solution
was used to detect other biomarkers instead of cTnI.
4. Summary
In conclusion, we have demonstrated that colloidal gold trian-
gular nanoprisms with high-purity (97%) can be achieved conve-
niently by taking advantage of the electrostatic aggregation and
shape effects through a seed-mediated, iodide ion- and CTABr-
assisted synthetic system. The separation process between the
produced gold nanoprisms and spherical gold nanoparticles can
be easily triggered by adjusting the anion concentration in the
reaction solution, without the need of centrifugation or filtration.
Further study confirms that this strategy is effective while flexible
 Z. Guo et al. / Journal of Colloid and Interface Science 348 (2010) 29–36
enough that ultra-small gold nanoprisms can also been achieved in
good-purity. These as-collected gold nanoprism solutions are
shown to possess a remarkably enhanced performance in surface
plasmon resonance and NIR absorbing compared with the original
mixtures. Furthermore, investigation on their potential as biosen-
sing platforms based on the changes of the SPR band induced by
the specific antibody–antigen recognition events clearly indicates
that gold nanoprisms will be a promising candidate for solution-
based plasmonic sensing. In addition, these colloidal gold nanop-
risms, with extremely flat surface and strong NIR absorption, could
also find practical applications for drug delivery and hyperthermia
treatment of tumors in vivo.
Acknowledgments
Financial assistance from the High-technology Platform of
Jiangsu Province for Molecular Diagnosis and Biological Therapy
of Critical Illness (XK200705), the National Natural Science
Foundation of China (Nos. 30870679 and 30970787) and China
Postdoctoral Science Foundation (20090451236) is gratefully
acknowledged. Thanks also to Dr. M. Wang and Dr. L. Huang for
help with preparation of the manuscript.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.jcis.2010.04.013. Additional
TEM images, FTIR and UV–vis–NIR absorption spectra.
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