Influence of the pH value of a colloidal gold solution on the absorption spectra of an

LSPR-assisted sensor
Jin Zhu, Wenbin Li, Mao Zhu, Wei Zhang, Wencheng Niu, and Guohua Liu

Citation: AIP Advances 4, 031338 (2014); doi: 10.1063/1.4869615

View online: https://doi.org/10.1063/1.4869615
View Table of Contents: http://aip.scitation.org/toc/adv/4/3
Published by the American Institute of Physics

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 AIP ADVANCES 4, 031338 (2014)

Influence of the pH value of a colloidal gold solution

on the absorption spectra of an LSPR-assisted sensor
Jin Zhu, Wenbin Li, Mao Zhu, Wei Zhang, Wencheng Niu, and Guohua Liua
College of Electronic Information and Optical Engineering, Nankai University,
Tianjin 300071, People’s Republic of China
(Received 12 November 2013; accepted 11 March 2014; published online 24 March 2014)

The localized surface plasmon resonances (LSPRs) of gold particles assembled on

a crystal plate are a powerful tool for biological sensors. Here, we prepare gold
colloids in different pH solutions. We monitor the effects of the particle radius
and particle coverage on the absorption spectra of AT-cut (r-face dihedral angle of
about 3◦ ) crystal plates supporting gold nanoparticles. The surface morphologies
were monitored on silicon dioxide substrates using ultraviolet and visible (UV-vis)
spectroscopy, and atomic force microscopy (AFM). The results showed that the gold
particle coverage decreases with increasing pH value of the gold colloid solution.
This phenomenon demonstrates that self-assembled gold surfaces were formed via
the electrostatic adsorption of gold particles on the positively charged, ionized amino
groups on the crystal plates in the acidic solution. The spectrum of gold nanoparticles
with different coverage degree on the crystal plates showed that the LSPR properties
are highly dependent on pH.  C 2014 Author(s). All article content, except where

otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported

License. [http://dx.doi.org/10.1063/1.4869615]

I. INTRODUCTION
In recent years, gold nanoparticles and other noble metal nanoparticles have attracted much
attention from researchers, particularly with reference to the electronic and optical properties of their
colloidal solutions.1–3 Localized surface plasmon resonance (LSPR) nanosensors based on metal
nanoparticle arrays are effective platforms for the detection of biological targets. Selecting optimized
nanoparticle structures can improve the sensitivity of LSPR-based sensors.4 In many studies, the
desired architecture consists of a two-dimensional array of nanoparticles supported on a substrate.5–10
However, relatively few studies have investigated the factors that govern the nanostructure within
this geometry. The optical properties of noble metal nanoparticles are determined by the size, shape,
dielectric properties, and local environment of the nanoparticle.13–15 Grabar’s group11, 12 reported
that the assembly time had an effect on the particle coverage and the interparticle spacing, but the
effects of other factors have not been reported.
We perform a detailed study of the kinetics of the binding of colloidal gold particles to
(3-aminopropyl)-trimethoxysilane (APTMS)-coated transparent quartz substrates. Colloidal gold
sols were prepared via the citrate reduction of HAuCl4 in aqueous solution. We aimed to change
the relative rates of the two independent nucleation and growth processes of the gold particles by
changing the relative amounts of reactants. The pH value is an important environmental factor,
especially in chemical and biomedical systems. The pH value affects the dissociation of functional
groups on the surface of self-assembled monolayers, and the attachment of gold particles to the
substrates; consequently, changes in the pH result in changes in gold particle coverage.
The fabrication of the self-assembling gold surfaces consisted of two major steps: (1) Preparation
of gold colloids in pH solutions varying from 4.0 to 10.8. (2) Self-assembly of the gold nanoparticles
on transparent quartz substrates.

a Author to whom correspondence should be addressed. Electronic address: liugh@nankai.edu.cn

2158-3226/2014/4(3)/031338/6 4, 031338-1 
C Author(s) 2014
031338-2 Zhu et al. AIP Advances 4, 031338 (2014)

II. EXPERIMENTAL
A. Materials
HAuCl4 · 3H2 O (Alfa, 97% purity), trisodium cirate dihydrate (Alfa, 99% purity) and APTMS
(Alfa, 97% purity) were used to prepare gold colloids. Substrates were 330-μm thick blank AT-cut
quartz plates with 1 inch diameter. Both surface of the quartz plates were carefully mechanically
polished to obtain smooth surface.

B. Preparation of gold colloids

Gold colloids were prepared by citrate reduction of HAuCl4 in aqueous solution. Aqueous
HAuCl4 · 3H2 O (1% g/mL, 0.6 mL) was added into deionized water(60 mL) in a round-bottom,
scratch-free flask, that had been washed in aqua regia and rinsed in water. When the solution was
heated to boiling, the solution of citrate ion (trisodium citrate dihydrate, 1% g/mL, 2 mL) was
injected. The solution changed from yellow to red.

C. Preparation of buffer solutions with different pH values

Acidic buffer solutions (pH 3.5–7.0) were prepared by combining different proportions of
trisodium citrate dihydrate and citric acid in aqueous solution. Highly alkaline pH buffer solutions
(pH > 10) were prepared by adding sodium hydroxide to an aqueous solution.

III. RESULTS AND DISCUSSION

A. Selection of buffer solution
To investigate LSPR properties of our gold particles, the gold sols prepared at different pH
values need to remain stable. We chose citric acid and trisodium citrate dihydrate to prepare the
acidic pH buffer solutions because: (1) The ions adsorbed on the surface of gold particles are OH−1
and citrate ions. Therefore the buffer solution does not introduce new species. (2) Citrate reduces the
impact of counter ions on the double ionization layer, and enhances the stability of colloidal gold
sols. Our tests showed that gold sols with a pH of 3.5 that were adjusted using the buffer solution
remained stable for 6 h, and only then did the color of the sol change to blue; in contrast, gold sols
with a pH of 3.5 that were adjusted using an aqueous HCl solution immediately aggregated. The
pH value of the gold sols changed significantly after the buffer solution was added. For example,
the pH value of the solution increased to 3.9 after gold sols (8 mL) were added to a buffer solution
(0.5 mL) of pH 3.5, because the low concentration of the buffer solution led to a weak buffer
capacity.

B. Spectral analysis of a LSPR-assisted sensor

We monitored the changes in the maximum LSPR extinction curve by varying the particle
diameter, particle size spacing, and molecular adsorbates on the gold colloids. Figure 1 shows
electron micrographs of gold nanoparticles with three different sizes; these particles were prepared
using reductant (trisodium citrate dehydrate)/gold ratios of 1.4:1, 3.5:1, and 4.6:1.16, 17 Figure 1(a)
to 1(c) show gold particles with diameters of 16, 20, and 30 nm, respectively. The particle size
increases when the amount of trisodium citrate dehydrate increased.
The influence of the pH of the gold sols on the particle coverage was investigated using
AFM. The gold particles were distributed homogeneously on the surface of crystal plates. The
coverage was measured as the number of gold particles in an area of 2 μm × 2 μm. Different
regions on the surface of the crystal plate showed approximately the same coverage value. The
experimental procedure was as follows: The pH value of the gold sols was adjusted to 4.0, 4.5, 4.8,
5.4, 6.4, and 10.8 by adding the pH buffer solution. The crystal plates were placed in gold sols
with different pH values for 4 h. After 4 h, only the gold sols in the buffer solution of pH 10.8
031338-3 Zhu et al. AIP Advances 4, 031338 (2014)

FIG. 1. TEM images of different size of gold particles and (a) reductant/gold ratio = 4.6:1, (b) reductant/gold ratio = 3.5:1,
(c) reductant/gold ratio = 1.4:1.

FIG. 2. The pH-dependence of the coverage of gold nanoparticles (the coverage was measured as the number of gold particles
in an area of 2 μm × 2 μm).

FIG. 3. Optical properties of different size of nanosphere at pH 6.4(a) and 4.8(b).

aggregated and turned blue. The quartz plates were then removed from the sols/buffer solutions
and cleaned with distilled water. The surface morphologies of crystal plates that were dipped in the
gold sols with a reductant/gold ratio of 4.6:1 were observed using AFM. Figure 2 shows that the
particle coverage varies significantly. When the pH value was increased from 4 to 8, the particle
coverage decreased sharply. For pH values greater than 8, the particle coverage approaches 0.
031338-4 Zhu et al. AIP Advances 4, 031338 (2014)

FIG. 4. Normalized absorption spectra of three different size gold nanoparticles varied with pH value of solution (a) large size
(d = 30 nm) nanoparticles prepared in solution of reductant/gold ratio of 4.6:1 (b) medium size (d = 20 nm) nanoparticles
prepared in solution of reductant/gold ratio of 3.5:1 (c) small size (d = 16 nm) nanoparticles prepared in solution of
reductant/gold ratio of 1.4:1.
031338-5 Zhu et al. AIP Advances 4, 031338 (2014)

When the particle coverage reaches a maximum value, the factors affecting the particle coverage
are the repulsive forces between particles, and the attractive interactions between particles and the
substrate.12
The pH value affects the binding affinity between the gold particles and functional groups.
It also affects the electrostatic repulsion between the gold particles, and consequently affects the
coverage. Some papers have reported the covalent binding of gold nanoparticles with amino groups.
The amino groups provide a lone electron pair more easily in an alkaline solution than in an acidic
solution, and consequently the gold particles assemble more easily on the substrate in the presence of
an alkaline solution. However, our experimental results showed that it was difficult for the particles
to assemble on the substrate in alkaline solutions; the particles assemble more easily on the substrate
in acidic solutions. When the pH value was lower than 6, most of the amino groups were protonated,
providing a maximum surface charge, and the particle coverage approached a maximum level. When
the pH value was higher than 10, the amino groups were not dissociated, and the particle coverage
was close to 0. In conclusion, we believe that the combination of the gold nanoparticles with the
amino groups occurred via electrostatic interactions.
Figure 3 shows the absorption curves of the substrates from gold sols with different reduc-
tant/gold ratios at pH 6.4 and pH 4.8. The absorption peak intensity of the 16-nm gold nanoparticles
is significantly higher than that of the 20-nm gold nanoparticles. The absorption peak intensity of
the 30-nm gold nanoparticles is similar to that of the 20-nm gold nanoparticles. This dependence is
governed by several factors. For very large metal particles, the number of nucleation centers provided
by the gold sols is extremely low.18 With increasing particle size, the decreasing surface area may
not have been large enough to absorb the same proportion of the wavelengths transmitted from the
solution with the same intensity.19 Smaller particles aggregate more easily, and the absorbance peak
red-shifts.
Figure 4 shows the in-solution, normalized absorption spectra for quartz substrates supporting
assemblies of nanoparticles of three different particle sizes. In all three graphs, the absorption peaks
showed a clear red-shift. These results demonstrated that the gold sols with a higher pH produced a
larger red-shift. According to the classic Mie theory, the variations in the absorption peak position,
the half peak width, and the peak intensity are affected by three factors: (1) the nanoparticle’s size;
(2) the conduction electron density of the particle surface plasma; and (3) the dielectric constant of
the metal particles.20, 21 With increasing pH value, the electrophoretic migration rate increased. The
particle surface adsorbed more negative ions, leading to stronger electrostatic repulsion between the
particles. As a result, the particle spacing increased, and the particles did not aggregate easily. In
contrast, the nanoparticles aggregated easily in the acidic solutions, and the absorption peak showed
an obvious red-shift. Figure 4(a) shows that there was no significant absorption peak in the substrates
produced using the gold sols with a pH of 10.8, because the particle coverage was close to 0 in the
alkaline solutions.

IV. CONCLUSION
This study compared the absorption spectra of LSPRs. By comparing the optical properties of
substrates covered with gold nanoparticles of different sizes and with different particle coverage
values, we showed that the optical properties of the gold particles depend on nanometer-scale
architecture of the substrate surface. The pH of the colloidal gold sols significantly affects the particle
coverage. In acidic solutions, most of the amino groups were protonated, and the gold nanoparticles
combined with the amino groups more easily via electrostatic interactions. The absorption peak
intensity varies with the nanoparticle size. The small nanoparticles showed greater absorption peak
intensities. With increasing particle size, the decreasing surface area may not have been large
enough to absorb the same proportion of the wavelengths transmitted from the solution with the
same intensity. The results demonstrate that the pH of the gold sols determined the gold particle
coverage, and also affected the red-shift of the LSPR band on the quartz substrates. This study
suggests that the particle size and particle coverage are both important factors affecting the optical
properties of LSPR-assisted sensors, and that rational nanometer-scale architectures will improve
the sensitivity of LSPR-assisted sensors.
031338-6 Zhu et al. AIP Advances 4, 031338 (2014)

ACKNOWLEDGMENTS
The authors thank the National Natural Science Foundation of China (Grant No.61271099),
Natural Science Founation of Tianjin (12JCZDJC20400), and National Research Foundation for
Doctoral Program of Higher Education of China (20120031110031) for their financial support to
complete this work.
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