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Visual detection of glyphosate in environmental water

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samples using cysteamine-stabilized gold nanoparticles

Cite this: Anal. Methods, 2013, 5, 917
as colorimetric probe
Jinmin Zheng,ab Haijuan Zhang,ab Jichun Qu,ab Qian Zhuab and Xingguo Chen*abc

Received 29th August 2012
Accepted 2nd December 2012
DOI: 10.1039/c2ay26391b
www.rsc.org/methods
In this study, a novel colorimetric method for rapid, sensitive and low-cost detection of glyphosate was
developed using cysteamine-stabilized gold nanoparticles (CS-AuNPs). The CS-AuNPs could be
aggregated easily in the presence of glyphosate through electrostatic interaction in acidic medium,
resulting in a shift in the surface plasmon band and a consequent color change from red to blue (or
purple). Therefore, the content of glyphosate could be determined by monitoring with the naked eyes
or a UV-Vis spectrophotometer. The detection limit of the present method for glyphosate was 5.88

108 M, with the linear range of 0.500–7.00 mM. The proposed method is a promising approach for on-
site screening of glyphosate content in environmental water samples without using any costly instruments.

Introduction chromatography-mass spectroscopy (GC-MS)21 as well as

Glyphosate (N-[phosphonmethyl]glycine) is a nonselective,
postemergence, and systemic herbicide used for weed and
vegetation control.1–3 In the past decades, glyphosate has
become the most frequently used herbicide all around the
world, especially aer the introduction of glyphosate-resistant
transgenic crops.2,4 However, the intensive use of glyphosate
raises the potential for residue accumulation in both soil,
through adsorption, and water due to their high solubility and
leaching.5,6 For decades, glyphosate residues have been found in
various samples, including natural waters,7 even the urine of
farmers who have applied it.8 Although glyphosate presents a
lower acute toxicity than other herbicides, recent studies
suggest that it affects cell cycle regulation,9 and inhibits the
secretion of steroid hormones in men, possibly resulting in a
loss of fertility.10 Furthermore, the potential adverse effects on
ecosystems and humans have made it a target of research and
discussion for a long time.11–15 Therefore, the determination of
glyphosate content in environmental samples is necessary and
important for environmental monitoring.
Different methods for analysis of glyphosate in various
samples were reported, including high performance liquid
chromatography (HPLC),16 ion exchange chromatography
coupled to a pulsed amperometric detector (PAD),17 ion chro-
matography (IC),18 capillary electrophoresis (CE),19,20 and gas
a
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou,
730000, China. E-mail: chenxg@lzu.edu.cn; Fax: +86-931-8912582; Tel: +86-931-
8912763
b
Department of Chemistry, Lanzhou University, Lanzhou, 730000, China
c
Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu
Province, Lanzhou, 730000, China
immunoassay (IA).2,22 Although each of these methods has high
sensitivity, many of them are complicated, time-consuming, or
require bulky instrumentation and have to be performed by
highly trained technicians. Moreover, they are not cost-effective.
Therefore, there is a pressing demand to develop a rapid,
portable, sensitive, reliable and high-throughput routine assay
for measuring glyphosate.
Recently, colorimetric detection based on metallic nano-
particles has covered a list of methodologies and drawn intense
attention in biological science and analytical chemistry.23,24
Owing to the intrinsic characteristics such as ease of prepara-
tion, biocompatibility, stability, and high extinction coefficient,
gold nanoparticles (AuNPs) have received much more consid-
eration.25,26 The well-dispersed AuNPs solution is red, whereas
aggregated AuNPs emerge as blue color. By rationally tailoring
the functional groups of the AuNPs, the target analyte can bind
to AuNPs through a tailor-made approach which eventually
changes the dispersion/aggregation states and thus the color of
the AuNPs.27 Based on this property, various colorimetric probes
for different analytes including DNA,28,29 proteins,30 small
molecules,31 and metal ions32,33 have been developed. Very
recently, Dasary et al.34 proposed a AuNPs-based surface
enhanced uorescence for detection of organophosphorus
compounds. In their system, uorescence originating from Eu3+
ions which were bound within the electromagnetic eld of gold
nanoparticles exhibited a strong enhancement. In the presence
of glyphosate, Eu3+ ions were released from the gold nano-
particles surface and thus a very distinct uorescence signal
change was observed. However; the method was rather complex
and expensive. Cysteamine modied AuNPs (CS-AuNPs) have
drawn great attention recently, due to their excellent properties
including particle uniformity, unique functional groups and

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Analytical Methods Paper

simple preparation procedure which just need one step without
heating. The CS-AuNPs have been widely applied for DNA-
transfection into cultivated cells,35 peroxidase mimic.36 The
CS-AuNPs-based colorimetric assay has also been developed for
the detection of various analytes.37,38 However, to the best of our
knowledge, glyphosate has not been studied with AuNPs-based
colorimetric sensing.
In this work, we designed a new strategy for efficient recog-
nition and detection of glyphosate with CS-AuNPs. The detec-
tion limit of the method was 5.88
108 M. The method was
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1.0 mM Ba(OH)2 was added, sonicating and centrifuging was
repeated to remove sulfate radical and most metal ions. Finally,
the supernatant was adjusted to pH 6.5. Then the solution was
centrifuged at 10 000 rpm for another10 min and the nal
solution was collected for further use.
Colorimetric assay
For detecting of glyphosate, 1.2 mL of the CS-AuNPs solution
and 1.5 mL of HAc–NaAc buffer (20 mM, pH 4.0) were pipetted

into 5.0 mL centrifuge tubes and mixed sufficiently. Then, 0.3

rather simple and rapid. The proposed method was applied
mL sample or doubly distilled H2O was added to the corre-
to detect glyphosate in environmental water samples with
sponding tube and the resulting solutions were incubated for 30
satisfactory results.
min before measuring their UV-Vis spectra. The concentration
of glyphosate was quantied based on the absorption ratio
Experimental (A650/A524). The color change of the mixture solution could be
Materials and characterization observed by the naked eye and recorded by digital camera.
Hydrogen tetrachloroaurate(III) tetrahydrate (HAuCl4$4H2O)
was purchased from Fengyue Chemical Reagent Company Results and discussion
(Tianjin, China). Cysteamine hydrochloride (2-amino- Detection principle of glyphosate using CS-AuNPs as
ethanethiol) was obtained from J&K Company (Beijing, China). colorimetric probe
Sodium borohydride was a product of Sinopharm Chemical
Reagent Company (Shanghai, China). All solvents and reagents The morphology of the as-prepared CS-AuNPs was characterized
in this work were of analytical grade and directly used without by a transmission electron microscope (TEM) and dynamic light
further purication. Doubly distilled water was used
throughout the experiments.
A TU-1901 double beam UV-Vis spectrophotometer (Beijing
Purkine General Instrument Co. Ltd., China) was used to record
absorption spectra and measure absorbance. Transmission
electron microscopy (TEM) measurements were carried out by a
Hitachi-600 transmission electron microscope (Hitachi, Japan).
Dynamic light scattering (DLS) was performed with a Malvern
Nano-ZS apparatus for characterization of the size distribution
of nanoparticles in solution.

Synthesis of cysteamine-stabilized AuNPs (CS-AuNPs)

CS-AuNPs was prepared according to the reported literature.35–38
All glassware was thoroughly cleaned overnight with freshly
prepared concentrated HCl/HNO3 (3 : 1, v/v) and rinsed with
doubly distilled water prior to use. Briey, 400 mL of 0.213 M
cysteamine hydrochloride and 40 mL of 1.40 mM HAuCl4$4H2O
were mixed in a 100 mL glass vial. The mixture was stirred for 20
min at room temperature in the dark. 10 mL of freshly prepared
NaBH4 solution (10 mM) was then quickly added into the above
aqueous solution under vigorous stirring, and the mixture was
further stirred for 30 min. The resulting wine-red solution was
ltered by 0.45 mm lter paper and stored in the refrigerator
(4  C) before use. The concentration of the prepared AuNPs was
0.6 nM as determined by UV-Vis spectrometry.39

Sample preparation
The water sample was prepared as follows: 4.0 mL of tap water
was placed into a 10 mL centrifuge tube and 4.0 mL of chloro-
form was added. The mixture was sonicated for 15 min and then Fig. 1 TEM images of CS-AuNPs in the absence (A) and the presence of 20.0 mM
centrifuged at 10 000 rpm for 10 min to eliminate the water- glyphosate (B). Size characterizations of CS-AuNPs by dynamics light scattering
insoluble organics. Aer the supernatant was collected and (DLS) in the absence (C) and the presence of 20.0 mM glyphosate (D).

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scattering (DLS). As shown in Fig. 1A and C, CS-AuNPs are a
highly dispersed multiphase system with an average size of 30.0
nm. The CS-AuNPs solution was wine-red in color and exhibited
an absorption peak at 524 nm (Fig. 2), which was ascribed to the
surface plasmon resonance of the AuNPs. Due to the supercial
–NH+3 groups, the CS-AuNPs were positively charged, resulting
in high stability against aggregation due to the electrostatic
repulsion force.37,38 In our experiments, when glyphosate (20.0
mM) was added to the CS-AuNPs solution, it could be observed
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that the Plasmon resonance dampened and had a red shi. The
absorption spectrum exhibited an obvious decrease at 524 nm
and a strong increase at 650 nm, and the color of the conjugates
clearly changed from wine-red to purple within several minutes,
indicative of the aggregation of CS-AuNPs. The glyphosate-
stimulated aggregation of CS-AuNPs was also veried by TEM
image and DLS measurements (Fig. 1B and D).
Glyphosate molecule contains functional groups of carboxyl
(–COOH) and phosphonyl (–PO3H2). The positively charged
amino groups (–NH+3) can attach each other with negatively
charged groups (–COOH and –PO3H2), with the result that
glyphosate molecules were attached to the surface of CS-AuNPs.
Fig. 2 The chemical structures of the series of herbicides studied (A), photo-
graphic images (B) and UV-vis spectra (C) of CS-AuNPs solution containing these
compounds: aminomethylphosphonic acid (AMPA), glufosinate, glyphosate. The
experiments were performed at 0.24 nM CS-AuNPs solution, HAc–NaAc buffer,
the NaAc concentration of 10 mM, the pH of 4.0, and reaction temperature of 15

C and time of 30 min.
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According to previous work,40 we proposed two assumptions to
explain the glyphosate-induced aggregation of CS-AuNPs.
On the one hand, the glyphosate adsorbed on the surface of
CS-AuNPs could lead to a decrease of the average surface charge,
which would break up the balance between electrostatic force
and van der Waals' force, with the result of aggregating of
CS-AuNPs. On the other hand, the glyphosate molecules could
cross-link the neighbor CS-AuNPs by two equivalent sites
(–COOH and –PO3H2), resulting in the aggregation of CS-AuNPs.
In order to validate which presumption was more reasonable,
the control experiment was carried out using glufosinate and
aminomethylphosphonic acid (AMPA) as substitutes of glyph-
osate (Fig. 2). Glufosinate and AMPA have a similar molecular
structure to glyphosate. However, the experimental results show
that only glyphosate could cause the aggregation of CS-AuNPs,
accompanied with appreciable changes in color and absorption
properties. Compared to glyphosate, the AMPA molecule just
contains a negatively charged phosphonyl group (–PO3H2), and
an amino groups (–NH2) instead of carboxyl group (–COOH).
Thus, AMPA molecules could not change the surface charge
density of CS-AuNPs, or cross-link the neighbor CS-AuNPs. As to
glufosinate, because of the static resistance of methyl and the
electrostatic repulsion force between –NH+3 groups, it could not
bridge up the neighbor CS-AuNPs smoothly. Therefore, the
principle of glyphosate recognition in the present work may
involve the decrease of surface charge density of CS-AuNPs in
combination with smooth cross-linking of the neighbor
CS-AuNPs with more than one negatively charged group.
Simultaneously, the citrate-capped AuNPs nanomaterials were
synthesized to be used as the control as well, and the d-potential
of the citrate-capped AuNPs was negative at pH 4.0. Experi-
ments show that glyphosate could not lead to the aggregation of
the negatively charged AuNPs (Fig. 3). Scheme 1 depicts the
mechanism for detecting glyphosate using CS-AuNPs. Consid-
ering the obvious changes in color and absorption properties of
CS-AuNPs toward glyphosate, a simple colorimetric detection of
glyphosate was proposed in the present work.
Optimization of the experimental conditions
To optimize the conditions for the glyphosate assay, various
factors, such as the concentration of CS-AuNPs, the concentra-
tion of NaAc in HAc–NaAc buffer solution, media pH, incuba-
tion time and temperature were investigated.
The concentration of CS-AuNPs is an important parameter in
this method. When the concentration of the CS-AuNPs was
varied from 0.12 to 0.39 nM, the absorption ratio (A650/A524) of
CS-AuNPs gradually decreased with increasing gold nano-
particle concentration, while the conjugates rstly increased
then decreased. It reached the highest point when the concen-
tration of CS-AuNPs was 0.24 nM. The optimization curve for
CS-AuNPs concentration is shown in Fig. 4. Therefore, the
concentration of CS-AuNPs of 0.24 nM was chosen as the
optimum for subsequent work.
The sensitivity and dynamic range of the colorimetric signal
was dependent on the resistance of AuNPs to aggregation and
could be adjusted by changing the buffer composition of the
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Fig. 3 Photographic images and UV-Vis spectra of citrate-capped AuNPs solu-
tion in the absence and presence of 20.0 mM glyphosate. The experiments were
performed at HAc–NaAc buffer, NaAc concentration of 10 mM, pH of 4.0, reaction
temperature of 15  C, and time of 30 min.
Scheme 1 Schematic representation of the strategy for glyphosate detection
using the CS-AuNPs.
AuNPs.41 Under conditions of low ionic strength, the slight
electrostatic repulsion between AuNPs provided a low barrier
for analytes-induced AuNPs aggregation.42 However, a high
Fig. 4 The plots of the ratio A650/A524 of CS-AuNPs in the absence and presence
of 20.0 mM glyphosate in the different concentrations of CS-AuNPs. The experi-
ments were performed at HAc–NaAc buffer, NaAc concentration of 10 mM, pH of
4.0, reaction temperature of 15  C, and time of 30 min.
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ionic strength may destroy the electrostatic binding between the
analytes and AuNPs.43 The HAc–NaAc buffer solution was chose
as reaction media in our experiments, and to obtain a lower
detection, the concentration of NaAc ranges from 0 to 20 mM
was used to investigate, and for comparison, the absorption
ratios (A650/A524) were obtained with and without glyphosate
respectively. As can be observed from Fig. 5, with a constant
concentration of the glyphosate (20.0 mM), the highest sensi-
tivity was obtained using 10 mM NaAc. The CS-AuNPs solution
did not show any color change at low concentration of NaAc,
and an obvious color change from red to blue was observed with
higher concentration of NaAc in the absence of glyphosate. The
latter resulted from the self-aggregation of CS-AuNPs induced
by the high concentrations of Na+ and Ac. So, 10 mM was
selected as the optimal concentration of NaAc in HAc–NaAc
buffer solution for further study.
Similar to the detection of other small molecules based on
AuNPs,44,45 the interaction between glyphosate and the
CS-AuNPs showed pH dependence. We investigated the effect of
media pH in the range of 3.0–7.0 by adjusting the 10 mM NaAc
buffer solution with acetic acid. As shown in Fig. 6, it could be
seen that a satisfactory result was obtained at pH 4.0. The
absorption ratio (A650/A524) was very low in spite of 20.0 mM
glyphosate in strong acidic media (pH ¼ 3.0) and the color
began to change without glyphosate when pH > 5.5. Glyphosate
is a weak polyprotic acid and its form can be affected by the pH
of the solution. At low pH (pH < 4.0) protonated glyphosate
could not decrease the surface charge density of CS-AuNPs or
cross-linking of the neighbor CS-AuNPs. Then the electrostatic
force counteracted the effects of van der Waals' force between
CS-AuNPs, which could not induce the aggregation of the
CS-AuNPs. However, as the pH increase, the ionization of the
–NH2 group in cysteamine on gold nanoparticle surface
decreased, and in turn the positive charges of the –NH+3 group
decreased. As stated above, the van der Waals' force between
CS-AuNPs became predominated, and at relatively high pH
Fig. 5 The plots of the ratio A650/A524 of CS-AuNPs in the absence and presence
of 20.0 mM glyphosate at different concentrations of NaAc. The experiments were
performed at 0.24 nM CS-AuNPs solution, HAc–NaAc buffer, pH of 4.0, reaction
temperature of 15  C, and time of 30 min.
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Fig. 6 The plots of the ratio A650/A524 of CS-AuNPs in the absence and presence
of 20.0 mM glyphosate under different pH conditions. The experiments were
performed at 0.24 nM CS-AuNPs solution, HAc–NaAc buffer, NaAc concentration
of 10 mM, reaction temperature of 15  C, and time of 30 min.
(pH > 5.5), the CS-AuNPs might partially aggregate and could
not interact with glyphosate as well.37,38 In addition, the ionic
strength of solution increased with the increasing pH value that
was due to the increases of the concentrations of Na+ and Ac
which can affect the electrostatic binding. The increasing ionic
strength of the solution also slightly aggravated the aggregation
of CS-AuNPs at high pH value, which resulted in the increase of
the absorption ratio of the blank. Considering the above factors,
pH 4.0 was chosen as the optimum condition.
Temperature and time were found to play important roles in
most reactions. The effects of incubation temperature and
reaction time on the absorbance of the CS-AuNPs with glyph-
osate system were examined in the range of 15–45  C within
30 min. As depicted in Fig. 7, the highest absorption ratio
(A650/A524) was obtained at 15  C, and the assay signal rapidly
increased to a maximum value within 8 min then tended to level
off up to 30 min. However, when the temperature increased, not
only the saturated signal decreased, but also the absorption
ratio came down with time. The possible reason was that high
temperatures could induce self-aggregation of CS-AuNPs, and
long incubation time would aggravate the process, which was
conrmed by a group of contrast experiments in the absence of
glyphosate. The absorption ratio without glyphosate increased
gradually along with the increase of temperature and time. So
taking into account sensitivity and accuracy, 15  C was chosen
as the operational temperature for all experiments and the
resulting solutions were incubated for 30 min before measuring
their absorbance.
Analytical performance of the CS-AuNPs–glyphosate sensing
system
To quantitatively detect glyphosate using the CS-AuNPs as
colorimetric probe, the sensitivity was evaluated under the
optimized conditions and the results are displayed in Fig. 8. The
color of CS-AuNPs gradually changed from wine-red to purple
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Analytical Methods
Fig. 7 The plots of the ratio A650/A524 of CS-AuNPs vs. the time and temperature
value in the absence and presence of 20.0 mM glyphosate. The experiments were
performed at 0.24 nM CS-AuNPs solution, HAc–NaAc buffer, NaAc concentration
of 10 mM, and pH of 4.0.
and nally to grey with gradually increasing glyphosate
concentration. These results were further conrmed by UV-Vis
spectroscopy. Along with the addition of glyphosate, the
absorption of CS-AuNPs solution at 524 nm gradually decreases,
and the absorption at 650 nm increases obviously, which sug-
gested more CS-AuNPs aggregated as the concentration of
glyphosate increased. The absorption ratio (A650/A524) enhanced
with increasing amount of glyphosate (see Fig. 9) and exhibited
a linear correlation to glyphosate concentration in the range
from 0.500 to 7.00 mM. The limit of detection of glyphosate is
based on 3d was 5.88
108 M, which is lower than the
permissible level in the United States and China (0.70 mg L1,
i.e., 1.12
108 M). A series of 10 repetitive measurements with
2.00 mM glyphosate was used for investigating the precision of
the CS-AuNPs response, and the relative standard deviation
(R.S.D.) was 2.71%, suggesting excellent reproducibility of the
proposed method.
Interference of other substances
The selectivity of this method for detection of glyphosate was
evaluated by testing the response of the assay to other
compounds. As shown in Fig. 10, 0.1 mM of glufosinate, AMPA,
dicamba, acetochlor, atrazine, and triuralin, are higher than
normal ambient levels, and were examined under the same
experimental conditions. To quantify the spectral changes at
524 nm and 650 nm, the absorbance ratio A650/A524 in the
presence of 20.0 mM tested analyte was also determined. The
change of color and high intensity variation of the A650/A524
value were observed only in the presence of glyphosate. Thus,
the colorimetric approach we developed here using CS-AuNPs
shows good selectivity toward glyphosate detection. This excel-
lent selectivity was mainly attributed to the specic topology
of glyphosate and the strong electrostatic interaction between
CS-AuNPs and glyphosate.
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Table 1 Recovery results using the proposed method to determine glyphosate

spiked in tap water

(Recovery 
Added R.S.D.) %
Sample (mM) Measured (mM) (n ¼ 3)

1 2.50 2.39 95.40  2.60

5.00 5.27 105.34  2.11
2 2.50 2.32 92.76  3.10
5.00 5.50 110.10  2.58
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Fig. 8 (A) Photo and (B) absorption spectra of CS-AuNPs incubated with various
concentrations of glyphosate (0, 0.500, 1.00, 2.00, 3.00, 4.00, 5.00, 6.00, 7.00,
8.00, 10.0, 12.0, 16.0, 20.0 mM). The experiments were performed at 0.24 nM
CS-AuNPs solution, HAc–NaAc buffer, NaAc concentration of 10 mM, pH of 4.0,
reaction temperature of 15  C, and time of 30 min.

Fig. 10 The selectivity of the proposed method for glyphosate. (A) Direct
observation of the corresponding color changes and (B) the absorbance ratio
A650/A524 of the CS-AuNPs in the presence of different substances. The concen-
tration of glyphosate was 20.0 mM, and the other substances were all 0.1 mM. The
experiments were performed at 0.24 nM CS-AuNPs solution, HAc–NaAc buffer,
NaAc concentration of 10 mM, pH of 4.0, reaction temperature of 15  C, and time
of 30 min.

Application of CS-AuNPs for the analysis of real water samples

Fig. 9 Plots of the absorption ratio (A650/A524) vs. glyphosate concentration. The
experiments were performed at 0.24 nM CS-AuNPs solution, HAc–NaAc buffer,
NaAc concentration of 10 mM, pH of 4.0, reaction temperature of 15  C, and time
of 30 min.
To investigate the practical application of this colorimetric
method, the detection of glyphosate in tap water was carried
out. The challenge for detecting glyphosate in water was how to
eliminate the potential interference of sulfate. The existence of
SO42 resulted in an obvious change in absorption ratio38 that
seriously interfered the detection of glyphosate in tap water. In
the study, we met this requirement by reducing the concentra-
tion of sulfate under the level of tolerance upon the addition of
Ba2+(Ba(OH)2) to tap water. Meanwhile, Al(III)46 and Cu(II)47
which could bind to analyte can be eliminated by coprecipita-
tion. The water samples were prepared and analyzed according
to the procedures described in the Experimental section. As
shown in Table 1, 2.50 mM or 5.00 mM glyphosate was spiked,

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and the measured recoveries were between 92% and 111%. The
results show that the recovery and precision of the proposed
method are satisfactory.
Conclusions
In conclusion, a sensitive, selective and simple colorimetric
assay using cysteamine-stabilized gold nanoparticles as a probe
to detect glyphosate is rst reported. The quantitative deter-
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mination of glyphosate was based on the distance-dependent
optical property of CS-AuNPs and the efficient electrostatic
interaction between CS-AuNPs and glyphosate. It could be
monitored by the color change of the solution as well as the
ratio of absorption coefficients. The method we developed
shows several advantages, including simplicity of preparation
and manipulation, without using any advanced instruments
compared to other methods for glyphosate detection. Moreover,
it demonstrated superior sensitivity with a detection limit of
5.88
108 M for glyphosate which satises the needs for
on-site rapid monitoring of trace glyphosate in water. This was
the rst application of a cysteamine-stabilized AuNP-based
probe for colorimetric recognition of glyphosate contamination.
Acknowledgements
This work was kindly supported by the National Natural Science
Foundation of China (no. 21075056).
References
1 E. A. Lee, L. R. Zimmerman, B. S. Bhullar and
E. M. Thurman, Anal. Chem., 2002, 74, 4937–4943.
2 M. Á. González-Martı́nez, E. M. Brun, R. Puchades,
Á. Maquieira, K. Ramsey and F. Rubio, Anal. Chem., 2005,
77, 4219–4227.
3 G. M. Dill, Pest Manage. Sci., 2005, 61, 219–224.
4 J. Bernal, M. T. Martin, M. E. Soto, M. J. Nozal, I. Marotti,
G. Dinelli and J. L. Bernal, J. Agric. Food Chem., 2012, 60,
4017–4025.
5 M. L. Rueppel, B. B. Brightwell, J. Schaefer and J. T. Marvel,
J. Agric. Food Chem., 1977, 25, 517–528.
6 O. K. Borggaard and A. L. Gimsing, Pest Manage. Sci., 2008,
64, 441–456.
7 N. J. Smith, R. C. Martin and R. G. St. Croix, Bull. Environ.
Contam. Toxicol., 1996, 57, 759–765.
8 J. F. Acquavella, B. H. Alexander, J. S. Mandel, C. Gustin,
B. Baker, P. Chapman and M. Bleeke, Environ. Health
Perspect., 2004, 112, 321–326.
9 J. Marc, O. Mulner-Lorillon and R. Bellé, Biol. Cell, 2004, 96,
245–249.
10 L. P. Walsh, C. McCormick, C. Martin and D. M. Stocco,
Environ. Health Perspect., 2000, 108, 769–776.
11 C. Accinelli, W. C. Koskinen, J. D. Seebinger, A. Vicari and
M. J. Sadowsky, J. Agric. Food Chem., 2005, 53, 4110–4117.
12 J. Schönherr and L. Schreiber, J. Agric. Food Chem., 2004, 52,
6546–6551.
This journal is ª The Royal Society of Chemistry 2013
View Article Online
Analytical Methods
13 M. C. Arregui, A. Lenardón, D. Sanchez, M. I. Maitre,
R. Scotta and S. Enrique, Pest Manage. Sci., 2004, 60, 163–
166.
14 J. A. Werth, C. Preston, I. N. Taylor, G. W. Charles,
G. N. Roberts and J. Baker, Pest Manage. Sci., 2008, 64,
417–421.
15 G. A. Kleter, C. Harris, G. Stephenson and J. Unsworth, Pest
Manage. Sci., 2008, 64, 479–488.
16 C. D. Stalikas and C. N. Konidari, J. Chromatogr., A, 2001,
907, 1–19.
17 K. Sato, J.-Y. Jin, T. Takeuchi, T. Miwa, K. Suenami,
Y. Takekoshi and S. Kanno, J. Chromatogr., A, 2001, 919,
313–320.
18 Y. Zhu, F. Zhang, C. Tong and W. Liu, J. Chromatogr., A, 1999,
850, 297–301.
19 M. Corbera, M. Hidalgo, V. Salvadó and P. P. Wieczorek,
Anal. Chim. Acta, 2005, 540, 3–7.
20 S. Y. Chang and C.-H. Liao, J. Chromatogr., A, 2002, 959, 309–
315.
21 F. Hernández, C. Hidalgo, J. V. Sancho and F. J. López, Anal.
Chem., 1998, 70, 3322–3328.
22 H. U. Lee, H. Y. Shin, J. Y. Lee, Y. S. Song, C. Park and
S. W. Kim, J. Agric. Food Chem., 2010, 58, 12096–12100.
23 N. Xiao and C. Yu, Anal. Chem., 2010, 82, 3659–3663.
24 Y. Ma, H. Niu, X. Zhang and Y. Cai, Analyst, 2011, 136, 4192–
4196.
25 N. L. Rosi and C. A. Mirkin, Chem. Rev., 2005, 105, 1547–
1562.
26 E. Katz and I. Willner, Angew. Chem., Int. Ed., 2004, 43, 6042–
6108.
27 Y. Jiang, H. Zhao, N. Zhu, Y. Lin, P. Yu and L. Mao, Angew.
Chem., 2008, 120, 8729–8732.
28 H. Li and L. J. Rothberg, J. Am. Chem. Soc., 2004, 126, 10958–
10961.
29 M. S. Han, A. K. R. Lytton-Jean, B.-K. Oh, J. Heo and
C. A. Mirkin, Angew. Chem., Int. Ed., 2006, 45, 1807–1810.
30 J. Liu and Y. Lu, Angew. Chem., 2006, 118, 96–100.
31 S. S. R. Dasary, A. K. Singh, D. Senapati, H. Yu and P. C. Ray,
J. Am. Chem. Soc., 2009, 131, 13806–13812.
32 T. Li, S. Dong and E. Wang, Anal. Chem., 2009, 81, 2144–
2149.
33 J. Liu and Y. Lu, J. Am. Chem. Soc., 2003, 125, 6642–6643.
34 S. S. R. Dasary, U. S. Rai, H. Yu, Y. Anjaneyulu, M. Dubey and
P. C. Ray, Chem. Phys. Lett., 2008, 460, 187–190.
35 T. Niidome, K. Nakashima, H. Takahashi and Y. Niidome,
Chem. Commun., 2004, 1978–1979.
36 Y. Jv, B. Li and R. Cao, Chem. Commun., 2010, 46, 8017–
8019.
37 R. Cao and B. Li, Chem. Commun., 2011, 47, 2865–2867.
38 M. Zhang, Y.-Q. Liu and B.-C. Ye, Analyst, 2011, 136, 4558–
4562.
39 W. Haiss, N. T. K. Thanh, J. Aveyard and D. G. Fernig, Anal.
Chem., 2007, 79, 4215–4221.
40 H. Ping, M. Zhang, H. Li, S. Li, Q. Chen, C. Sun and T. Zhang,
Food Control, 2012, 23, 191–197.
41 F. Wei, R. Lam, S. Cheng, S. Lu, D. Ho and N. Li, Appl. Phys.
Lett., 2010, 96, 133702–133703.
Anal. Methods, 2013, 5, 917–924 | 923
 View Article Online

Analytical Methods Paper

42 C.-Y. Lin, C.-J. Yu, Y.-H. Lin and W.-L. Tseng, Anal. Chem.,
2010, 82, 6830–6837.
43 Z. P. Li, X. R. Duan, C. H. Liu and B. A. Du, Anal. Biochem.,
2006, 351, 18–25.
44 S.-H. Wu, Y.-S. Wu and C.-h. Chen, Anal. Chem., 2008, 80,
6560–6566.
Published on 03 December 2012. Downloaded by FAC DE QUIMICA on 3/7/2023 10:23:43 PM.
45 S. K. Ghosh and T. Pal, Chem. Rev., 2007, 107, 4797–
4862.
46 R. J. Motekaitis and A. E. Martell, J. Coord. Chem., 1985, 14,
139–149.
47 P. G. Daniele, C. De Stefano, E. Prenesti and S. Sammartano,
Talanta, 1997, 45, 425–431.

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