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Separation, identification and fast determination of organophosphate

pesticide methidathion in tea leaves by thin layer chromatography-surface-
enhanced Raman scattering

Article in Analytical Methods · October 2013

DOI: 10.1039/C3AY41152D

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Separation, identification and fast determination of

organophosphate pesticide methidathion in tea leaves
Published on 15 August 2013. Downloaded by Sichuan University on 10/09/2013 14:51:23.

Cite this: DOI: 10.1039/c3ay41152d

by thin layer chromatography–surface-enhanced Raman
scattering†
Chaoping Yao,ab Fansheng Cheng,b Cong Wang,b Yonghong Wang,e Xiaowei Guo,a
Zhengjun Gong,c Meikun Fan*c and Zhiyou Zhang*d

Received 12th July 2013
Accepted 14th August 2013
DOI: 10.1039/c3ay41152d
www.rsc.org/methods
In this work, a fast, sensitive and convenient method for the on-site separation, identification and
determination of organophosphate pesticide methidathion in tea leaves was reported, by the use of
thin layer chromatography (TLC) in combination with surface-enhanced Raman spectroscopy (SERS). Five
different organophosphate pesticides have been successfully separated and identified. Factors that
affect the SERS detection sensitivity of methidathion, such as the brand of TLC plate, material and
concentration of metallic nanoparticles (NPs), have been examined. It is found that the limit of
quantification for methidathion is 0.1 ppm. Spiked tea samples of different kinds and brands containing
methidathion at the ppm level have been tested, with recovery rates in the range of 86–113%. The
proposed method for the fast on-site determination of pesticide may help to address food safety
concerns in the general public.

Introduction instruments suitable for portable analysis, and simple sample

Pesticides and insecticides are of great importance for agri-
culture. There are reports1,2 indicating that up to 50% of crops
are saved with the help of pesticides and insecticides. It is thus
natural to estimate that pesticide residue contamination in
foods is common. Nowadays, with the establishment of
modern analytical techniques such as HPLC, GC, and HPLC/
GC-MS, the detection of these residues could be realized in
central laboratories. Nevertheless, the practice of using these
modern analytical techniques generally takes a long time and
is not suitable for eld testing. These limits have greatly
hindered the trend of monitoring food quality at each
step during the manufacturing process – a movement to satisfy
the concerns of consumers in the modern food industry –
during which high sensitivity and specicity, miniaturized
a
Department of Optoelectronic Information, University of Electronic Science and
Technology of China, Chengdu, Sichuan, 610051, China
b
Chengdu Green Energy and Green Manufacturing R&D Centre, Chengdu, Sichuan,
610207, China
c
Faculty of Geosciences and Environmental Engineering, Southwest Jiaotong
University, Chengdu, 610031, China. E-mail: meikunfan@gmail.com
d
Institute of Nanophotonics Technology, School of Physical Science and Technology,
Sichuan University, Chengdu, 610064, China. E-mail: zhangzhiyou@scu.edu.cn
e
Center for Animal Disease Control and Prevention of Chongqing, Chongqing, 401147,
China
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c3ay41152d
pretreatment are required.3
Discovered in the 1970s, surface-enhanced Raman scattering
(SERS) has become one of the most important spectroscopic
analytical methods.4–6 The advantages of SERS are two-fold: it is
ultra-sensitive, and single-molecule SERS analysis has been
widely reported;7 SERS can also give identity information on the
analytes since it can provide characteristic vibrational nger-
prints of molecules. Furthermore, Raman spectrometers can be
easily miniaturized for eld applications with little or no
sacrice on their performance.8 Thus, there is tremendous
interest in taking advantage of this technique for applications
within different elds, such as biomedicine,9–11 homeland
security,8 environmental monitoring,12–14 and food quality
assurance.15–20
Thin layer chromatography (TLC) is a well developed tech-
nique for the fast separation of organic chemicals. Generally,
the identication of chemicals using TLC relies greatly upon
the retention time, which of course is not reliable in compli-
cated situations. The coupling of TLC with SERS has gained
wide attention since very early stages of SERS development.21,22
For example, apomorphine in human plasma has been
detected using TLC coupled with a LABRAM-HR800 system.23
Pozzi et al.24 used the TLC–SERS technique to analyze the main
alkaloid constituents in Syrian rue based on RAM II Vertex 70
spectrometer. Other works include the analysis of amino
acids,25 carotenoids26 and carotenoid components in indi-
vidual pollen grains,27 organic dyes and pigments.28,29

This journal is ª The Royal Society of Chemistry 2013 Anal. Methods


Analytical Methods
Evaluation of experimental conditions that inuence the TLC–
SERS performance has been reported.30,31 Nevertheless, as
pointed out by Li et al.,13 almost all these reports are per-
formed within a laboratory environment. That is, the TLC–
SERS method based on a portable Raman instrument for
on-site analysis is still scarce.
Methidathion is an organophosphate insecticide; its use is
banned in the European Community. The maximum residue
level in tea is 0.1 ppm.32 Up to now, various methods have been
developed, such as Gas Chromatography (GC) and High
Performance Liquid Chromatography (HPLC) with UV or uo-
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rescence spectroscopic detection.33 The limit of detection (LOD)
of 0.01 mg g
1 for methidathion in orange juice by GC coupled
with a ame photometric detector and 0.02 mg L
1 by HPLC has
been reported.34–36 However, these methods are more suitable
for accurate analysis within a central laboratory. A fast, on-site
screening method for this insecticide still needs to be
developed.
Here in this work, we demonstrate that by using the TLC–
SERS technique, Dursban, phoxim, parathion, methidathion
and isocarbophos can be successfully separated and identied
using a portable Raman spectrometer. For the rst time, the
rapid on-site determination of methidathion based on the
TLC–SERS technique has also been realized. The linear range is
0.1–10 ppm. Parameters that affect the sensitivity of the SERS
determination are also discussed. Different types of tea samples
spiked with methidathion at the ppm level have been analyzed.
The recovery rate is between 86 and 113%. These results
demonstrate that TLC–SERS can be applied for the rapid on-site
screening of methidathion in tea samples.
Experimental
Material
Silver nitrate (99%), sodium citrate (99%), Dursban, phoxim,
parathion, and methidathion, and isocarbophos were
purchased from Sigma-Aldrich. Trihydrate chloroauric acid was
purchased from Sinopharm. Jasmine tea, green tea, and oolong
tea were purchased from a local supermarket. TLC plates were
from Merck, Qingdao Haiyang and Anhui Liangchen, respec-
tively. 18.2 MU water was used throughout the experiments. All
other chemicals were of analytical reagent grade and used as
received.
Instruments
All 785 nm experiments were performed using a B&W Tek
innoRAM system. A 20 objective (N.A. ¼ 0.4) and 10% of laser
power (24 mW) was used. A 2F-2 UV lamp (Shanghai An-ting,
China) was used to identify the spots on the TLC plates (high
concentration only). A UWave-1000 microwave (Sineon Micro-
wave) was used to synthesize the Ag NPs. GC-MS analysis was
performed using a Thermo Scientic DSQ II Series Single
Quadrupole GC/MS, USA. High-purity water was from a Nano-
pure system from Thermo Scientic. Gaussian calculation was
done on a Westgrid computer cluster at the University of
Victoria using Gaussian 09.
Anal. Methods
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Methods
Preparation of metallic NPs
Synthesis of Ag NPs. 1 mM silver colloids were prepared
according to the method of Lee and Meisel.37 Typically, 50 mL of
1.0 mM of AgNO3 aqueous solution was heated to boiling in a
microwave oven with vigorous stirring and sonicating and then
2 mL 1% (w/v) trisodium citrate was quickly added. The solution
was kept boiling for 1 h and the color changed to pale yellow.
Aer that, the solution was allowed to cool to room temperature
with continuous stirring. This solution is named 1 mM Ag NPs
thereaer. The preparation of 0.5 and 2 mM Ag NPs followed
the same procedure but with the concentration of silver nitrate
and sodium citrate changed accordingly.
Preparation of gold colloids. For 40 nm Au NPs, the method of
Bauer et al.38 was used. 200 mL of 0.01% w/v HAuCl4 aqueous
solution was heated to boiling by microwave with vigorous
stirring and sonicating. 2 mL of 1% sodium citrate aqueous
solution was injected into the boiling solution. The mixture was
kept stirring and boiling for 10 min under sonication. Then the
heating was stopped but stirring was continued until the solu-
tion cooled down to room temperature.
13 nm gold colloids were prepared according to the method
of Natan and co-workers.39 50 mL of 1 mM HAuCl4 aqueous
solution was heated to boiling by microwave with vigorous
stirring and sonicating. 5 mL of 38.8 mM sodium citrate
aqueous solution was injected into the boiling solution. Then
the solution was kept boiling for 15 min under sonication and
then the solution was allowed to cool to room temperature with
continuous stirring.
Chromatography. All the TLC plates were activated in an
oven at 80  C for 30 min. On each plate, a line parallel to the
short side was drawn with a pencil, where the distance to the
edge is about 5 mm, slightly higher than the developing solvent.
For the separation of different organophosphate pesticides,
5 mL of sample solution containing pesticides at 50 ppm
(10 ppm for methidathion), respectively, was spotted onto the
line, and allowed to develop.
For the determination of methidathion, 5 mL aliquots of
sample solution at different concentration levels were spotted
on the line, along with 5 mL of 1000 ppm methidathion standard
solution spotted side by side. The latter serves as a position
mark, through which the exact spot of the methidathion in the
sample aer development was calculated. Chromatography was
performed in a developing chamber with the optimal eluent
(9 : 1 v/v petroleum ether/ethyl acetate). Aer that, the position
of the high concentration standard was marked with a hand-
held UV lamp with 254/365 nm wavelength. The exact position
of the methidathion in the sample was then calculated and
marked with a pencil. Later, to each spot 10 mL of a solution of
the prepared silver colloids was added. Finally, the SERS spectra
for each separated spot were recorded using a portable Raman
spectrometer (24 mW laser power, and 800 ms  5 integration
time).
Sample pretreatment. The TLC–SERS method was designed
with the on-site detection of organophosphorus pesticide
(especially methidathion) within tea in mind. For each type of
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Paper Analytical Methods

tea, into two beakers labeled as spike and control, 1g of tea

leaves were weighed and added, respectively. Then, 55.4 mL of
50 ppm methidathion–ethyl acetate solution was added into the
spike group, at the same time 55.4 mL of ethyl acetate was added
into the control group. The beaker was then sealed with Paraf-
ilm and allowed to stand for 10 min. Later, 3.185 mL acetone
was added into the each beaker. It was sealed again and allowed
to stand for another 10 min. The mixture was then ltered, and
the ltrate was poured into another beaker, which was then
placed in a fume hood and allowed air-dry. Then, 0.637 mL
acetone was added in the beaker to dissolve the insecticide.
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Finally, 5 mL of the solution was analyzed according to the

procedure introduced ealier.
Fig. 2 SERS spectra of methidathion (5 mL, 5 ppm) using TLC plates (Anhui
Result and discussion Liangchen) with different metal colloids (silver colloids and gold colloids) and
concentrations. Top to bottom: the concentrations of silver colloids and gold
SERS analysis of sample spots on TLC plate: effect of the TLC colloids were 0.5 mM Ag NPs (a), 1 mM Ag NPs (b), 2 mM Ag NPs (c), 13 nm
plate material Au NPs (d), 40 nm Au NPs (e), respectively. Laser power, 24 mW; integration time:
800 ms  5.
When examining the Raman spectra of the sample spots on the
TLC plates, the background Raman scattering of the TLC plate
may also contribute a positive or negative effect.40,41 Therefore,
5 ppm methidathion was sampled on the TLC plate. Then, 10 mL
before coupling of TLC with SERS for methidathion detection, it
NPs made of silver or gold at different sizes and concentrations
is necessary to investigate how different TLC plate brands affect
were added onto the insecticide spot. SERS spectra were recor-
the SERS spectrum of the analyte. As shown in Fig. 1, TLC plates
ded using a B&W Tek innoRAM spectrometer (BWS445-785S). As
are generally weak Raman scatterers and give little background
depicted in Fig. 2, the SERS signal of the methidathion sample
interference. However, the SERS intensity does vary with TLC
shows an obviously increased signal with a colloidal silver
plates from different producers. It is clear that TLC plates with
concentration over 0.5–2 mM. This is not surprising, since silver
uorescent indicators from AnHui Liangchen (silica 80-GF254)
NPs are considered a much better SERS substrate compared
gave the best SERS signal of the pesticide. Therefore, we decided
to use this TLC plate for our on-site pesticide detection.42

SERS analysis of sample spots on the TLC plate: effect of the

material and concentration of NPs
The material and concentration of NPs are very important
parameters to obtain a strong SERS signal,43 and here we eval-
uate the effects of both the NPs material and concentration on
the SERS signal of methidathion on the TLC plate. First, 5 mL of

Fig. 1 SERS spectra of methidathion (5 mL, 5 ppm) using different TLC plate
materials. All TLC plates were spotted with 10 mL Ag NPs with a concentration of
1 mM. SERS spectra obtained for a–c used TLC plates from Anhui Liangchen,
Merck, and Qingdao Haiyang, respectively; d was the blank spectrum of Anhui
Liangchen.
Fig. 3 (a) Photograph of the separated spots on the TLC plate under UV light
irradiation. (b) SERS spectra obtained from the spots on the TLC plate after
separation: (a–e) analyte concentration in the sample: 50 ppm, 50 ppm, 50 ppm
and 10 ppm, 50 ppm for Dursban, phoxim, parathion and methidathion, iso-
carbophos, respectively. Laser power: 24 mW; integration time: 800 ms  5.

This journal is ª The Royal Society of Chemistry 2013 Anal. Methods


Analytical Methods
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Fig. 4 (a–g) SERS spectra of methidathion with concentrations of 0, 0.1, 0.5, 1,
2.5, 5, and 10 ppm, respectively. Inset shows the linear regression of methidathion
SERS intensity. The data points are obtained from an average of 5 experiments
and the error bar is given in the inset. Equation: Y ¼ 1854.21X + 2789.4; r2 ¼
0.9529.
Table 1 Test of methidathion in spiked tea samples
Tea type Jasmine tea Oolong tea
Spiked/ppm 5.00 5.00
Detected/ppm 5.66 4.87
Recovery rate (%) 113.2 97.5
GC-MS/ppm 4.94 5.36
with other metals in the visible range. On the other hand, we
found that with the increasing concentration of the silver
colloid, the SERS signal of the pesticide increases. It should be
noted that for 2 mM Ag NPs, the colloidal solution is not stable
due to stronger NPs interaction. Furthermore, as can be seen in
Fig. s2c,† the shape and size varies a lot for 2 mM Ag NPs. As a
result, the SERS signal varies among batches. Hence, 1 mM was
chosen for the concentration of the silver colloids to carry out
the next experiments.
Combination of TLC with SERS for simultaneous on-site
detection of methidathion in tea
Combination of TLC with SERS for simultaneous on-site qual-
itative detection was investigated for synthetic samples con-
taining a number of common organophosphorus pesticides.
The components in the synthetic sample were separated using a
silica 80-GF254 TLC plate (eluent of 9 : 1 v/v petroleum ether/
ethyl acetate). The separated spots were then located under UV
illumination (Fig. 3a). Finally the SERS spectra were recorded in
the presence of 1 mM silver colloids, which were shown in
Fig. 3b.
In addition to qualitative detection, the quantitative detec-
tion of methidathion was also investigated. Methidathion
solutions of different concentrations were prepared with ethyl
acetate. 5 mL of methidathion–ethyl acetate solution was placed
on the right at the bottom of a TLC plate; at the same time, 5 mL
of 1000 ppm methidathion–ethyl acetate solution was spotted
on the le at the bottom as the position marker, and then
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chromatographic separation was performed in a chamber with
the optimized eluent. Next, to each spot, 10 mL of 1 mM silver
colloids was added. Fig. 4 illustrates the SERS spectra of
methidathion concentrations ranging from 0.1 to 10 ppm,
respectively. Then, the peak intensity at 500 cm
1, which
belongs to O–P–O and S–P]S stretching according to Gaussian
calculation, was plotted against the concentration, as shown in
the inset of Fig. 4. It is clear that a linear relationship was
observed. The band at 405 cm
1 can be assigned as C]N–N
wagging and P–O–C scissoring. The shoulder at 517 cm
1 can
be assigned as C–S–C scissoring.
Facile on-site detection of methidathion in spiked tea samples
To further show the application of the proposed method, TLC–
SERS was employed for the on-site detection of methidathion
spiked tea samples. Preparation of the spiked samples, sepa-
ration by TLC, and analysis using SERS were as described above.
In the experiment, three kinds of tea (jasmine tea, green tea,
and oolong) were examined. Furthermore, it was validated
using the GC-MS technique. All results are shown in Table 1.
Further information on the GC-MS detection of methidathion
Green tea can be found in Fig. s4 and Table s1.†
5.00
5.09
101.9
Conclusion
5.43
The results presented herein demonstrate that the proposed
TLC–SERS technique is an excellent candidate for simulta-
neously detecting various organophosphate pesticides in tea,
both qualitatively and quantitatively. More importantly, TLC–
SERS is preferable for the on-site detection of such a type of
pesticides residue since the time needed for analysis is very
short compared with techniques used in a central laboratory.
This may help to address the urgent food safety concerns of the
general public.
Acknowledgements
The authors thank the support from the National Natural
Science Foundation of China (NSFC, grant no. 21105092,
21277131). The authors also thank Dr Irina Paci and Ms Tatiana
Popa for helping the Gaussian calculation.
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