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pubs.acs.org/ac

A Novel Photoelectrochemical Sensor for the Organophosphorus

Pesticide Dichlofenthion Based on Nanometer-Sized Titania Coupled
with a Screen-Printed Electrode
Hongbo Li,, Jing Li, Zhanjun Yang, Qin Xu, and Xiaoya Hu*,

College of Chemistry and Engineering, Yangzhou University, 88 South University Avenue, Yangzhou 225002, P. R. China
College of Chemistry and Biology Engineering, Yancheng Institute of Technology, 9 Yingbin Avenue, Yancheng 224051, P. R. China
ABSTRACT: A novel photoelectrochemical sensor for detection of the organophosphorus pesticide (OP) dichlofenthion
using nanometer-sized titania coupled with a screen-printed
electrode is presented. Nonelectroactive dichlofenthion can be
indirectly determined through the photocatalytical degradation
of dichlofenthion with nanometer-sized titania. The electrochemical characterization and anodic stripping voltammetric
performance of dichlofenthion were evaluated using cyclic
voltammetric (CV) and dierential pulse anode stripping
voltammetric (DPASV) analysis, respectively. DPASV analysis was used to monitor the amount of dichlofenthion and provide a
simple, fast, and facile quantitative method for dichlofenthion. Operational parameters, including the photocatalysis time, pH of
buer solution, deposition potential, and accumulation time have been optimized. The stripping voltammetric response is linear
over the 0.02
0.1 and 0.2
1.0 mol/L ranges with a detection limit of 2.0 nmol/L. The assay result of dichlofenthion in green
vegetable with the proposed method was in acceptable agreement with that of the gas chromatograph
mass spectrometer
(GC
MS) method. The promising sensor opens a new opportunity for fast, portable, and sensitive analysis of OPs in
environmental samples.

rganophosphate pesticides (OPs), one group of the most

commonly used pesticides in agriculture, can disrupt cholinesterase and lead to cholinergic dysfunction and death, which
endanger the health of both humans and animals.1
6 In concern
over health and the environment, limiting the amount of OPs in
agriculture and prohibiting the use of hypertoxic OPs are critical
worldwide. Recently, some hypertoxic OPs, such as parathion
and methyl parathion, were banned or severely restricted in
agriculture by the United Nations Environment Programme
(UNEP) and the Food and Agricultural Organization (FAO).6
In view of the major concerns regarding the toxicity of OPs, the
addition of OPs residue determination in environment samples
and agricultural products is urgently needed. Although, instrumental methods such as GC
MS and liquid chromatogram

mass spectrometer (LC
MS) oer high sensitivity and specicity and have the potential for simultaneous determination of
multiple analogues,7
11 the associated high costs and timeconsuming labor requirements are necessary. Enzyme-based
biosensors have emerged in the past few years as the most
promising alternative for direct monitoring of pesticides.12,13
Various inhibition and noninhibition biosensor systems, based
on the immobilization of acetylcholinesterase (AChE) or OP
hydrolase (OPH) onto various electrochemical or optical transducers, have been proposed for eld screening of OP neurotoxins.14
25 However, the method needs long analysis time and
extensive sample handling with multiple washing steps. In recent
r 2011 American Chemical Society

years, OP pesticide kits have become commercially available that

oer advantages, including portability, rapid turnaround time,
and cost-eectiveness. Drawbacks of these test kits include the
complicated handling procedure and often a lack of sensitivity
(only ppm level) and precision. Moreover, in most cases, these
tests are qualitative or semiquantitative and show false positive
and negative results. To avoid the use of enzymes and antibodies,
molecular imprint technologies with high selectivity toward
specic OP species have been developed and applied to the
detection of pesticides in environmental samples.26,27 Electrochemical detection of nitroaromatic OPs showed great promise
when it was coupled with dierent separation technologies, such
as high-performance liquid chromatography28 or capillary electrophoresis.29 Lin and co-workers fabricated an electrochemical
sensor for nitroaromatic OPs based on a gold electrode modied
with zirconia nanoparticles.4 Electrochemical detections combined with chromatography are used as reference methods but
present some drawbacks that are similar to GC
MS or LC
MS
methods, and the reproducibility and stability of the modied
electrode are not easily ensured for long-term assay. Therefore,
these methods are also restricted to a limited analyte spectrum.
Received: March 19, 2011
Accepted: May 23, 2011
Published: May 23, 2011
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Analytical Chemistry
Searching for a new, simple, low-cost, portable, and sensitive
analytical method is of considerable interest.
Titanium dioxide has been demonstrated to be a very ecient
catalyst and especially suitable to work by solar UV light.30 The
mechanism of the photocatalytic decomposition of various organic
molecules on TiO2 surfaces has been reported elsewhere.31
35
When TiO2 is irradiated by photons whose energy exceeds the
TiO2 band gap (3.2 eV), electrons are excited from the valence
band to the conduction band, resulting in the formation of
charge carrier pairs, that is, a hole (h) and an electron (e
).
These charge carriers can migrate to the surface and react with
adsorbed molecules, unless recombination occurs rst. The hole
typically oxidizes adsorbed water to a hydroxyl radical (OH),
whereas the electron reduces adsorbed molecular oxygen to a superoxide radical anion (O2
). These oxidizing radicals react with
adsorbed organic molecules, inducing electroactive product production and oxidative degradation to carbon dioxide and water nally.36,37
The OPs insecticides are comprised within the 10 most widely
used pesticides, such as dichlofenthion, bromophos ethyl, and
parathion ethyl, which can be changed into electroactive hydroxysubstituted aromatic ring compounds by photocatalytic degradation.38 However, to the best of our knowledge, photocatalytic
degradation combined with electrochemistry for determination
of OPs insecticide residues has not been reported at present. In
this paper, we describe a novel and simple photoelectrochemical
sensor for dichlofenthion (Figure 1) based on nanometer-sized
titania photocatalysis coupled with a screen-printed carbon electrode (SPCE). The proposed method is promising for detecting
dichlofenthion residue in eld-screening scenarios.

EXPERIMENTAL SECTION
Reagents and Solutions. The UV light (20 W, = 254 nm)
was obtained from Wisbay M&E Co., Ltd. (Shenzhen, China).
Dichlofenthion for calibration was purchased from SigmaAldrich, and a 0.003 mmol/L stock solution was prepared with
pH 4.0 phosphate buffer solutions (PBS), which was used as the
supporting electrolyte. The working solutions were prepared by
diluting the corresponding standard stock solution by PBS.
Titanium dioxide (Degussa P25), a known mixture of 65%
anatase and 35% rutile form with an average particle size of
30 nm that was nonporous with a reactive surface area (BET) of
50 ( 15 m2/g, was used as received for all photocatalytic
experiments, and the 0.125 mmol/L solution was also prepared
with pH 4.0 PBS. Other reagents were commercially available
and were of analytical reagent grade. Solutions were prepared
with ultrapure water from a Millipore Milli-Q water purification
system (Billerica, MA).
Apparatus. The cyclic voltammograms were recorded between 0.0 and 1.2 V at a scan rate of 100 mV/s and differential
pulse anode stripping voltammograms with an amplitude of
50 mV, a pulse width of 0.2 s, and a pulse period of 0.5 s.
Measurements were performed using an electrochemical analyzer (CHI760D, CH Instruments, Shanghai, China) connected to
a personal computer. SPCEs were obtained from Gwent group
(Torfaen, United Kingdom) that included a three-electrode
configuration printed on the same strip. The strips had a 2 mm
diameter disk screen-printed carbon working electrode, a counter electrode, and a Ag/AgCl pseudoreference electrode, an
insulating layer serves to define the working electrode area.
Electrochemical experiments were carried out at room temperature (25 C). The model surveyor apparatus used in this study

ARTICLE

Figure 1. Structure of dichlofenthion.

was a GC
MS [QP 5000 Shimadzu equipped with capillary

column (DB-1701, 30 m  0.25 mm 0.25 m)]. For GC
MS,
the column temperature was maintained at 40 C for 1 min and
then programmed to 110 C at 30 C/min, to 230 C at 5 C/
min, and then to 280 C at 10 C/min, and held for 5 min. The
carrier gas at a rate of 1.2 mL/min was helium, with purity of
99.999%. The injection port temperature was 280 C, and the
splitless mode was used for injection of 1 L volume with the
valve opened for 30 s. The ionization energy was 70 eV. The ion
source and the GC
MS interface were kept at 220 and 280 C,
respectively.
Photocatalysis and Electrochemical Detection. Ten milliliters of the dichlofenthion solution containing the TiO2 powder
(0.1 mmol/L) were magnetically stirred before the illumination.
The suspension was left for 30 min in the dark in order to achieve
the maximum adsorption of pesticides onto the semiconductor
surface. Subsequently, a drop of suspension was dripped into the
fixed cylindrical cell and then was irradiated under the UV
radiation for 20 min with the distance of 10 cm between the
UV light and liquid level. Afterward, the photocatalytic degradation compound of dichlofenthion was detected by differential
pulse anode stripping voltammetric (DPASV) analysis, and the
oxidation peak current was proportional to the concentration of
dichlofenthion. The procedure is shown in Figure 2. DPASV
experiments comprised an electrochemical deposition step
at
0.2 V for 180 s, an equilibration period of 2.0 s, and a
differential pulse voltammetric (DPV) stripping scan usually
from 0.6 to 0.9 V. Before each measurement a preconditioning
step (for cleaning of the electrode) at a potential of 1.0 V was
applied for 60 s.
Preparation and Detection of Green Vegetable Samples.
The green vegetable samples were prepared as follows: 4 g of
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Figure 2. Scheme of the photoelectrochemical sensor for dichlofenthion: (A) diagram of the SPCE, (B) a drop of suspension was
dripped into the cylindrical cell xed of the SPCE, (C) the suspension
was irradiated by UV, and (D) dierential pulse anode stripping
voltammogram of the irradiated dichlofenthion.

green vegetable leaves were chopped into small pieces and then
equably sprayed with a known amount of dichlofenthion stock
solution. After placed in a glass disk for 8 h, the contaminated
sample was taken out and washed with water three times.
Subsequently, the residual dichlofenthion on the leaves was
extracted with hexane. All the extract liquid was collected for
concentration and then diluted with anhydrous ethanol. Afterward, the liquid was filtered through a 0.45 m membrane filter,
transferred into a 10 mL volumetric flask that was brought to
volume with ethanol, and reserved for GC
MS assay. For
electrochemical measurement, 10.0 L samples were added to
10.0 mL of PBS medium and then analyzed by the same DPASV
procedure as the dichlofenthion standard solution. Then, a
quantitative dichlofenthion stock solution was added into the
above measured sample system, and DPASV was started under
the same condition.

RESULTS AND DISCUSSION

Choice of Extractant. Green vegetables contain large amounts
of ascorbic acid and other components. It is necessary to separate
ascorbic acid from the matrix because much ascorbic acid can
interfere with the electrochemical determination of dichlofenthion.
Ascorbic acid is easily dissolved in water but it is difficult to
dissolve in low-polarity organic solution; the opposite is true for
dichlofenthion. So, the low-polarity organic solvent hexane was
chosen as the extractant for dichlofenthion.
Electrochemical Behavior of Dichlofenthion and Its
Photolysis Compound. The electrochemical behaviors of dichlofenthion and its photolysis compound were studied, respectively. As can be seen in Figure 3A, there is no oxidation peak at
curve a or b in PBS (pH 4.0), which indicates that the oxidation
reaction of PBS or dichlofenthion does not take place at the
potential window from 0.0 to 1.2 V. However, one oxidation peak
markedly appears at curve c for the 10.0 mol/L photocatalyzed
dichlofenthion, which demonstrates that the photolysis compound of dichlofenthion has good electrochemical activity. The
photodegradation products of dichlofenthion have been reported by Konstantinous team, and 2,4-dichlorophenol and
p-chlorophenol were two of the species.38 Moreover, 2,4-dichlorophenol and p-chlorophenol are electroactive species, and their

Figure 3. (A) CV curves of photocatalysis before and after in 0.1 mol/L

pH 4.0 PBS containing 10.0 mol/L dichlofenthion at SPCE: (a) blank
buer, (b) in the presence of dichlofenthion, and (c) in the presence
of photocatalyzed dichlofenthion. (B) The cyclic voltammograms of
10.0 mol/L of 2,4-dichlorophenol (a) and p-chlorophenol (b) in
0.1 mol/L pH 4.0 PBS.

circulation voltammetric behaviors are demonstrated in Figure 3B.

As can be seen from the oxidation peak of 2,4-dichlorophenol,
p-chlorophenol, and the photolysis compound, three oxidation
peaks nearly appeared at 0.83 V, which confirms that the curve c
in Figure 3A can be attributed to the oxidation of 2,4-dichlorophenol and p-chlorophenol. Therefore, dichlofenthion can be
indirectly detected by its photolysis compounds.
Optimization of the Experimental Conditions for Dichlofenthion Measurement. Since the proposed method for the
determination of dichlofenthion is based on the electrochemical
signal being proportional to the concentration of photocatalyzed
dichlofenthion, it is more important to improve the sensitivity of
the proposed method. The effect factors for measurements
concerning photocatalysis time, pH of buffer solution, deposition
potential, and accumulation time were studied in detail.
Optimal Conditions for Photocatalysis Time. The analytical
performance of the photoanalysis was related to the concentration of electroactive hydroxy-substituted aromatic ring compounds in the measuring system. As can be seen in Figure 4,
the DPV peak current increased with the increasing photocatalysis time from 2 to 25 min, and the photoelectrochemical sensor
showed the increasing response until a photocatalysis time of
20 min (inset of Figure 4). Longer photocatalysis time did
not obviously improve the response. It can be explained that
more photodegraded species chlorophenols were produced as
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Figure 4. DPV responses of the photoelectrochemical sensor with

increasing photocatalysis time in 0.1 mol/L pH 4.0 PBS containing
10.0 mol/L dichlofenthion (a
g). The inset shows the eects of
photocatalysis time of dichlofenthion on the amperometric response of
the photoelectrochemical sensor.

Figure 6. Eects of deposition potential (A) and accumulation time

(B) on DPASV peak current of photocatalyzed dichlofenthion, the other
conditions being the same as in Figure 5.

Figure 5. Eect of PBS buer solution pH on the DPV peak current

of photocatalyzed dichlofenthion, the other conditions are the same
as in Figure 4.

the photodegradation progresses with the increase of the time.

Meanwhile, some of other photodegraded species may be
absorbed on the titanium dioxide surface and prevent the process
of photodegradation; i.e., the titanium dioxide catalyst may be
poisoned. In addition, the resulting charge carrier pairs, a hole
(h) and an electron (e
), recombined first, resulting in fewer
hydroxyl radicals and superoxide radical anions being obtained,
so that it was very difficult to completely photodegrade dichlofenthion. Considering the optimal sensitivity and analysis efficiency, therefore, the photocatalysis time of 20 min was chosen
as the optimal photocatalysis condition for the detection of
dichlofenthion.
Optimal Conditions for pH. Variation of the peak current as a
function of solution pH in the range of 3.0
8.0 is shown in
Figure 5. Due to the acidic hydroxyl group of 2,4-dichlorophenol
and p-chlorophenol, the photoproducts of dichlofenthion,38 the
pKa value of them is about 7.9 and 9.4, respectively.39 Therefore,
the DPV peak current for chlorophenol is expected for a pH less
than 9.4. In fact, under the optimal condition of photocatalysis
time, it was clear that the DPV peak current of chlorophenol
increased gradually with the increasing buffer solution pH and

reached maximum at pH 4.0. Afterward, it gradually decreased up

to pH 7.0 and then decreased rapidly at higher pH. It can be
explained that the concentration of neutral chlorophenol reached
the maximum at pH 4.0 and the more neutral chlorophenol can
be oxidated on the SPCE. Therefore, pH 4.0 was chosen as the
optimum pH in the subsequent measurements.
Optimum of Deposition Potential and Accumulation Time.
Under aforesaid optimal conditions, the more sensitive electrochemical response depends on the accumulation of photocatalyzed dichlofenthion at the SPCE. As shown in Figure 6A, when
the accumulation time was first fixed at 60 s and the deposition
potential changed from
0.6 to 0.2 V, the peak current for
10.0 mol/L photocatalyzed dichlofenthion first increased rapidly
until it reached maximum at
0.2 V and then gradually
decreased. It may be explained that the concentration of neutral
chlorophenol reached a maximum in pH 4.0 buffer solutions and
the deposition potential of
0.2 V was close to the zero charge
potential. Therefore, more or less than
0.2 V would result in
gathering of more negative or positive charge on the surface of
SPCE and further prevent the neutral chlorophenol from reaching on the surface of the SPCE. So a negative potential of
0.2 V
was favorable to the deposition of photocatalyzed dichlofenthion. Then,
0.2 V was fixed during the optimizing of accumulation time. With the increasing accumulation time, the peak
height dramatically increased until it reached a maximum at 180 s
and then remained a constant value (Figure 6B), indicating
that the accumulation of photocatalyzed dichlofenthion on
the electrode surface nearly reached a saturation state at 180 s.
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Table 1. Measurement Results of Dichlofenthion in Green

Vegetable Sample (n = 3)a
GC
MS this method

Figure 7. DPASV analysis of increasing dichlofenthion concentration,

from bottom to top, 0.02, 0.04, 0.06, 0.08, 0.1, 0.2, 0.4, 0.6, 0.8, and
1.0 mol/L, respectively. The inset shows the calibration curve.
Electrochemical stripping detection condition is the same as in Figure 6.

Thus,
0.2 V and 180 s were selected as the optimal deposition

potential and accumulation time, respectively.
Analytical Performance. The DPASV analysis of dichlofenthion showed a strong signal under optimum experimental
conditions. Well-defined peaks, proportional to the concentration of the corresponding dichlofenthion, were observed. A linear
relationship between the stripping current and the concentration
of dichlofenthion was obtained covering the concentration
ranges from 0.02 to 0.1 and 0.2 to 1.0 mol/L, the linear
regression equations being I (A) = 0.5210C 0.6009 and
I (A) = 2.111C 0.3944, with two correlation coefficients of
0.9993 and 0.9967, respectively (Figure 7). The detection limit of
2.0 nmol/L was determined at a signal-to-noise ratio of 3, which
was lower than that reported (4 ng/mL, 12.7 nmol/L) so far with
a polyclonal antibody-based biosensor.40 The assay precision of
the photoelectrochemical sensor was evaluated by assaying
dichlofenthion at two levels for nine replicative measurements.
The assay variation coefficients with this method were 2.6% and
3.5% at 0.05 and 0.8 mol/L concentrations of dichlofenthion,
respectively, showing a good repeatability. The assay variation
coefficients at these concentrations on nine photoelectrochemical sensors made independently were 3.9% and 5.7%, respectively, indicating acceptable fabrication reproducibility.
Interference of Foreign Species. Under the optimal conditions, each interferent was mixed with TiO2 and irradiated. The
effects of various coexisting substances were studied by introducing each one to the buffer solution containing 0.1 mol/L
dichlofenthion. Each one was considered as an interfering agent,
when the electrochemical signal exhibited a deviation more than
(5%. The interference of some substances on the stripping
voltammetric measurements was examined. A 103-fold mass ratio
of NH4, K, Na, Zn2, Ca2, Mg2, Ba2, Al3, Cu2, SO42-,
Cl
, NO3
, and PO43
; 100-fold mass ratio of amino acid,
glucose, and sucrose, 50-fold mass ratio of Fe3, Fe2, Co2, and
Ni2; 10-fold mass ratio of parathion methyl, parathion, and
chlorpyrifos; and 5-fold ascorbic acid had no influence on the
determination of dichlofenthion. However, 20 nmol/L phenol and
chlorophenol could increase the current response and brought
positive interference for 0.1 mol/L dichlofenthion measurement.
Analysis of Real Sample. To demonstrate the feasibility of
the sensor applied to the practical samples, the determination
of dichlofenthion in green vegetable was performed. The green

added

found

(mol/L) (mol/L)

recovery

analyte

(mol/L)

(mol/L)

(%)

dichlofenthion

0.078
0.075

0.076
0.072

0.1
0.4

0.172
0.493

96.0
105.3

0.081

0.079

0.8

0.871

99.0

n is the repetitive measurements number.

vegetable samples were pretreated as mentioned in section 2.4

and diluted with ethanol to the required volume. The sample
solution was injected directly into 10 mL of PBS (pH 4.0), and
the residual dichlofenthion content was detected by means of
DPASV analysis using the dichlofenthion sensor. Subsequently,
an amount of standard dichlofenthion solution was added into
the above solution, and the recovery of the added dichlofenthion
was observed to be good for three determinations. The results
obtained by the proposed method also accorded very well with
those obtained by GC
MS. The results were summarized in
Table 1. These results implied that the sensor was capable of
practical applications.

CONCLUSIONS
We have demonstrated a sensitive, simple, fast, and portable
photoelectrochemical sensing protocol for the organophosphorus pesticide dichlofenthion based on the use of nanometersized titania coupled with SPCE. The promising DPASV characteristics provide a facile quantitative method for dichlofenthion.
The results obtained from this work implied that the combination of a disposable SPCE with a portable electrochemical
instrument would benet the eld monitoring of dichlofenthion.
The proposed photoelectrochemical sensing technology is thus
expected to monitor the other nonelectroactive OPs and opens
new opportunities for detecting OPs in the environment, public
places, or workplaces and for monitoring the exposures of
individuals to chemical warfare agents.
AUTHOR INFORMATION
Corresponding Author

*Tel.: 86 514 87971818. Fax: 86 514 87311374. E-mail:

xyhu@yzu.edu.cn.

ACKNOWLEDGMENT
We gratefully acknowledge the nancial support from the
Natural Science Foundation (no. 20705030, no. 20875081, no.
21075107, no. 21005070) of China, projects of the 863 Plan
(2009AA03Z331), and the Natural Science Foundation (XKY2009009) of Yancheng Institute of Technology.
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