Microchim Acta (2010) 169:367–373
DOI 10.1007/s00604-010-0366-5
ORIGINAL PAPER
Square wave voltammetric determination of Hg(II) using
thiol functionalized chitosan-multiwalled carbon nanotubes
nanocomposite film electrode
Wenfang Deng & Yueming Tan & Yunyong Li & Yanqing Wen & Zhaohong Su &
Zhao Huang & Suqing Huang & Yue Meng & Qingji Xie & Yueping Luo & Shouzhuo Yao
Received: 6 February 2010 / Accepted: 18 April 2010 / Published online: 30 April 2010
# Springer-Verlag 2010
Abstract Covalent tethering of cysteamine to chitosan
using glutaraldehyde yields thiol-functionalized chitosan
(CS-SH). It was cast on a glassy carbon electrode which is
found to be very stable in acidic solutions and to possess a
strong affinity for Hg(II) ions as confirmed by quartz
crystal microbalance measurements. A glassy carbon
electrode modified with a nanocomposite made from CS-
SH and multiwalled carbon nanotubes was applied for
square wave voltammetric determination of Hg(II). The
procedure comprises the steps of (a) chemical accumulation
of Hg(II) under open-circuit condition and (b) electrochem-
ical determination of Hg(II). Linear responses are obtained
in the range from 10 to 140 nM, with a limit of detection of
3 nM (S/N=3) under optimized conditions. The electrode
was applied to the determination of Hg(II) in water samples
with satisfactory recoveries.
Keywords Thiol functionalized chitosan . Multiwalled
carbon nanotubes . Hg(II) . Square wave stripping
voltammetry
W. Deng : Y. Tan : Y. Li : Y. Wen : Z. Su : Z. Huang : S. Huang :
Y. Meng : Q. Xie (*) : S. Yao
Key Laboratory of Chemical Biology and Traditional Chinese
Medicine Research (Ministry of Education of China),
College of Chemistry and Chemical Engineering,
Hunan Normal University,
Changsha 410081, China
e-mail: xieqj@hunnu.edu.cn
Y. Luo
Environmental Monitoring Center of Hunan Province,
Changsha 410004, China
Introduction
Mercury is one of the most well-known toxic metals
possessing a great danger for people and the environment,
so its trace analysis is important. In recent decades, a
number of optical sensors have been reported for the
determination of mercury, which generally have good
sensitivity, selectivity and reproducibility [1–3]. Electro-
chemical techniques, especially the anodic stripping vol-
tammetry, have also been applied to the determination of
mercury with chemically modified electrodes, which offer
several advantages, including remarkable sensitivity, suffi-
cient selectivity, inherent miniaturization and portability,
low cost, and high compatibility with advanced micro-
machining technologies [4–9].
Chitosan (CS) is a polysaccharide derived by deacetyla-
tion of chitin that displays excellent film-forming ability,
good adhesion, high mechanical strength, and susceptibility
to chemical modifications due to the presence of reactive
hydroxyl and amino functional groups [10]. CS as a
popular biocompatible polymer has been used for protein
immobilization and for the development of biosensors [10–
12]. In addition, because CS has a high content of hydroxyl
and amino groups along its chains and possesses a high
metal-chelating ability, it is widely studied as a material for
wastewater treatment [13, 14] and electrochemical determi-
nations of metals ions in aqueous solutions [15, 16].
Moreover, the chemical modifications of CS can introduce
new chelating groups along the CS chains, which can not
only prevent its dissolution in acidic solutions but also
improve the adsorption capacity and selectivity of an
existing group for a specific metal ion [17–19]. Carbon
nanotubes (CNTs) as a kind of relatively new nanomaterial,
which display attractive structural, mechanical, and elec-
tronic properties, including improved electrochemical ac-
368
tivity [20], have proven potential as superior sorbents for
removing divalent metal ions from aqueous solution based
on chemical interactions between the metal ions and the
surface functional groups of the CNTs [21]. In fact, CNTs
(or their nanocomposites) modified electrodes are favorable
in voltammetric and electrochemical stripping methods for
determination of metal ions [22–24]. In our opinion, it is
interesting to explore the applications of new structure-
modified CS-CNTs nanocomposite for anodic stripping
voltammetric determination of metal ions.
Herein, we synthesize thiol functionalized CS (CS-SH)
via covalent attachment of cysteamine to CS chains with
glutaraldehyde, followed by sodium borohydride reduction.
The electrode-supported CS-SH film is highly stable in
acidic solutions and can chelate with Hg(II), as confirmed
by quartz crystal microbalance (QCM). A glassy carbon
electrode (GCE) modified with a CS-SH-multiwalled
carbon nanotubes (MWCNTs) nanocomposite is applied
for square wave voltammetric determination of Hg(II) with
good performance.
Experimental
Instrumentation and reagents
All electrochemical experiments were performed on a
CHI660C electrochemical workstation (CH instrument
Co., USA, http://www.chinstruments.com/). A conventional
three-electrode electrolytic cell was used. The three-
electrode system consisted of a GCE (3.0 mm diameter)
as the working electrode, a KCl-saturated calomel electrode
(SCE) as the reference electrode, and a platinum foil as the
counter electrode. All potentials in this work are reported
versus SCE. QCM studies were carried out with a
computer-interfaced HP4395A impedance analyzer (Agi-
lent, USA, http://www.home.agilent.com/). AT-cut 9-MHz
gold-coated piezoelectric quartz crystals (PQCs, 12.5 mm
diameter, Model JA5, Beijing Chenjing Electronics Co.,
Ltd., China, http://www.china707crystal.com/) were used.
The gold electrode of 6.0-mm diameter on one side of the
PQC was exposed to the solution, while the other side of
the PQC faced air. Fourier transform infrared (FT-IR)
spectra were collected on a Nicolet Nexus 670 FT-IR
instrument (Nicolet Instrument Co., USA, http://www.
thermo.com/) in its transmission mode. Scanning electron
microscopy (SEM) pictures were collected on a JEM-6700F
field emission scanning electron microscope (JEOL, Tokyo,
Japan, http://www.jeol.com/). A pH-3B pH meter (Leici
Instrumental Co., Shanghai, China, http://www.spsic.com/)
was used for pH measurements.
Cysteamine was purchased from Sigma-Aldrich (http://
www.sigmaaldrich.com/). CS from crab shells (90% deace-
W. Deng et al.
tylated) was purchased from Sinopharm Chemicals Co., Ltd
(Shanghai, China, http://www.sinoreagent.com/). MWCNTs
(20–40 nm diameter) were purchased from Shenzhen
Nanotech Port Co., Ltd (Shenzhen, China, http://www.
nanotubes.com.cn/). The MWCNTs were purified and
acidified prior to use by stirring them in 2 M aqueous
nitric acid for 20 h. All other chemicals were of analytical
grade. A 0.5 wt% CS solution was prepared by dissolving
CS solid in 0.10 M acetic acid. After the undissolved
material was filtered, the solution pH was adjusted to pH
5.1 via careful additions of concentrated NaOH under
vigorous stirring. All solutions were prepared using
ultrapure Milli-Q water (>18 MΩ cm, Millipore, USA,
http://www.millipore.com/), and all experiments were
conducted at room temperature (25 ± 2°C) under air
atmosphere.
Procedures
The CS-SH was prepared as follows. The covalent
attachment of cysteamine to CS chains relied on the
formation of Schiff bases by crosslinking the amino groups
of cysteamine and CS with glutaraldehyde. The synthesis of
CS-SH product involved three steps, as demonstrated in
Scheme 1. In step I, a glutaraldehyde functionalized CS
was prepared by drop-by-drop addition of 20 mL 0.50 wt%
CS solution into 20 mL 50% glutaraldehyde under
magnetic stirring and then allowed to react for 48 h at
room temperature. To confirm only one aldehyde group of
glutaraldehyde reacting with the amino groups of CS, a
high molar ratio of glutaraldehyde to CS glucosamine units
was used here [12, 25]. The unreacted glutaraldehyde was
removed from the solution by dialyzing the reaction
mixture for 12 h against acetate buffer solution (pH 5.0),
and a glutaraldehyde functionalized CS was obtained. In
step II, the glutaraldehyde functionalized CS was allowed
to react with cysteamine for 12 h, and the cysteamine
amount was equivalent to the content of glucosamine units
of CS in the solution. Again, the dialysis was used to
remove unreacted cysteamine from the reaction mixture. In
step III, the obtained Schiff bases were reduced to more
stable secondary amines using sodium borohydrate, and a
final CS-SH solid was obtained after centrifugation. The
prepared CS-SH was characterized by FT-IR spectropho-
tometry (Fig. 1A). The two bands in 580 and 1,640 cm-1 are
assigned to the thiol groups of CS-SH [5].
To examine the stability of the CS-SH film in acidic
solution and the adsorbability of the CS-SH film to Hg(II),
5 μL of DMF containing 2 mg mL-1 CS-SH was cast on a
PQC electrode and air-dried for QCM studies, which
resulted in -6.0 kHz dry frequency shift (Δf0d) and 15 Ω
resistance increase (ΔR1). The value of -Δf0d/ΔR1 is
significantly larger than that theoretically calculated for a
Square wave voltammetric determination of Hg(II) using thiol 369

Scheme 1 Synthesis pathway

H OH H OH
of CS-SH
H O H O
glutaraldehyde cysteam ine

H O step I H O step II
H NH 2 H
N
OH H n OH H n

CH (CH 2 ) 3 CH O

H OH
H OH

H O H O
NaBH 4
H O
step III H O
H
H
N
OH H n NH
OH H n
CH (CH 2 ) 3 C
(CH 2 ) 5

N(CH 2 ) 2 SH NH (CH 2 ) 2 SH

net viscodensity, 10 Hz Ω-1, indicating that the dry CS-SH
film is sufficiently rigid and the Sauerbrey equation is
applicable for mass estimation [11].
One milligram MWCNTs was dispersed in 1 mL N,N-
dimethylformamide (DMF) containing 2 mg mL-1 CS-SH
by sonication. To fabricate a CS-SH-MWCNTs/GCE, 2 μL
of the above mixture was cast on a GCE and dried in air for
electrochemical studies. The morphology of the CS-SH-
MWCNTs nanocomposite was examined by SEM, giving
that the MWCNTs are well coated by CS-SH (Fig. 1B). For
comparison, 1 mg MWCNTs was dispersed in 1 mL DMF
by sonication, and 1 μL of MWCNTs solution was cast on
the GCE and dried in air for electrochemical studies.
The electrochemical detection of Hg(II) using square
wave stripping voltammetry was conducted after the
chemical accumulation of Hg(II) under open-circuit condi-
tion and electrochemical reduction of the accumulated Hg
(II) into Hg metal. Preconcentration was achieved by
placing the CS-SH-MWCNTs/GCE in 1 M aqueous HCl
containing Hg(II) under open-circuit condition. The solu-
tion was kept under constant stirring, and after an
appropriate accumulation time the electrode was promptly
removed, rapidly rinsed with water and transferred to the
voltammetric cell containing 1 M aqueous HCl. The
electrode was kept at -0.3 V for 2 min to reduce the
accumulated Hg(II), and the square wave stripping voltam-
mograms were recorded between -0.3 and 0.3 V.
Results and discussion
Quartz crystal microbalance characterization of the Au
electrode modified with thiol-functionalized CS
The protonation/deprotonation effects of the CS amino
groups make CS water-soluble at pH sufficiently below its
pKa (ca. 6.3) but insoluble at pH near or above its pKa [11].
Hence, the direct applicability of a CS film in acidic
solutions is still a challenge to date. However, the chemical
modifications of CS can introduce new groups along the CS

Fig. 1 A FT-IR spectra of CS

(a) and CS-SH (b). B SEM A B
image of CS-SH-MWCNTs
a a
nanocomposite

b
b

-1
580 cm
-1 1640 cm-1
580 nm 1640 cm
-1

0.5 μm
600 800 1000 1200 1400 1600 1800 2000

σ / cm-1
370 W. Deng et al.

Fig. 2 A QCM response at the t/s

CS-SH/Au electrode to the ad- 0 200 400 600 800 1000 1200 1400 1600
dition of 1 M aqueous HCl 1000
0
(final concentration) into stirred A B
0

Δ f0 / Hz
20 mL water. Arrows indicate -2000
the moment for HCl addition. B -1000 -4000
The time-dependent frequency
-2000 -6000
responses at CS-SH/Au to suc-
cessive injection of Hg(II) into -3000 300 -8000
0
stirred 1 M aqueous HCl. C The
frequency shifts at CS-SH/Au as 200 -2000

Δ R1 / Ω

Δ f0 / Hz
a function of Hg(II) concentra- -4000
100
tion. -6.0 kHz CS-SH was C -6000
modified on Au 0
-8000
0 1000 2000 3000 4000 5000 6000 0 2 4 6 8 10 12 14 16 18
t/s c / mM

chains, which can weaken or even prevent its dissolution in
acidic solutions [17–19]. Herein, we examined the stability
of the CS-SH film on Au in acidic solution via the QCM
technique, which can detect minute changes in mass
loading and viscoelasticity of a film modified on the
electrode [26, 27]. As shown in Fig. 2A, the frequency
shift (f0) and resistance change (R1) of the CS-SH/Au were
initially very stable in water. The HCl addition suddenly
decreased the f0 and simultaneously increased the R1, and
the value of -Δf0/ΔR1 of 10 Hz/Ω here should indicate that
the f0 and R1 responses originate from a net viscous effect
[12, 27]. Thereafter, the f0 and R1 kept very stable in the
next 5,500 s, proving that the CS-SH film is highly stable in
and applicable to acidic media.
The thiol group is a good functional group for Hg(II)
chelation [5, 18]. We examined the adsorbability of a -
6.0 kHz CS-SH film with the QCM technique. As shown in
Fig. 2B, when Hg(II) was added into stirred 1 M aqueous
HCl, the frequency of the CS-SH/Au electrode kept
dropping and became stable later, indicating that Hg(II)
was attracted from bulk solution to the electrode surface. As
shown in Fig. 2C, -Δf0 at CS-SH/Au increased with the
increase of the concentration of Hg(II) from 0 to 14.5 mM,
and reached a plateau and thus saturated adsorption of Hg
(II) at higher concentrations. Because the dry CS-SH film
was sufficiently rigid, dry frequency shifts (Δf0d) can be
used to evaluate the adsorbability of the CS-SH film more
accurately. The dry frequency of a CS-SH/Au electrode was
recorded in air (f0d1). The electrode was immersed in 1 M
HCl containing 14.5 mM Hg(II) for saturated adsorption,
then gently rinsed with pure water and air-dried, and the dry
frequency of this electrode was recorded again in air (f0d2).
We obtained a dry frequency shift ðΔf0d ¼ f0d2  f0d1 Þ of -
2.5 kHz for the adsorbed Hg(II) (i.e. 4.0 μg calculated from
the Sauerbrey equation). Since the dry frequency shift for
the pristine CS-SH film is -6.0 kHz (i.e. 9.5 μg calculated
from the Sauerbrey equation), the saturated adsorption
capacity of CS-SH for Hg(II) is calculated to be 42% mass
percentage (0.42 g Hg(II) per gram CS-SH), proving that
the CS-SH possesses strong adsorbability toward Hg(II)
due to abundant thiol groups involved in the CS-SH.
Comparison among different modified electrodes for Hg(II)
determination
Because of the strong adsorbability toward Hg(II), the CS-
SH/GCE might be applied for sensitive determination of Hg
(II) using square wave stripping voltammetry. Preconcen-
tration was comparatively examined by placing a bare
GCE, a MWCNTs/GCE, and a CS-SH-MWCNTs/GCE in
1 M aqueous HCl containing 0.15 μM Hg(II) under open-
circuit condition for 10 min, respectively. Each electrode
was then transferred into a blank solution and potentio-
stated at -0.3 V for 2 min to reduce the tethered Hg(II). The
square wave stripping voltammograms were recorded
between -0.3 and 0.3 V, as shown in Fig. 3. No obvious
stripping peak was observed at the bare GCE. Under
comparable conditions, the MWCNTs/GCE produced a
CS-SH-MWCNTs
10 μ A
MWCNTs
GC
-0.4 -0.2 0.0 0.2 0.4
E / V vs SCE
Fig. 3 Square wave stripping voltammograms at GCE, MWCNTs/
GCE, or CS-SH-MWCNTs/GCE in 1 M aqueous HCl. Amplitude:
0.025 V, increment potential: 0.004 V, frequency: 15 Hz. Preconcen-
tration was achieved by dipping the working electrodes in 1 M
aqueous HCl containing 0.15 μM Hg(II) under open-circuit condition
for 10 min followed by potentiostatic deposition at -0.3 V for 2 min
Square wave voltammetric determination of Hg(II) using thiol 371

Fig. 4 The effect of MWCNTs 35 36

content a, preconcentration time a b
b, deposition potential c, and
HCl concentration in voltam- 30 32
metric cell d on the stripping
current of Hg(II) at the CS-SH- 25
MWCNTs/GCE. Other experi- 28

mental conditions are the same

ip / μ A
ip / μ A
as in Fig. 3 except for the 20
24
optimized one
15
20

10
16

5
0 1 2 3 2 4 6 8 10 12 14
-1
cMWCNTs / mg mL t / min
45 34
c d
40 32

35
30

30
ip / μ A

28

ip / μ A
25
26
20

24
15

10 22

5 20
-.6 -.4 -.2 0.0 .5 1.0 1.5 2.0 2.5 3.0

E / V vs SCE cHCl / M

small stripping signal at -0.01 V. In fact, with acidic

treatment of MWCNTs, some oxygenous groups, such as
30
carboxyl, carbonyl and hydroxyl, could form at the ends 50
ip / μ A

20
and defect sites on the surface of the MWCNTs. These
functional groups of limited abundance can chelate with Hg 10
(II) [21], resulting in the accumulation of Hg(II) to some 40 0
degree and the observed small stripping peak at the
i / μA

0.00 0.06 0.12 0.18

MWCNTs/GCE. The highest stripping peaks at 0 V for
30 c/ M
Hg(II) was observed at the CS-SH-MWCNTs/GCE. Be-
cause the abundant thiol groups in the CS-SH film can
deposit Hg(II) in bulk solution on the electrode surface, as 20
validated by the QCM studies, the stripping peak current
was increased. Note here that the thiol groups in the CS-SH
film were not oxidized to S-S bonds in the potential region 10
-0.2 0.0 0.2 0.4 0.6
from -0.3 to 0.3 V, but their oxidation occurred at ca. 1.0 V
(data not shown). E / V vs SCE
Fig. 5 Square wave stripping voltammograms and calibration curve
Optimization of experimental conditions for Hg(II) on CS-SH-MWCNTs/GCE in 1 M aqueous HCl. Precon-
centration was achieved by dipping the CS-SH-MWCNTs/GCE in
1 M aqueous HCl containing Hg(II) at different concentrations under
The MWCNTs content was optimized, as shown in Fig. 4a. open-circuit condition for 10 min followed by potentiostatic deposi-
The stripping peak height increased with the increase of tion at -0.3 V for 2 min. Other experimental conditions are the same as
MWCNTs content from 0 to 1 mg mL-1, because the added in Fig. 3
372
MWCNTs can lead to formation of good conduction
pathway in the CS-SH film for better electroanalysis, in
addition to their positive effect on preconcentration. Hence,
1 mg mL-1 MWCNTs was added in the cast solution.
The preconcentration time was studied in the range of
4∼12 min in 1 M aqueous HCl containing 0.15 μM Hg(II)
under open-circuit condition. As shown in Fig. 4b, the
stripping peak height increased sharply up to 10 min, then
increased slightly. Taking both the sensitivity and the
efficiency into account, a preconcentration period of
10 min was employed in the next experiments.
The deposition potential was also optimized, as shown in
Fig. 4c. The negative shift of the deposition potential
increased the stripping peak current of Hg(II), but at too
negative potentials some other chemicals may also be
reduced and interfere the determination of Hg(II). There-
fore, a deposition potential of -0.3 V is recommended to
reduce the accumulated Hg(II) for further study.
The concentration of HCl in the voltammetric cell was
studied in the range of 0.5∼2.5 M, as shown in Fig. 4d.
Here the ion strength and solution pH are dependent on the
concentration of HCl. The largest stripping current of Hg
(II) at the CS-SH-MWCNTs/GCE was observed in 1 M
HCl aqueous solution. Therefore, all the voltammetric
measurements are conducted in 1 M HCl.
Determination of Hg(II) by square wave stripping
voltammetry
The measurements of Hg(II) were performed by square
wave stripping voltammetry under optimized conditions. A
series of stripping voltammograms for 0∼0.17 μM Hg(II)
are shown in Fig. 5. The Inset shows the calibration plot of
Hg(II). The peak currents increased linearly with Hg(II)
concentration from 0.01 to 0.14 µM with a sensitivity of
212 µA·µM-1 (r2 =0.9942). The limit of detection for Hg(II)
(S/N=3) is 3 nM, which is lower than the reported values
using electrodes modified with other organic compounds,
ion-exchange resin, or inorganic compounds [4–9]. The
relative standard deviation for five successive determina-
tions of 0.15 μM Hg(II) was 4.8%.
The interference study was performed by adding various
metal ions into a perconcentration solution containing
0.15 μM Hg(II). In general, 100-fold Cd2+, 100-fold Pb2+,
50-fold Zn2+, 25-fold Cu2+, 10-fold Ag+, 10-fold Fe2+, and
10-fold Mn2+ caused within ±5% changes of voltammetric
signals for Hg(II).
The CS-SH-MWCNTs/GCE was employed for the
determination of Hg(II) in river water (from the Xiangjiang
river, Changsha, China) for the examination of practical
applicability. The water sample was irradiated for 2 h with a
400-W UV lamp for elimination of organic matter in
advance. After that, the water sample was filtered with a
W. Deng et al.
0.22 μm Millipore membrane, and then 1 M HCl (final
concentration) was added. Then the electroanalytical
procedures were conducted, and the anodic stripping peak
current was recorded for the determination of Hg(II) with
the addition of Hg(II) standard solution to the samples
under optimized condition. Adding 0.03, 0.05, or 0.10 μM
Hg(II) in the river water samples and applying the standard
addition method led to a recovery of (91±3)%, (94±4)% or
(90±3)% (n=3 for each), respectively, indicating that the
CS-SH-MWCNTs/GCE can be applied to the determination
of Hg(II) in real water samples.
Conclusions
The applicability of the CS-SH-MWCNTs/GCE to the
square wave voltammetric determination of Hg(II) has been
investigated. The MWCNTs content, deposition time,
deposition potential, and concentration of HCl in the
voltammetric cell were optimized to obtain the highest
sensitivity. The CS-SH-MWCNTs/GCE exhibited excellent
performance due to the strong adsorbability of abundant
thiol groups in the CS-SH to Hg(II) and good conductivity
of the CS-SH-MWCNTs nanocomposite film. The CS-SH-
MWCNTs/GCE with a well-defined stripping response
could be successfully applied to the determination of trace
Hg(II) in real samples.
Acknowledgments This work was supported by the National
Natural Science Foundation of China (20675029, 90713018,
20335020), the State Special Scientific Project on Water Treatment
(2009ZX07212-001-06), the Foundation of the Hunan Provincial
Education Department (05K009), and the State Key Laboratory of
Electroanalytical Chemistry. W. Deng and Y. Tan contributed equally
to this work.
References
1. Oehme I, Wolfbeis OS (1997) Optical sensors for determination of
heavy metal ions. Microchim Acta 126:177
2. Bowels KC, Apte SC (1998) Determination of methylmercury in
natural water samples by steam distillation and gas chromatography-
atomic fluorescence spectrometry. Anal Chem 70:395
3. Tu Q, Qvarnstrom J, Frech W (2000) Determination of mercury
species by capillary zone electrophoresis-inductively coupled
plasma mass spectrometry: a comparison of two spray chamber-
nebulizer combinations. Analyst 125:705
4. Cai X, Kalcher K, Lintschinger J, Neuhold C (1993) Stripping
voltammetric determination of trace amounts of mercury using a
carbon paste electrode modified with 2-mercapto-4(3H)-quinazo-
linone. Microchim Acta 112:135
5. Cesarino I, Cavalheiro ÉTG (2008) Thiol-functionalized silica
thin film modified electrode in determination of mercury ions in
natural water. Electroanalysis 20:2301
6. Jeong ED, Won MS, Shim YB (1994) Simultaneous determination
of lead, copper, and mercury at a modified carbon paste eletrode
containing humic acid. Electroanalysis 6:887
Square wave voltammetric determination of Hg(II) using thiol
7. Navratilova Z (1991) Hg(II) voltammetry on a 1, 5-
diphenylcarbazide containing carbon paste electrode. Electroanal-
ysis 3:799
8. Agraza R, Sevilla MT, Hernándeza L (1993) Chemically modified
electrode for the simultaneous determination of trace metals and
speciation analysis. Anal Chim Acta 273:205
9. Agraz R, Sevilla MT, Hernandez L (1995) Voltammetric quanti-
fication and speciation of mercury compounds. J Electroanal
Chem 390:47
10. Zhang MG, Smith A, Gorski W (2004) Carbon nanotube-chitosan
system for electrochemical sensing based on dehydrogenase
enzymes. Anal Chem 76:5045
11. Zhou Q, Xie Q, Fu Y, Su Z, Jia X, Yao S (2007) Electrodeposition
of carbon nanotubes-chitosan-glucose oxidase biosensing com-
posite films triggered by reduction of p-benzoquinone or H2O2. J
Phys Chem B 111:11276
12. Tan Y, Deng W, Ge B, Xie Q, Huang J, Yao S (2009) Biofuel cell
and phenolic biosensor based on acid-resistant laccase-
glutaraldehyde functionalized chitosan–multiwalled carbon nano-
tubes nanocomposite film. Biosens Bioelectron 24:2225
13. Bailey SE, Olin TJ, Bricka RM, Adrian DD (1999) A review of
potentially low-cost sorbents for heavy metals. Water Res 33:2469
14. Guibal E (2004) Interactions of metal ions with chitosan-based
sorbents: a review. Sep Purif Technol 38:43
15. Marcolino-Junior LH, Janegitz BC, Lourenção BC, Fatibello-
Filho O (2007) Anodic stripping voltammetric determination of
mercury in water using a chitosan-modified carbon paste
electrode. Anal Lett 40:3119
16. Janegitza BC, Marcolino-Juniorb LH, Campana-Filhoc SP, Fariaa
RC, Fatibello-Filhoa O (2009) Anodic stripping voltammetric
determination of copper(II) using a functionalized carbon nano-
tubes paste electrode modified with crosslinked chitosan. Sens
Actuat B 142:260
373
17. Qu R, Sun C, Ma F, Zhang Y, Ji C, Xu Q, Wang C, Chen H
(2009) Removal and recovery of Hg(II) from aqueous solution
using chitosan-coated cotton fibers. J Hazard Mater 167:717
18. Merrifield JD, Davids WG, MacRae JD, Amirbahman A (2004)
Uptake of mercury by thiol-grafted chitosan gel beads. Water Res
38:3132
19. Ngah WSW, Endud CS, Mayanar R (2002) Removal of copper(II)
ions from aqueous onto chitosan and crosslinked chitosan beads.
React Funct Polym 50:181
20. Haddon RC (2002) Carbon nanotubes. Acc Chem Res 35:977
21. Rao GP, Lu C, Su F (2007) Sorption of divalent metal ions from
aqueous solution by carbon nanotubes: a review. Separ Purif
Techno 58:224
22. Liu G, Lin Y, Tu Y, Ren Z (2005) Ultrasensitive voltammetric
detection of trace heavy metal ions using carbon nanotube
nanoelectrode array. Analyst 130:1098
23. Deng W, Tan Y, Fang Z, Xie Q, Li Y, Liang X, Yao S (2009)
ABTS-multiwalled carbon nanotubes nanocomposite/Bi film
electrode for the sensitive determination of Cd and Pb by
differential pulse stripping voltammetry. Electroanalysis 21:2477
24. Sun D, Xie X, Cai Y, Zhang H, Wu K (2007) Voltammetric
determination of Cd2+ based on the bifunctionality of single-
walled carbon nanotubes-Nafion film. Anal Chim Acta 581:27
25. Wei X, Cruz J, Gorski W (2002) Integration of enzymes and
electrodes: spectroscopic and electrochemical studies of chitosan-
enzyme films. Anal Chem 74:5039
26. Martin SJ, Granstaff VE, Frye GC (1991) Characterization of a
quartz crystal microbalance with simultaneous mass and liquid
loading. Anal Chem 63:2272
27. Xie Q, Wang J, Zhou A, Zhang Y, Liu H, Xu Z, Yuan Y, Deng M,
Yao S (1999) A study of depletion layer effects on equivalent
circuit parameters using an electrochemical quartz crystal imped-
ance system. Anal Chem 71:4649