ISSN 10619348, Journal of Analytical Chemistry, 2012, Vol. 67, No. 8, pp. 687–693. © Pleiades Publishing, Ltd., 2012.

ARTICLES

Fabrication of an Optical Sensor Based on the Immobilization

of Qsal on the Plasticized PVC Membrane
for the Determination of Copper(II)1
B. Rezaei, H. Hadadzadeh, and A. Azimi
Department of Chemistry, Isfahan University of Technology, Isfahan, 8415683111 Iran
Received June 10, 2010; in final form May 5, 2011

Abstract—A novel optical sensor has been proposed for sensitive determination of Cu(II) ion in aqueous
solutions. The copper sensing membrane was prepared by incorporating Qsal (2(2hydroxyphenyl)3H
anthra[2,1d]imidazole6,11dione) as ionophore in the plasticized PVC membrane containing tributyl
phosphate (TBP) as plasticizer. The membrane responds to Cu(II) ion by changing color reversibly from yel
low to dark red in acetate buffer solution at pH 4.0. The proposed sensor displays a linear range of 6.3 × 10–7–
1.00 × 10–4 M with a limit of detection of 3.3 × 10–7 M. The response time of the optical sensor was about 3–
5 min, depending on the concentration of Cu(II) ions. The selectivity of the optical sensor to Cu(II) ions in
acetate buffer is good. The sensor can readily be regenerated by hydrochloric acid (0.1 M). The optical sensor
is fully reversible. The proposed optical sensor was applied to the determination of Cu(II) in environmental
water samples.

Keywords: optical sensor, ionophore, PVC membrane, plasticizer, absorbance, semiempirical PM6 calcula
tions.
DOI: 10.1134/S1061934812080060

1
The development of optical sensors has become a
rapidly expanding area of analytical chemistry. Optical
sensors offer the advantages of simple preparation as
they may easily be incorporated into lowcost, easy to
use kits. Yet at the same time, they have reasonable
selectivity and sensitivity and do not require separate
devices [1–10].
Copper is widely used in electrical and electronic
industry. The metalbased alloys (aluminum, cobalt,
manganese, nickel, zinc) have been introduced for the
fabrication of bridges and dental crowns. Copper is an
important bioelement for both plants and animals
including humans. Following zinc and iron, copper
ranks the third in abundance in human bodies among
the essential heavy metals. One notable function of
copper is its influence on the metabolism of iron.
Another function is its direct influence on the activity
of some enzymes. Nevertheless, copper is highly toxic
to some organisms such as many bacteria and viruses.
It is both vital and toxic to many biological systems,
depending on the level of concentration [11], Thus,
the determination of trace amount of copper ions in
various samples is of great importance for environ
ment and human health.
Commonly, the analytical methods for the quanti
fication of zinc and copper are neutron activation
analysis (NAA), atomic absorption spectrometry
1 The article is published in the original.
(AAS) and inductively coupled plasma mass spec
trometry (ICPMS), which all are based on expensive
and sophisticated instruments [12]. Flame atomic
absorption spectrometry (FAAS) is available in most
laboratories but it requires the use of a preconcentra
tion step in order to reach an appropriate level of sen
sitivity. In recent years a large number of publications
are dealing with optical copper sensing [13–15].
EXPERIMENTAL
Reagents and apparatus. Standard copper(II) ion
solutions were prepared daily by appropriate dilution
of stock solution 0.1 M Cu(NO3)2 · 6H2O. Other
reagents such as orthonitrophenyl octyl ether
(oNPOE), dibutyl phthalate (DBP), dioctyl sebacate
(DOS), tributylphosphate (TBP), high molecular
weight poly(vinylchloride) (PVC), tetrahydrofurane
(THF), all from Fluka or Merck chemical companies,
were used as received. All other chemicals were of
reagent grade and were used without further purifica
tion.
UVvis spectra were obtained with a UV/VIS/NIR
JASCO spectrophotometer, Model V570, connected
to a Pentium IV computer. The reference cell con
tained a membrane without any Qsal reagent. A
Metrohm pH meter (model 780) with a combined
double junction glass electrode, calibrated against two

687
688 REZAEI et al.

H N H N H
H
H C C C C C H
H
H C
Cu Copper C C C C C C
C C

C C C C C
O Oxygen H C C C
C C C C H
N H H C C N
N Nitrogen H
N N C H N H
N C
H
C Carbon H
C C N Cu H C
(A) (B) H H N C
H Hydrogen N C
C C H H
H N H
C
H H
C C C
C
H
H H
H

Fig. 1. Optimal conformation of Qsal (2(2hydroxyphenyl)3Hanthra[2,1d]imidazole6,11dione) (A) before and (B) after
complexation with Cu2+.

standard buffer solutions at pH 4.0 and 7.0, was used
for monitoring pH values. The pH of the solutions was
kept constant by using 0.1 M acetate buffer at pH 4.0.
Preparation of Qsal. Salicylaldehyde (244 mg,
2 mmol) and 1,2Diamino anthraquinone (476 mg,
2 mmol) were dissolved in nitrobenzene (20 mL) and
stirred at 130°C for 24 h. Once the starting materials
were consumed, as indicated by TLC, the reaction
mixture was cooled to room temperature. Petroleum
ether was added to precipitate out the crude product.
The supernatant organic layer was decanted off, and
the procedure was repeated several times until most of
nitrobenzene had been removed. The product was
finally purified by column chromatography over silica
gel to yield the pure compound as a goldencolored
solid in 67% yield. The pure compound was eluted out
with 8–10% MeOH in CHCl3.
Preparation of membrane. The membrane solution
was prepared by dissolving a mixture of active compo
nents: 50 mg PVC, 100 mg TBP as plasticizer, 2.0 mg
anionic additive and 3.0 mg of Qsal in 1.5 mL of THF.
The solution was immediately shaken vigorously to
achieve complete homogeneity. A glass plate with a
rectangular frame 0.9 × 3 cm was cleaned with pure
THF to remove organic impurities and dust. Then,
25 μL of the membrane solution was transferred onto
the glass plate and was spread evenly using a capillary
glass tube to construct the membrane on the surface of
the glass plate (membrane sensor). Then, the mem
brane was allowed to dry in air for a few minutes. A
membrane solution without Qsal reagent was used to
fabricate a reference membrane sensor.
Absorbance measurements. The prepared mem
branes were put in an acetate buffer solution of pH 4.0
for 10 min to reach equilibrium. After drying, the
membrane sensor was immersed into a solution of
Cu(II) in acetate buffer (pH 4.0) for 4 min at ambient
temperature. Then, it was washed with water for
removing excess reagents and the loosely trapped indi
cator. The membrane sensor was finally washed with
distilled water and dried . The prepared sensor was
perpendicularly placed and fixed in a quartz cell that
was directly mounted in the spectrophotometer. The
absorbance was measured over the wavelength range of
350–650 nm.
The membrane response may be defined as the
ratio of the concentration of the uncomplexed ligand,
[c], to the total amount present in the membrane, [cT],
i.e. α = [c]/[cT]. Then, the α value can be calculated
by absorbance measurements at the λmax of complexed
ligand as α = (AC – A)/(AC – AL), where AC is the
absorbance value of the membrane for complete com
plexation (i.e. at α = 0), AL is the absorbance value of
the membrane for the free ligand (i.e. at α = 1) [16]
and A is absorbance measured at any time during the
titration procedure.
RESULTS AND DISCUSSION
Spectral characteristics and complexation. Due to
sufficient insolubility of Qsal in water and the presence
of two available donor atoms (NO) in its structure, it
was expected to act as a suitable ion carrier in the PVC
membranes for complex formation with Cu(II) ions
(Fig. 1). According to the principle of hard and soft
acids and bases (HSAB), Cu(II) ion is classed as bor
derline hard acid and forms stable complexes with
both N and O donor atoms. Previous studies have been
shown that the Qsal derivatives are monoanionic tri
dentate or neutral bidentate ligands and coordination
of these Iigands to metal ions leads to the formation of
a chelate ring [17–21]. The chelating agent Qsal acts
as a bidentate (N, O) or a tridentate (N,O2) ligand
with respect to pH. At the optimized pH of 4, Qsal is a
bidentate chelate and can bind to Cu(II) ion via N and
O donor atoms. For more investigation, the semiem

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 FABRICATION OF AN OPTICAL SENSOR BASED ON THE IMMOBILIZATION 689

pirical PM6 calculations [22] were performed to inves
tigate the interaction between the Qsal ligand and
Cu(II) to predict the complex structure and coordina
tion mode. The results have revealed that the Cu(II)–
Qsal complex with twodentate N, O (one nitrogen
atom of the imidazole ring, and one oxygen of the
anthraquinone ring) and three aqua ligands with the
Qsal to Cu(II) stoichiometric ratio of 1 : 1 is the most
possible structure (Fig. 1). The Qsal/Cu(II) ratio was
presumed to be 1 : 1. Due to the fact that the Qsal
ligands are fixed in the membrane and only one Qsal can
be available in the vicinity of each Cu(II) ion (Fig. 1).
The structure of the Cu⎯Qsal complex consists of a
sixmembered ring formed by N and O donor atoms of
the Qsal ligand with the copper center and also the bite
angle is more normal for this ion rather than other
metal cations. As can be seen in Fig. 1, the chelate ring
is characterized by bite angle of 92.543° for N–Cu–O.
The bond lengths between the Cu(II) and each donor
atom of the Qsal and aqua ligands are listed in Table 1.
The bite angle and bond lengths cause the formation of
Cu⎯Qsal ring to be relatively favorable.
Figure 2 shows the absorption spectra of the immo
bilized Qsal on PVC membrane which were obtained
after being equilibrated in acetate buffer solution
(pH 4.0). The spectral change (decrease in absorption
band at 419 nm and increase in the absorption band at
541 nm) is a result of exposure of membrane in contact
of copper solution which is due to the extraction of
copper ion into the membrane. In the Cu⎯Qsal com
plex, the intense absorption band at 541 nm (Fig. 2) is
assigned to ligandtometal charge transfer (LMCT)
by analogy to other Cu(II) complexes [23].
In fact, Fig. 2 shows the absorption spectra of the
immobilized Qsal and complexation of Qsal and cop
per that is response of optical sensor. The formation of
Table 1. Bond lengths (Å) for [ Cu ( Qsal ) ( H 2 O ) 3 ]
2+
complex
Bond length (Å)
Cu–N 1.952
Cu–O 2.035
Cu–OH2 2.158
Cu–OH2 2.148
Cu–OH2 2.093
the complex causes a change in color of the reagent
phase from yellow to dark red.
Effect of pH and the type of buffer on the sensor
response. The influence of pH on the complex forma
tion was studied in the range of 1.0–6.5. The absor
bance measurements were made for 1.0 × 10–5 M cop
per ion at different pH values at 541 nm. The blank
membrane (membrane without Qsal in buffer solu
tion) was taken as reference. Figure 3 shows the effect
of pH on the response of the optical sensor membrane.
The absorbance measurements were expressed as
absorbance difference, which was defined as the dif
ference between the absorbance of the immobilized
Qsal alone and the absorbance of the Cu⎯Qsal com
plex at 541 nm. pH Values were adjusted by the addi
tion of dilute NaOH or HCl.
As can be seen from Fig. 3, as pH increases from 1.5
to 4.0 the difference between absorbance value
increases. At pH values more than 4.0, the response
decreases. Protonation of the ligand at low pH values
prevents its reaction with Cu(II), resulting in lower
sensor response. The pH values > 6.5 were not exam
ined because Cu(II) precipitates in alkaline solutions.
Also at pH values above 4 the ligand had leakage from
the membrane, while at pH 4.0 no leakage of the

Absorbance Difference in absorbance

0.42 0.045
0.37 0.040
Qcal 0.035
0.32
0.030
0.27
0.025
0.22 0.020
0.17 Cu–Qcal 0.015
0.12 0.010
0.005
0.07
0
0.02 1 2 3 4 5 6 7
350 400 450 500 550 600 650 700 –0.005 pH
Wavelength, nm

Fig. 2. Absorption Spectra for PVC⎯Qsal and PVC⎯Cu⎯ Fig. 3. Effect of pH on the response of membrane in
Qsal complex membranes at pH 4.0. 1.0 × 10–5 M Cu(II) at 443 nm.

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690 REZAEI et al.

Table 2. Composition of the optical sensor membrane casting solution and results for different amount of plasticizer
Composition of membrane
Number
Cationic additive Dynamic range, M
of membrane PVC, mg Plasticizer (100 mg) Ionophore (Qsal), mg
(NaTPB), mg
1 50 DOS 4.0 2.0 5.0 × 10–6–1.7 × 10–4
2 50 DBP 4.0 2.0 7.1 × 10–7–1.7 × 10–5
3 50 TBP 4.0 2.0 6.3 × 10–7–1.0 × 10–4
4 50 oNPOE 4.0 2.0 –

membrane was observed. Thus, pH 4.0 was selected
for further studies.
Response studies of this membrane to various
buffer solutions including acetate, citrate, universal
and phthalate (pH 4.0 and 0.1 M) showed that it
responded the best to acetate buffer. In acetate buffer,
the membrane optical sensor showed better sensitivity
and response time. Therefore, acetate buffer was
selected as the optimum buffer for further studies.
Effect of membrane composition. Choice of solvent
mediator (plasticizer). Because of the effect of nature of
the plasticizer on the membrane characteristics such
as dielectric constant, the mobility and state of iono
phers, it was expected to play a key role in determining
the ion selectivity of the membrane [24–26]. Several
different plasticizers such as oNPOE, DBP, DOS,
TBP were tested for preparing the membrane. The
membranes were prepared from a mixture of PVC
(50 mg), plasticizer (100 mg), Qsal (3 mg) and NaTPB
(2 mg) in THF (1.5 mL) as described in the procedure
above. The results are shown in Table 2. As can be
seen, for the case of TBP the membrane response
towards Cu(II) ions gives the widest working dynamic
range. The membranes containing TBP revealed the
best physical properties with maximum sensitivities.
This is most probably due to the presence of phosphate
group, which facilitates the extraction–complexation
of the copper ions into the bulk of PVC–membranes.
Effect of the amount of Qsal on the optical sensor
response. In addition to the optimization of the type of
plasticizer, it is also necessary to optimize the amount
of ligand. The influence of the amount of Qsal was
studied by preparing membranes containing 0–5.0 mg
of Qsal (Fig. 4). The absorbance measurements were
made for 10–5 M copper ion for membranes with dif
ferent amounts of Qsal at 541 nm. The blank mem
brane (membrane without Qsal) was taken as the ref
erence. Increase in the amount of Qsal up to 1.94%
results in an increase in the absorbance. However,
higher amounts of Qsal (more than 1.94%) did not
improve the sensitivity and were not suitable due to the
leakage of Qsal. Thus, ~3% (w/w) of ligand (Qsal) in
the membrane was selected for further studies.
Effect of the amount of NaTPB on the optical sensor
response. The effect of the amount of NaTPB on the
response of the membrane is illustrated in Fig. 5. As
can be seen, increase in the amount of NaTPB up to
more than 2.0 mg results in an increase of interference

Difference in absorbance Difference in absorbance

0.045 0.050
0.045
0.040 0.040
0.035
0.035 0.030
0.025
0.030 0.020
0.015
0.025 0.010
0.005
0.020 0 1 2 3 4 5
0 1 2 3 4 5 6 NaTPB, mg
Ionophore, mg

Fig. 5. Effect of amount of anionic additive on the

Fig. 4. Effect of amount of ionophore on the response of response of membrane in 1.0 × 10–5 M Cu(II) at pH 4.0,
membrane in 1.0 × 10–5 M Cu(II) at pH 4.0, 541 nm. 541 nm.

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 FABRICATION OF AN OPTICAL SENSOR BASED ON THE IMMOBILIZATION
of foreign ions. Also, ~2% (w/w) anionic additive
(NaTPB) in the membrane was selected for further
studies.
Based on the results of the above mentioned studies,
the membrane obtained from a mixture of PVC (50 mg,
31.5%), TBP (100 mg, 63%), Qsal (3.0 mg, 1.94%)
and NaTPB (2.0 mg, 1.29%) in THF (1.5 mL) was
used as the membrane with optimized composition.
Response time. The response time of the optical
sensor is controlled by the time required for the ana
lyte to diffuse from the bulk of the solution toward the
membrane interface to associate with ligand. The
response time was tested by recording the absorbance
change from a pure buffer (pH 4.0) to a buffered
1.0 × 10–5 M copper solution. The data show that the
response times of the membranes can reach to 95% of
its final (steady state) value in about 3–5 min depend
ing on the concentration of Cu(II). Response time is
lower in concentrated solutions than in dilute solu
tions.
Analytical figures of merit. Dynamic range and cal
ibration curve. Figure 6 shows the response of the opti
cal sensor membrane to various concentrations of
Cu(II) ion. A concentration of 5.0 × 10–3 M has been
found as the concentration of Cu(II) ion that saturates
the membrane optical sensor. As can be seen from this
figure, the plot of (1 – α) versus logarithm of copper
ion concentration (M) exhibits a linear portion in the
concentration range of 6.3 × 10–7–1.00 × 10–4 M with
equation of Y = 0.225 log[Cu2+] + 1.4370
(R2 = 0.9983) where Y is (1 – α).
Detection limit. Detection limit of the sensor mem
brane, which is defined as the average blank signal plus
three times of its standard deviation (n = 7) is equal to
3.3 × 10–7 M Cu(II).
Regeneration of the optical sensor membrane. After
the contact of the sensor with Cu(II) solution, the sen
sor membrane must be regenerated by using a suitable
stripping reagent. Preliminary experiments were per
formed to select a suitable regenerating solution.
Among several compounds including EDTA, sodium
fluoride, 5sulfosalicylic acid dihydrate, NaSCN,
HCl, HNO3 and H2SO4, the last three acids were
found to be the most suitable stripping solutions and
among them HCl (0.1 M) was the best one for regen
erating optical sensor. Other reagents were not suitable
regenerating solutions, because there can not compete
with Qsal for Cu(II) ions.
The membrane sensor was used many times to
determine Cu(II) concentration. Each time mem
brane was regenerated by stripping reagent and after
conditioning absorbance was measured. Again after
five times regeneration, a drift of about 3.5% was
obtained in the response of the sensor. According to
low drift on the sensor response after five times regen
eration, it is obvious that the membrane components,
such as ionophore entrapped onto the membrane,
have not leached to the solution after each using.
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 67
691
1–α
1.2
1.0
0.8
0.6
0.4
0.2
0
–8 –7 –6 –5 –4 –3 –2
log[Cu2+]
Fig. 6. Calibration curve for the determination of Cu(II)
ion at pH 4.0 and 541 nm.
The regeneration time, defined as the time taken
for the sensor to reach the baseline signal (the signal
observed in 0.1 M acetate buffer at pH 4.0), where
minimum absorbance had been reached at the wave
length of 541 nm, was 4 min for the optimized sensor
in contact with 5.0 × 10–5 M of Cu(II).
The response characteristics of the proposed opti
cal sensor were compared with previously reported
sensor for the determination of Cu(II) ion [27–31]
and the results are summarized in Table 3. As it is obvi
ous from Table 3, the linear range, detection limit, and
response time of the proposed sensor are better or
comparable to those of other sensors reported in liter
ature. The proposed sensor has a short response time
in comparison to other sensors (except for [30]). Also,
it has lower detection limit and wider dynamic range
compared to the sensors referred as [27–30]. Further
more, in this work we use entrapment method for
immobilization of indicator that eliminates the
agglomeration of indicator on the membrane.
Agglomeration of the indicator is a severe problem in
physical adsorption immobilization.
Effect of foreign ions. The metal ion complexing
properties of nonmacrocyclic ligands such as Qsal in
aqueous solution have been discussed [32]. The affin
ity that metal ions have for ligands is controlled by
size, charge and electronegativity. This can be refined
further by noting that for some metal ions their chem
istry is dominated by size and charge, while for others
it is dominated by their electronegativity.
To determine the selectivity of the optical sensor
membrane, the membrane was tested for the determi
nation of 1.0 × 10–5 M of Cu(II) ions in the presence
of different metal ions. Table 4 summarizes the toler
ance ratio for several cationic and anionic species. The
tolerance limit was taken as the concentration of the
interfering species causing an error of not more than
No. 8 2012
692 REZAEI et al.

Table 3. Comparison of proposed sensor with other methods for the determination of Cu(II)
Detection
Method Linear range, M Response time References
limit, M
Optical sensor (PVC membrane) 1.0 × 10–4–6.3 × 10–7 3.3 × 10–7 3–5 min This work
Optical sensor (triacetylcellulose membrane) 2.0 × 10–4–7.5 × 10–6 8.0 × 10–7 8 min [27]
Flowthrough optode (PVC membrane) 1.0 × 10–3–5.0 × 10–5 5.0 × 10–6 – [28]
Optical sensor (triacetylcellulose membrane) 1.6 × 10–5–8.3 × 10–7 2.0 × 10–7 5–8 min [29]
Fluorescence optode (PVC membrane) 1.0 × 10–2–1.0 × 10–6 7.5 × 10–7 40 s [30]
Fluorescence optode (PVC membrane) 5.0 × 10–5–4.0 × 10–8 – 7 min [31]

Table 4. Effect of foreign ions on the determination of 1.0 × Analytical application. To test the practical applica
10–5 M copper ion tion of the present sensor for the determination of
Tolerance limit Cu(II) in real samples, some river water samples were
Species used. The content of copper ions in the real samples
(Mion/MCu(II))
was measured using atomic absorption spectroscopy
– 500 and the results showed that the initial content of
Na+, K+, Mg2+, Mn2+, Br–, Cl–, BrO 3 ,
– 2–
Cu(II) is lower than the detection limit of the pro
NO 3 , SO 4 posed sensor. In order to verify Cu(II) in environmen
100 tal samples and to study the matrix effect, the different
Zn2+, Hf+, Tl+, La3+, Pb2+, V3+, Ba2+, spiked water solutions were used for testing recovery.
In3+, Cd2+, Rh3+, F– pH of river water was adjusted by the addition of 5 mL
Cr2+, Al3+, Pd2+, Fe3+, Ga3+ 50 of acetate buffer (pH 4.0) to 20 mL of river water. The
+a 2+
Ag , Co , Fe , Ni2+ 2+ 10 results for 3 replicate measurements have been
reported in Table 5. The results show that by the use of
Hg 2+ 5 the proposed optical sensor very satisfactory recoveries
a In the presence of Cl– ions. are obtained for the determination Cu(II) in real water
samples with complex matrixes.
Table 5. Results of copper(II) ion determination in spiked
water samples ***
Reco An optical sensor based on immobilization of Qsal
Sample Added Founda
very % on PVC membrane that is described in this work pro
– <D.L.b – vides a simple means for the determination of Cu(II)
Drinking ions. The membrane is easily prepared and is fully
5.00 × 10–6 (4.68 ± 0.30) × 10–6 93.6
water reversible, as it can be easily regenerated with 0.1 M
5.00 × 10–5 (5.06 ± 0.06) × 10–5 101.2
hydrochloric acid solution. The membrane responds
– <D.L. – to Cu(II) ion by changing color from yellow to dark
River water 5.00 × 10–6 (4.98 ± 0.35) × 10–6 99.6.0 red. The proposed optical sensor was successfully
5.00 × 10–5 (5.17 ± 0.63) × 10–5 103.1 applied as a probe for determination of Cu(II) ion in
– <D.L. – river water samples.
Waste water 5.00 × 10–6 (5.13 ± 0.45) × 10–6 102.6
5.00 × 10–5 (4.72 ± 0.63) × 10–5 94.4 ACKNOWLEDGMENTS
a Average of three determinations.
b Detection limit. The authors wish to thank Isfahan University of
Technology (IUT) Research Council and Center of
Excellence in sensor (IUT) for support of this work.
±3SD in the determination of copper, where SD is the
standard deviation obtained in the replicate measure
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