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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 (AAS) and inductively coupled plasma mass spec
rapidly expanding area of analytical chemistry. Optical trometry (ICPMS), which all are based on expensive
sensors offer the advantages of simple preparation as and sophisticated instruments [12]. Flame atomic
they may easily be incorporated into lowcost, easy to absorption spectrometry (FAAS) is available in most
use kits. Yet at the same time, they have reasonable laboratories but it requires the use of a preconcentra
selectivity and sensitivity and do not require separate tion step in order to reach an appropriate level of sen
devices [1–10]. sitivity. In recent years a large number of publications
Copper is widely used in electrical and electronic are dealing with optical copper sensing [13–15].
industry. The metalbased alloys (aluminum, cobalt,
manganese, nickel, zinc) have been introduced for the
fabrication of bridges and dental crowns. Copper is an EXPERIMENTAL
important bioelement for both plants and animals
Reagents and apparatus. Standard copper(II) ion
including humans. Following zinc and iron, copper
solutions were prepared daily by appropriate dilution
ranks the third in abundance in human bodies among
of stock solution 0.1 M Cu(NO3)2 · 6H2O. Other
the essential heavy metals. One notable function of
copper is its influence on the metabolism of iron. reagents such as orthonitrophenyl octyl ether
Another function is its direct influence on the activity (oNPOE), dibutyl phthalate (DBP), dioctyl sebacate
of some enzymes. Nevertheless, copper is highly toxic (DOS), tributylphosphate (TBP), high molecular
to some organisms such as many bacteria and viruses. weight poly(vinylchloride) (PVC), tetrahydrofurane
It is both vital and toxic to many biological systems, (THF), all from Fluka or Merck chemical companies,
depending on the level of concentration [11], Thus, were used as received. All other chemicals were of
the determination of trace amount of copper ions in reagent grade and were used without further purifica
various samples is of great importance for environ tion.
ment and human health. UVvis spectra were obtained with a UV/VIS/NIR
Commonly, the analytical methods for the quanti JASCO spectrophotometer, Model V570, connected
fication of zinc and copper are neutron activation to a Pentium IV computer. The reference cell con
analysis (NAA), atomic absorption spectrometry tained a membrane without any Qsal reagent. A
Metrohm pH meter (model 780) with a combined
1 The article is published in the original.
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 removing excess reagents and the loosely trapped indi
for monitoring pH values. The pH of the solutions was cator. The membrane sensor was finally washed with
kept constant by using 0.1 M acetate buffer at pH 4.0. distilled water and dried . The prepared sensor was
Preparation of Qsal. Salicylaldehyde (244 mg, perpendicularly placed and fixed in a quartz cell that
2 mmol) and 1,2Diamino anthraquinone (476 mg, was directly mounted in the spectrophotometer. The
2 mmol) were dissolved in nitrobenzene (20 mL) and absorbance was measured over the wavelength range of
stirred at 130°C for 24 h. Once the starting materials 350–650 nm.
were consumed, as indicated by TLC, the reaction The membrane response may be defined as the
mixture was cooled to room temperature. Petroleum ratio of the concentration of the uncomplexed ligand,
ether was added to precipitate out the crude product. [c], to the total amount present in the membrane, [cT],
The supernatant organic layer was decanted off, and i.e. α = [c]/[cT]. Then, the α value can be calculated
the procedure was repeated several times until most of by absorbance measurements at the λmax of complexed
nitrobenzene had been removed. The product was ligand as α = (AC – A)/(AC – AL), where AC is the
finally purified by column chromatography over silica absorbance value of the membrane for complete com
gel to yield the pure compound as a goldencolored plexation (i.e. at α = 0), AL is the absorbance value of
solid in 67% yield. The pure compound was eluted out the membrane for the free ligand (i.e. at α = 1) [16]
with 8–10% MeOH in CHCl3. and A is absorbance measured at any time during the
Preparation of membrane. The membrane solution titration procedure.
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. RESULTS AND DISCUSSION
The solution was immediately shaken vigorously to Spectral characteristics and complexation. Due to
achieve complete homogeneity. A glass plate with a sufficient insolubility of Qsal in water and the presence
rectangular frame 0.9 × 3 cm was cleaned with pure of two available donor atoms (NO) in its structure, it
THF to remove organic impurities and dust. Then, was expected to act as a suitable ion carrier in the PVC
25 μL of the membrane solution was transferred onto membranes for complex formation with Cu(II) ions
the glass plate and was spread evenly using a capillary (Fig. 1). According to the principle of hard and soft
glass tube to construct the membrane on the surface of acids and bases (HSAB), Cu(II) ion is classed as bor
the glass plate (membrane sensor). Then, the mem derline hard acid and forms stable complexes with
brane was allowed to dry in air for a few minutes. A both N and O donor atoms. Previous studies have been
membrane solution without Qsal reagent was used to shown that the Qsal derivatives are monoanionic tri
fabricate a reference membrane sensor. dentate or neutral bidentate ligands and coordination
Absorbance measurements. The prepared mem of these Iigands to metal ions leads to the formation of
branes were put in an acetate buffer solution of pH 4.0 a chelate ring [17–21]. The chelating agent Qsal acts
for 10 min to reach equilibrium. After drying, the as a bidentate (N, O) or a tridentate (N,O2) ligand
membrane sensor was immersed into a solution of with respect to pH. At the optimized pH of 4, Qsal is a
Cu(II) in acetate buffer (pH 4.0) for 4 min at ambient bidentate chelate and can bind to Cu(II) ion via N and
temperature. Then, it was washed with water for O donor atoms. For more investigation, the semiem

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 67 No. 8 2012


FABRICATION OF AN OPTICAL SENSOR BASED ON THE IMMOBILIZATION 689

pirical PM6 calculations [22] were performed to inves Table 1. Bond lengths (Å) for [ Cu ( Qsal ) ( H 2 O ) 3 ]
2+
complex
tigate the interaction between the Qsal ligand and
Cu(II) to predict the complex structure and coordina Bond length (Å)
tion mode. The results have revealed that the Cu(II)–
Qsal complex with twodentate N, O (one nitrogen Cu–N 1.952
atom of the imidazole ring, and one oxygen of the Cu–O 2.035
anthraquinone ring) and three aqua ligands with the Cu–OH2 2.158
Qsal to Cu(II) stoichiometric ratio of 1 : 1 is the most Cu–OH2 2.148
possible structure (Fig. 1). The Qsal/Cu(II) ratio was Cu–OH2 2.093
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 complex causes a change in color of the reagent
The structure of the Cu⎯Qsal complex consists of a phase from yellow to dark red.
sixmembered ring formed by N and O donor atoms of
the Qsal ligand with the copper center and also the bite Effect of pH and the type of buffer on the sensor
angle is more normal for this ion rather than other response. The influence of pH on the complex forma
metal cations. As can be seen in Fig. 1, the chelate ring tion was studied in the range of 1.0–6.5. The absor
is characterized by bite angle of 92.543° for N–Cu–O. bance measurements were made for 1.0 × 10–5 M cop
The bond lengths between the Cu(II) and each donor per ion at different pH values at 541 nm. The blank
atom of the Qsal and aqua ligands are listed in Table 1. membrane (membrane without Qsal in buffer solu
The bite angle and bond lengths cause the formation of tion) was taken as reference. Figure 3 shows the effect
Cu⎯Qsal ring to be relatively favorable. of pH on the response of the optical sensor membrane.
The absorbance measurements were expressed as
Figure 2 shows the absorption spectra of the immo absorbance difference, which was defined as the dif
bilized Qsal on PVC membrane which were obtained ference between the absorbance of the immobilized
after being equilibrated in acetate buffer solution Qsal alone and the absorbance of the Cu⎯Qsal com
(pH 4.0). The spectral change (decrease in absorption plex at 541 nm. pH Values were adjusted by the addi
band at 419 nm and increase in the absorption band at tion of dilute NaOH or HCl.
541 nm) is a result of exposure of membrane in contact
of copper solution which is due to the extraction of As can be seen from Fig. 3, as pH increases from 1.5
copper ion into the membrane. In the Cu⎯Qsal com to 4.0 the difference between absorbance value
plex, the intense absorption band at 541 nm (Fig. 2) is increases. At pH values more than 4.0, the response
assigned to ligandtometal charge transfer (LMCT) decreases. Protonation of the ligand at low pH values
by analogy to other Cu(II) complexes [23]. prevents its reaction with Cu(II), resulting in lower
sensor response. The pH values > 6.5 were not exam
In fact, Fig. 2 shows the absorption spectra of the ined because Cu(II) precipitates in alkaline solutions.
immobilized Qsal and complexation of Qsal and cop Also at pH values above 4 the ligand had leakage from
per that is response of optical sensor. The formation of 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 best physical properties with maximum sensitivities.
for further studies. This is most probably due to the presence of phosphate
Response studies of this membrane to various group, which facilitates the extraction–complexation
buffer solutions including acetate, citrate, universal of the copper ions into the bulk of PVC–membranes.
and phthalate (pH 4.0 and 0.1 M) showed that it Effect of the amount of Qsal on the optical sensor
responded the best to acetate buffer. In acetate buffer, response. In addition to the optimization of the type of
the membrane optical sensor showed better sensitivity plasticizer, it is also necessary to optimize the amount
and response time. Therefore, acetate buffer was of ligand. The influence of the amount of Qsal was
selected as the optimum buffer for further studies. studied by preparing membranes containing 0–5.0 mg
of Qsal (Fig. 4). The absorbance measurements were
Effect of membrane composition. Choice of solvent
mediator (plasticizer). Because of the effect of nature of made for 10–5 M copper ion for membranes with dif
the plasticizer on the membrane characteristics such ferent amounts of Qsal at 541 nm. The blank mem
as dielectric constant, the mobility and state of iono brane (membrane without Qsal) was taken as the ref
phers, it was expected to play a key role in determining erence. Increase in the amount of Qsal up to 1.94%
the ion selectivity of the membrane [24–26]. Several results in an increase in the absorbance. However,
different plasticizers such as oNPOE, DBP, DOS, higher amounts of Qsal (more than 1.94%) did not
TBP were tested for preparing the membrane. The improve the sensitivity and were not suitable due to the
membranes were prepared from a mixture of PVC leakage of Qsal. Thus, ~3% (w/w) of ligand (Qsal) in
(50 mg), plasticizer (100 mg), Qsal (3 mg) and NaTPB the membrane was selected for further studies.
(2 mg) in THF (1.5 mL) as described in the procedure Effect of the amount of NaTPB on the optical sensor
above. The results are shown in Table 2. As can be response. The effect of the amount of NaTPB on the
seen, for the case of TBP the membrane response response of the membrane is illustrated in Fig. 5. As
towards Cu(II) ions gives the widest working dynamic can be seen, increase in the amount of NaTPB up to
range. The membranes containing TBP revealed the 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 691

of foreign ions. Also, ~2% (w/w) anionic additive 1–α


(NaTPB) in the membrane was selected for further 1.2
studies.
Based on the results of the above mentioned studies, 1.0
the membrane obtained from a mixture of PVC (50 mg,
31.5%), TBP (100 mg, 63%), Qsal (3.0 mg, 1.94%) 0.8
and NaTPB (2.0 mg, 1.29%) in THF (1.5 mL) was
used as the membrane with optimized composition. 0.6
Response time. The response time of the optical
sensor is controlled by the time required for the ana 0.4
lyte to diffuse from the bulk of the solution toward the
membrane interface to associate with ligand. The 0.2
response time was tested by recording the absorbance
change from a pure buffer (pH 4.0) to a buffered
0
1.0 × 10–5 M copper solution. The data show that the –8 –7 –6 –5 –4 –3 –2
response times of the membranes can reach to 95% of log[Cu2+]
its final (steady state) value in about 3–5 min depend
ing on the concentration of Cu(II). Response time is Fig. 6. Calibration curve for the determination of Cu(II)
lower in concentrated solutions than in dilute solu ion at pH 4.0 and 541 nm.
tions.
Analytical figures of merit. Dynamic range and cal
ibration curve. Figure 6 shows the response of the opti The regeneration time, defined as the time taken
cal sensor membrane to various concentrations of for the sensor to reach the baseline signal (the signal
Cu(II) ion. A concentration of 5.0 × 10–3 M has been observed in 0.1 M acetate buffer at pH 4.0), where
found as the concentration of Cu(II) ion that saturates minimum absorbance had been reached at the wave
the membrane optical sensor. As can be seen from this length of 541 nm, was 4 min for the optimized sensor
figure, the plot of (1 – α) versus logarithm of copper in contact with 5.0 × 10–5 M of Cu(II).
ion concentration (M) exhibits a linear portion in the The response characteristics of the proposed opti
concentration range of 6.3 × 10–7–1.00 × 10–4 M with cal sensor were compared with previously reported
equation of Y = 0.225 log[Cu2+] + 1.4370 sensor for the determination of Cu(II) ion [27–31]
(R2 = 0.9983) where Y is (1 – α). and the results are summarized in Table 3. As it is obvi
Detection limit. Detection limit of the sensor mem ous from Table 3, the linear range, detection limit, and
brane, which is defined as the average blank signal plus response time of the proposed sensor are better or
three times of its standard deviation (n = 7) is equal to comparable to those of other sensors reported in liter
3.3 × 10–7 M Cu(II). ature. The proposed sensor has a short response time
in comparison to other sensors (except for [30]). Also,
Regeneration of the optical sensor membrane. After it has lower detection limit and wider dynamic range
the contact of the sensor with Cu(II) solution, the sen compared to the sensors referred as [27–30]. Further
sor membrane must be regenerated by using a suitable more, in this work we use entrapment method for
stripping reagent. Preliminary experiments were per immobilization of indicator that eliminates the
formed to select a suitable regenerating solution. agglomeration of indicator on the membrane.
Among several compounds including EDTA, sodium Agglomeration of the indicator is a severe problem in
fluoride, 5sulfosalicylic acid dihydrate, NaSCN, physical adsorption immobilization.
HCl, HNO3 and H2SO4, the last three acids were
found to be the most suitable stripping solutions and Effect of foreign ions. The metal ion complexing
among them HCl (0.1 M) was the best one for regen properties of nonmacrocyclic ligands such as Qsal in
erating optical sensor. Other reagents were not suitable aqueous solution have been discussed [32]. The affin
regenerating solutions, because there can not compete ity that metal ions have for ligands is controlled by
with Qsal for Cu(II) ions. size, charge and electronegativity. This can be refined
The membrane sensor was used many times to further by noting that for some metal ions their chem
determine Cu(II) concentration. Each time mem istry is dominated by size and charge, while for others
brane was regenerated by stripping reagent and after it is dominated by their electronegativity.
conditioning absorbance was measured. Again after To determine the selectivity of the optical sensor
five times regeneration, a drift of about 3.5% was membrane, the membrane was tested for the determi
obtained in the response of the sensor. According to nation of 1.0 × 10–5 M of Cu(II) ions in the presence
low drift on the sensor response after five times regen of different metal ions. Table 4 summarizes the toler
eration, it is obvious that the membrane components, ance ratio for several cationic and anionic species. The
such as ionophore entrapped onto the membrane, tolerance limit was taken as the concentration of the
have not leached to the solution after each using. interfering species causing an error of not more than

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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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