Documente Academic
Documente Profesional
Documente Cultură
DOI 10.1007/s00706-009-0167-x
ORIGINAL PAPER
Received: 7 January 2009 / Accepted: 25 July 2009 / Published online: 22 August 2009
Springer-Verlag 2009
Abstract The characterization of an optical sensor In most cases, a thin layer of polymer containing an
membrane is described for the determination of tin (II) immobilized indicator dye is the core element of such
based on the immobilization of dithizone on a triacetyl- sensors [1]. Both the methods of immobilization and the
cellulose membrane. The membrane responds to tin (II) class of matrix exert a significant effect on the performance
ions by changing color reversibly from green to red in of ion-selective layers [2]. Optochemical sensors based on
buffer solution at pH 6 and wavelength 611 nm. This op- organic polymeric thin or thick films have been investi-
tode has a linear range of 0.36.33 lg cm-3 (2.52 gated extensively in the last decade [3, 4]. Organic
53.32 lmol dm-3) of Sn2? ions with a limit of detection of indicator dyes and immobilization techniques play impor-
0.15 lg cm-3 (1.26 lmol dm-3). The response time of the tant roles in the development and design of the optode.
optode was about 810 min depending on the concentra- Normally, the immobilization of the indicator is achieved
tion of Sn2? ions. The selectivity of the optode to tin (II) by absorption [5], chemical bonding [6], or physical
ions at pH 6 was good. The sensor can be readily regen- entrapment [7] into the support materials. Reaction with
erated by exposure with EDTA solution. The color is fully the analyte changes the absorbance, fluorescence, reflec-
reversible, and the optical sensor could be fully regener- tance, and reflective index behavior of the sensitive layer
ated. Experimental results showed that the optode could be [811]. The development of optical sensors in analytical
used as an effective tool in analyzing the tin content in chemistry is of great interest because of their possible
canned foods. application in biology, biotechnology, and ecology [12,
13], and also because of their advantages such as small
Keywords Optode Sn2? ions EDTA Dithizone size, freedom from electrical interference, low cost, safety,
Canned foods the possibility of remote sensing, easy fabrication, good
sensitivity, and selectivity.
Tin is a widely sought metal and used in hundreds of
Introduction industrial processes, tin plates, pewter sheets, or jewelers
models, amalgam powder (in biological cases such as
There is a huge variety of different chemical sensors, and dental filling) throughout the world. Interest in tin has
over the past 2 decades, the development and applications focused on its toxic potential in humans through the contact
of optical chemical sensors have grown rapidly. An optode of foods with tin-coated cans and tinfoil. Large amounts of
or optrode is an optical device that practically measures a tin can accumulate in foods in contact with tin plates unless
specific substance by absorbance, chemical bonding, or these are lacquered or coated with resin [14, 15].
physical entrapment [1]. The sensing element consists of Tin can enter foods either from natural sources, envi-
reagent dyes immobilized in organic or inorganic matrices. ronmental pollution, packaging material, or pesticides.
Higher concentrations are found in processed food and
canned foods. Dissolution of the tinplate depends on the
H. Tavallali (&) S. Daneashian
Chemistry Department, Payame Noor University, Shiraz, Iran food matrix, acidity, presence of oxidizing reagents
e-mail: tavallali@pnu.ac.ir; tavallali@yahoo.com (anthocyanin, nitrate, iron, and copper), presence of air
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1150 H. Tavallali, S. Daneashian
Abs.
0.8
the length of time after manufacture. After a can has been
opened, the amount of dissolved tin rapidly increases.
Fortunately, there are no long-term effects due to normal
0.4
intakes from tin in the food even if it is present in higher
levels. Several analytical methods have been developed for
the detection and determination of tin, including spectro-
0
photometry [20, 21], atomic absorption spectrometry [22, 400 450 500 550 600 650 700
23], atomic emission spectrometry [24], electrochemical /nm
[25], and spectrofluorimetric methods [26, 27]. 0.6
These methods have good selectivity, but they require (b)
well-controlled experimental conditions and careful sample 0.5
preparation. Although there are many reports on the
development of optodes for metal ion determinations, to 0.4
the best of our knowledge there has been no report on the
Abs.
The optode membrane response to different metal ions was the reagent is in excess and the aqueous phase is acidic
investigated in universal buffer (0.04 M) at pH 6. The with pH 6, tin in the aqueous phase reacts with dithizone
membrane was first exposed to the buffer solution, and the dissolved in an organic solvent (ethylenediamine) to give a
absorbance was measured at 611 nm. Then the sample highly colored red complex that distributes into the organic
solution was added and the absorbance at 611 nm was phase. The absorption spectra of the membrane obtained
again measured after 10 min. after being equilibrated in universal buffer solution (pH 6)
Dithizone (sym-diphenylthiocarbazone) contains azo containing different concentrations of tin (II) ions are
and hydrosulfide groups (S,N donating ligand), which can shown in Fig. 2a. The spectral change (decrease in
form stable complexes with many metal ions under proper absorption band at 611 nm and increase in absorption band
conditions and is widely used in extraction spectropho- at 507 nm) is a result of the increase of tin ion concen-
tometry. The structure of dithizone is depicted in Fig. 1. If tration in the membrane, which is due to the extraction of
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Design and characteristics of tin (II) optode 1151
tin ion into the membrane. In fact, the mechanism of the 0.5
response of optode is believed to be based on complexation
of dithizone and tin (II), which is accompanied by the
deprotonation of the ligand dithizone and release of proton 0.4
in the solution.
Abs.
Figure 2a and b shows the absorption spectra for free and
immobilized dithizone, which were obtained after being 0.2
equilibrated in buffer solutions (pH 6) containing different
concentrations of tin (II). The spectral changes are the
result of the addition of Sn2? ions and their reaction with
0.1
dithizone. The spectral characteristic of this sensor showed
two maxima at 611 and 507 nm. And those of the free dye
at 570 and 469 nm were observed. It is important to note
0
that the absorption spectrum of the immobilized indicator 0 1 2 3 4 5 6 7 8
is red shifted (or bathochromic shifted) in comparison to c (Sn 2+)/g cm-3
that of the soluble form (611 instead of 570). This suggests
that the structured conformation of the immobilized indi- Fig. 4 The optode film response versus Sn2? ion concentrations in
the range 07 lg cm-3 (059 lmol dm-3) at pH 6
cators is more planar than of its soluble analogue [28].
The effect of pH
dithizone alone and the absorbance of the membrane in the
The effect of pH on the complex was studied in the range presence of tin (II) ions. Figure 4 shows the absorption
of 19 by changing the universal buffer from 1 to 9. A signals of the optode film to the various concentrations
maximum value in the sensor response was obtained at pH of Sn2? ions in the range of 0.37 lg cm-3 (2.52
6 and can be seen in Fig. 3. This pH was selected for 59 lmol dm-3) for tin (II) ions.
further studies. In this case, 6.5 lg cm-3 (54.73 lmol dm-3) was found
as the concentration of Sn2? ions that saturate the film. As
Dynamic range can be seen, the plot of the difference in absorbance versus
Sn2? ion concentration exhibited a linear range between
The absorbance measurements were expressed as the 0.3 and 6.33 lg cm-3 (2.5253.32 lmol dm-3). The
absorbance difference, which is defined as the difference detection limit that was estimated as the concentration of
between the absorbance of membrane with immobilized analyte producing an analytical signal equal to three times
the standard deviation of the blank signal was found to be
0.15 lmol dm-3 for tin (II).
0.03
Response time
123
1152 H. Tavallali, S. Daneashian
Fig. 5 Typical response curve of the film optode at 507 nm as a To determine the selectivity of the optode film, the film
functional of time when the film was exposed to 8.42 lmol dm-3 was tested for the determination of 8.42 lmol dm-3 Sn2?
Sn2? ions ions in the presence of other metal ions, including Pb2?,
Cd2?, Cu2?, Hg2?, Ag?, Mg2?, Zn2?, Ni2?, Al3?, Co2?,
Bi3?, Fe2?, V4?, Na?, K?, and Ba2?. The tolerance limit
Life time of optical sensor was taken as the concentration causing an error of 5% in
the determination of Sn2?. Samples containing a fixed
The life time of membrane was determined by adding a concentration of Sn2? ions, 8.42 lmol dm-3, and different
buffer solution (pH 6) in a cuvette including the film. The concentrations of other metal ions were analyzed by the
signal was recorded at a wavelength of 611 nm over a method. At the applied pH value no interference was
period of about 5 h. No significant loss of the indicator observed from even 100-fold excess of the above metal
occurs during this time. When the membrane was ions except Co2?, Cu2?, and Ni2?. However, the interfer-
exposed to light, no drift in signal was observed, and the ence from these ions can be eliminated by using murexide
sensing phase was stable over the experiment with no as the masking agent. Ions such as Cd2?, Hg2?, Ag?, Fe2?,
leaching of the indicator. However, prepared membranes Al3?, and Zn2? were precipitated at this pH.
were kept under water when not in use to prevent them It is apparent from this study that discrimination among
from drying out. Additionally, the stability of response of different metals can be achieved by the control of several
the film was investigated over 1 month under ambient parameters, including the absorption wavelength, the pH,
conditions, which indicated that the film was stable over and the sample contact time in addition to the use of
this period. masking agents.
Reproducibility Application
The reproducibility and reversibility of the membrane in To evaluate the analytical applicability of the proposed
the determination of tin (II) were evaluated by repeatedly method, it was applied to determine tin in mineral water
exposing the membrane to 8.42 lmol dm-3 tin solution. samples and also in canned products. The water sample
The repeatability was evaluated by performing seven was prepared by Kohrang mineral water factory, Shiraz,
determinations with the same standard solution of Sn2?. Iran. The canned fish was prepared by the Sahele fac-
The relative standard deviation (RSD) for the response of tory, Iran, and the fruit juice samples were prepared by
one membrane towards a 8.42 lmol dm-3 of tin solution Shani factory, Iran. These samples were spiked with a
was 1.9%. The reproducibility of the response of different standard stock solution of tin (II) and determined by the
membranes was also studied. Six different membranes proposed optical membrane. The results are shown in
were prepared from the same batch, and they were evalu- Table 1.
ated by performing the determination of 8.42 lmol dm-3 This proposed method also was applied to determine the
tin. The RSD for the response between membranes was concentration of tin in different canned products (fruit juice
3.2% for Sn2? ions. The results show the reproducibility to and fish). Prior to the determination, samples were digested
be satisfactory. and diluted. The results are given in Table 2.
123
Design and characteristics of tin (II) optode 1153
Table 2 The total tin content of canned products (after digestion) reversible, has a low detection limit, and can be applied to
Type of sample Content of tina (mg kg-1)
the monitoring of tin in real samples.
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1154 H. Tavallali, S. Daneashian
meter (model jenway) with a Metrohm double junction Acknowledgment The authors wish to acknowledge the support of
glass electrode was used for pH adjustment. this work by Payame Noor University Research Council.
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