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Analytical Letters
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Development of a Highly Sensitive and Selective Bismuth Optical Sensor Based on (2E,4E)-5-(2,4-Dinitrophenyl Amino)penta-2,4-dienal
Majid Arvand & Mojtaba Eskandarnejad
a a a

Department of Chemistry, Faculty of Science, University of Guilan, Rasht, Iran Version of record first published: 02 Dec 2008.

To cite this article: Majid Arvand & Mojtaba Eskandarnejad (2008): Development of a Highly Sensitive and Selective Bismuth Optical Sensor Based on (2E,4E)-5-(2,4Dinitrophenyl Amino)penta-2,4-dienal, Analytical Letters, 41:15, 2877-2892 To link to this article: http://dx.doi.org/10.1080/00032710802424164

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Analytical Letters, 41: 28772892, 2008 Copyright # Taylor & Francis Group, LLC ISSN: 0003-2719 print=1532-236X online DOI: 10.1080/00032710802424164

SENSORS

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Development of a Highly Sensitive and Selective Bismuth Optical Sensor Based on (2E,4E)-5(2,4-Dinitrophenyl Amino)penta-2,4-dienal
Majid Arvand and Mojtaba Eskandarnejad
Department of Chemistry, Faculty of Science, University of Guilan, Rasht, Iran

Abstract: An optical sensor based on (2E,4E)-5-(2,4-dinitrophenyl amino)penta2,4-dienal as ionophore has been developed for the determination of bismuth(III) ions in aqueous solutions. This proposed membrane works on the basis of a cation-exchange mechanism and shows a significant absorbance signal change on exposure to 1 M HCl solution of pH 0.0 containing bismuth ions. The optode membrane shows a reproducible and reversible response toward bismuth in the concentration range 0.2 to 60.5 ppm with a detection limit of 0.095 ppm. This sensor has been used for determination of bismuth in real samples. Keywords: Bismuth ion, neutral ionophore, optode, poly(vinyl chlorid), UV=vis

INTRODUCTION The ion-selective optode is one of the optical chemical sensors (so-called optodes or optrodes) that have attracted interest since the 1970s (Seitz

Received 29 June 2008; accepted 1 August 2008. The authors are thankful to the postgraduate office of Guilan University for the support of this work. Address correspondence to Majid Arvand, Department of Chemistry, Faculty of Science, University of Guilan, P. O. Box 1914, Rasht, Iran. E-mail: arvand@ guilan.ac.ir 2877

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1991; Arnold 1992; Janata 1992). Generally, the essence of the usefulness of the ion-selective optode is the ion selectivity associated with the highly selective complexation of an ionophore (either neutral or charged) with an analyte ion in optical chemical sensing. In this case, highly selective neutral ionophores developed so far for the application to polymeric membrane ion-selective electrodes (ISEs) (Suzuki et al. 1993; Suzuki et al. 1995, 1996; Siswanta et al. 1996) can be utilized without any chemical modifications. This is one of the reasons why the development of the ion-selective optode has progressed only during the past 20 years, although ISEs have a history of more than 40 years. In other words, this methodology has progressed together with the development of polymeric membrane ISEs. In this connection, chemical sensors based on optical signal measurement use advanced techniques in analytical chemistry, and they have been accepted as advantageous because they can be miniaturized and can be manufactured easily for low cost. Optical sensors that make use of plasticized polymeric membranes containing a reagent that reacts with the analyte to produce a distinctive color change are of great interest for, among other applications, the trace analysis of heavy-metal ions (Seiler and Simon 1992; Oehme and Wolfbeis 1997). Bismuth, a heavy, brittle, white crystalline trivalent-poor metal, has a pink tinge and chemically resembles arsenic and antimony (Earnshaw 1997). Bismuth has been used in medicines for the treatment of helicobacter pyloricinduced gastritis (Slikkerveer and de Wolf 1989; Sadler 1997). Bismuth and its compounds are also used in semiconductors, cosmetic preparations, alloys, and metallurgical additives and in the preparation and recycling of uranium nuclear fuels (Thomas 1991). As the uses of bismuth increase, it has spread in the environment, and the chance of exposure of organisms to bismuth has increased. Several methods have been developed for the determination of bismuth. These include hydride generationinductively coupled plasma atomic emission spectrometry (HG-ICP-AES) (Morrow, Witshire, and Huvsthous 1997), electrothermal vaporizationICPmass spectrometry (ETV-ICP-MS) (Hinds, Gregoie, and Ozaki 1997), atomic absorption spectrometry (AAS) (Tokalioglu, Kartal, and Elci 1997; Hall et al. 1997), potentiometric stripping analysis (PSA) (Ostapczuk 1993), anodic stripping voltammetry (ASV) (Ye and Khoo 1997; Wang, Sun, and Li 1997), and cathodic stripping voltammetry (CSV) (Ferri, Paci, and Morabito 1996). In many of these methods for the determination of bismuth (Morrow, Witshire, and Huvsthous 1997; Hinds, Gregoie, and Ozaki 1997; Tokalioglu, Kartal, and Elci 1997; Hall et al. 1997), there is no in situ measurement of the free Bi(III) concentration. In view of this fact, the optode has become a rapidly expanding area of analytical chemistry (Wang 1995; Hisamoto and Suzuki 1999; Wolfbeis 2000;

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Hisamoto et al. 1995) because it offers the advantages of simple preparation, reasonable selectivity, and reasonable sensitivity. The main purpose of this work is to construct a highly sensitive and selective optical chemical sensor for measurement of bismuth using (2E,4E)-5-(2,4 dinitrophenyl amino)penta-2,4-dienal (HL) as complexing agent. This ionophore can selectively extract Bi3 from aqueous sample solution into organic membrane phase and forms a complex, which results in a decrease in the ionophore absorbance and produces a new absorbance peak at a lower wavelength. The design and construction of optode to determination of bismuth ion has not, to our knowledge, been previously reported.

EXPERIMENTAL Reagents Relatively high-molecular-weight poly(vinyl chloride) (PVC), nitrobenzene (NB), acetophenone (AP), dibutiyl phthalate (DBP), o-nitrophenyl octyl ether (o-NPOE), tetrahydrofuran (THF), and all other reagents were obtained from Merck. A stock solution of 100 ppm Bi3 was prepared by dissolving an appropriate amount of Bi(NO3)3 (Merck) in a 100-mL volumetric flask and diluted with doubly distilled water. Working standard solutions with lower concentrations were prepared by a suitable dilution of the stock solution. The pH adjustments were made with hydrochloric acid solution (1 M and 0.1 M) to achieve the desired pH. The structure of the ionophore is depicted in Scheme 1.

Synthesis of the Ionophore (HL) The synthetic scheme of the ionophore HL is as follows: 0.5 g (1.8 mmol) of the N-(2,4-dinitrophenyl)pyridinium chloride was dissolved in 5 mL methanol (solution A). This solution was stirred for 15 min at room temperature. During this time, 0.13 g (1.8 mmol) pyrrolidine was dissolved in 3 mL methanol. In an individual vessel, the amount of 0.1 g (0.94 mmol) sodium carbonate was dissolved in 5 mL of water and then the contents of these two beakers were added to each other. This solution was slowly added to the solution A during 10 min. The color of solution changed to red. The obtained precipitate was filtered and recrystallized from an acetone-water mixture. The precipitate was washed with cold methanol. The melting point of the red crystalline form of the HL ionophore was 176178 C; IR (Nujol): 3291, 3113,

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Scheme 1. The structure of ionophore.

3068, 1601, 1518, 1337, 1240, 1163, 1128, 989, 710 cm1;1H NMR (500 MHz, DMSO-d6): 6.09 (dd, J 5.1, 15 Hz, 1H), 6.64 (t, J 12 Hz, Hz, 1H), 7.43 (dd, J 11.5, 15 Hz, 1H), 7.78 (d, J 9.5 Hz, 1H), 7.98 (d, J 12.7 Hz, 1H), 8.43 (dd, J 2.7, 9.5 Hz, 1H), 8.83 (d, J 2.7 Hz, Hz, 1H), 9.47 (d, J 8.1 Hz, 1H), 10.43 (br, 1H) ppm; 13C NMR (125 MHz, DMSO-d6): 114.3, 117.9, 123.8, 128.7, 130.7, 138.4, 139.3, 142.5, 153.4 ppm; C11H9N3O5 (263.21): calcd. C 50.20, H 3.45, N 15.96, O 30.39; found C 50.35, H 3.63, N 15.77, O 30.25. Apparatus A Cary 100 UV-vis spectrophotometer with a 1-cm cell was used for recording all spectra and absorbance measurements. A Metrohm pH meter (model 827) with a combined double junction glass electrode was used for monitoring pH values. All measurements were made in the absorbance mode. Membrane Preparation The optode membranes were prepared from 8 mg of ionophore, 120 mg of acetophenone, and 80 mg of PVC. The membrane components were dissolved in 1.5 mL of freshly distilled THF in a glass vial. The solution was immediately shaken vigorously to achieve complete homogeneity. An aliquot of 40 mL of this solution was dropped onto a dust-free glass plate and allowed to stand in ambient air for 1 h before use.

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Recommended Procedure An easily handled, small, and low-cost ion-sensing film optode that can be utilized as a handy sensing tool has been developed (Hisamoto and Suzuki 1999). These film optodes were a plasticized PVC-matrix membrane containing a lipophilic ionophore. For simple and easy use of this ion-sensing film, the PVC membrane was attached to the surface of an 8mm 25-mm thin glass plate whose size fits into a conventional glass vessel used as a standard optical cell for a spectrophotometer as shown in Fig. 1. Consequently, the determination of an analyte ion using the film optode can be achieved by simply immersing it into the glass vessel for monitoring the absorbance change as the response of the optode (Seiler and Simon 1992). The prepared membrane was put vertically inside the sample cell containing 3 mL hydrochloric acid solution with pH 0.0, and a membrane (without ionophore) at the same conditions was used as a blank membrane. The sample cell was titrated with standardized metal ion solutions, and the absorbance value of the system was measured after 20 s (required to reach the equilibrium). The membrane response may be defined as the difference between the absorbance of the ionophore alone and the absorbance of the Bi3-ionophore complex at 318 nm.

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Figure 1. Schematic views of the film-type ion-sensing plate and experimental setup (Hisamoto and Suzuki 1999).

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RESULTS AND DISCUSSION Spectral Characteristics of Ionophore in the Solution A 5.07 104 M ionophore solution was prepared by dissolving 2 mg of the ionophore in 15 mL of THF. Eleven solutions of different cations (Cd2, Mn2, Cu2, Bi3, Co2, Ba2, Zn2, Mg2, Ca2, Pb2, Tl) with equal concentrations were selected. Then, 3 mL of them and 1 mL of ionophore solution were dropped into the glass vial. The solutions were immediately shaken vigorously to achieve complete homogeneity. Finally, obtained solutions were injected to the cells, and absorbance values were measured after 20 s (because of the time required to reach the equilibrium). The reference cell contains 1 mL ionophore solution and 3 mL distilled water. The absorbance was measured over the wavelength range of 300 to 700 nm. The spectral change (decrease in absorption band at 406 nm and increase in the absorption band at 318 nm) shows that the ionophore is a selective complexing agent for bismuth ions (Fig. 2). As can be seen, the complexation was accomplished by a relatively strong shift of the absorption band of the ligand HL, with kmax at 406 nm toward shorter wavelength, 318 nm, for the complex, at which the ligand has

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Figure 2. Absorption spectra of ionophore in the solution at the presence of different cations: (1) Bi3, (2) HL, (3) Mn2, (4) Cd2, (5) Pb2, (6) Zn2, (7) Ca2, (8) Ba2, (9) Mg2, (10) Cu2, (11) Co2, and (12) Tl.

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low absorbance. Such a pronounced effect on the electronic spectra of the ligand could be related to strong complexation with Bi(III) ions (Winkler 1972). To determine the stoichiometry of the resulting complex, the absorption spectra containing 1.67 104 M of the ligand solution at a fixed ionic strength of 0.05 M (maintained by TEAP) and varying amounts of the bismuth ion were obtained at 318 nm in THF solution. The absorbance versus [Bi3]=[HL] molar ratio plot revealed an inflection point at [Bi3]=[HL] molar ratio of about 0.5, emphasizing the formation of a 1:2 (metal-to-ligand) complex in the solution. Spectral Characteristics of Ionophore in the Membrane After HL was incorporated in the PVC membrane, the spectral properties of the ligand in the membrane remained the same as those measured in organic solvent (Fig. 3). This is the basis of the optical sensing device in this investigation. Therefore, the wavelength 318 nm has been used in all subsequent measurements of absorbance. It is noticeable that the absorbance of ionophore into the membrane at 406 nm is almost constant and does not decrease with increasing Bi3 concentration. This is probably due to the excess amount of HL ionophore into the membrane and saturation of membrane phase that causes the amounts of absorption not to change by complexation with Bi3 ion.

Figure 3. Absorption spectra of plasticized PVC bismuth bulk-optode membrane doped with HL measured in acidic solution, pH 0.0, and at varying bismuth concentrations: 0.1, 0.2, 4.1, 12.3, 28.0, 40.0, 52.7, and 60.5 ppm. The peak absorbance at 318 nm increased monotonically with increasing bismuth concentration. Inset: calibration curve for determination of Bi(III) using the optimum conditions for the range of 0.0265 ppm Bi(III).

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Effect of Membrane Composition Choice of Plasticizer Plasticizers for plastics are additives, most commonly phthalates, that give hard plastics like PVC the desired flexibility and durability. Plasticizers work by embedding themselves between the chains of polymers, spacing them apart (increasing the free volume), and thus significantly lowering the glass transition temperature for the plastic and making it softer. For plastics such as PVC, the more plasticizer added, the lower its cold flex temperature will be. This means that it will be more flexible, though its strength and hardness will decrease as a result of it (Bakker, Bu hlmann, and Pretsch 1997). Optode films with a high amount of plasticizer have optimum physical properties and ensure relatively high mobility of their constituents. To give a homogeneous organic phase, the membrane solvent must be physically compatible with the polymer, i.e., have plasticizer properties. Otherwise, it exudes, yielding membranes of unstable composition. For various reasons, it also has an influence on the selectivity behavior. Four plasticizers (DBP, o-NPOE, NB, and AP) were selected for preparing the membrane. The membranes were prepared from a mixture of PVC (80 mg), plasticizer (100 mg), and ionophore (8 mg) in THF (1.5 mL). The absorbance measurements (at wavelength 318 nm) were made for 40 ppm bismuth ions for membranes with different types of plasticizer. The membranes containing acetophenone showed the best physical properties with maximum sensitivities. For determination of the effect of the amount of plasticizer on the optode response, membranes that contain different amounts of solvent mediator (80, 90, 100, 110, 120, 130 mg) were prepared. Absorption measurements showed that membranes containing 120 mg AP revealed the best physical properties and maximum absorption.

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Effect of the PVC Amount In general, the thickness and hardness of the membrane depend on the amount of PVC used. At lower PVC contents, the membrane becomes mechanically weak and swells up easily in aqueous solution, and leaching of the membrane is significant. By increasing the amount of PVC, the membrane becomes dense, preventing the leaching of ionophore from membrane into aqueous solution (Gholivand et al. 2005). In this work, we examined the various amounts of PVC on the response characteristic of membrane. The results illustrated that increasing the amount of PVC

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(more than 80 mg) did not improve the sensitivity and were not suitable because of the decreasing of ion diffusion into the bulk of membrane. Effect of the Amount of Ionophore Ionophores play a key role in the selectivity of ion selective optodes. The rational design of synthetic carriers takes advantages of the different elements of molecular recognition. The creation of suitable binding sites and proper topology in the ionophore that are complementary to the size and charge of a particular ion can lead to very selective interaction (Singh et al. 2007). The effect of the amount of ionophore on the response of the membrane is illustrated in Fig. 4. The absorbance measurements at 318 nm were made for 28.0 ppm bismuth ions using membranes with different amounts of ionophore. The blank membrane (membrane without ionophore in the acidic solution with pH 0) was taken as the reference. The absorbance measurements were expressed as absorbance difference, which was defined as the difference between the absorbance of the ionophore alone and the absorbance of the Bi3-ionophore complex at 318 nm. As can be seen from Fig. 4, increase in the amount of ionophore results in an increase in absorbance. Membranes containing high amounts of ionophore (more than 8 mg) showed slightly leakage of ionophore-bismuth complex. Finally, the optimized membrane was selected as the membrane containing a mixture of PVC (80 mg), AP (120 mg), and ionophore (8 mg).

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Figure 4. Effect of different amounts of ionophores on the response of membrane in the presence of 28.0 ppm bismuth ions.

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Effect of pH on the Membrane Response The effect of pH values on the optode response in the presence of Bi3 ions is shown in Fig. 5. The response curve data were obtained by measuring the absorbance values for Bi3 at different pH values. Absorption value reached to the highest value at the pH 0 and with increasing pH, absorption value decreased. It is noticeable that when the pH increases to high values, the bismuth(III) ions are converted to hydroxyl species or precipitated. In subsequent experiments, a bismuth solution with pH 0 was selected as an ideal experimental condition.

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Calibration Range and Detection Limit The absorption spectra of the proposed membrane optode in the presence of varying concentrations of bismuth ion at pH 0 was obtained, and the resulting calibration graph of absorbance vs. concentration of bismuth at the wavelength of 318 nm is shown in Fig. 3 (inset). As seen, the dynamic concentration range of the optical membrane sensor is 0.260.5 ppm. Detection limit of the sensor film, which is defined as the concentration of the sample yielding a signal equal to the blank signal three times its standard deviation, was found to be 0.095 ppm.

Figure 5. Effect of pH on the response of membrane in the presence of bismuth ions at 318 nm.

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Effect of Foreign Ions The effect of foreign ions on the determination of Bi3 by the proposed sensor was investigated. An ion was considered to be an interferent when it caused an error greater than 5% in the determination of bismuth. The resulting relative error is defined as Error (%) [(A A0)=A0 100], in which A0 and A denote the absorbance of the membrane in the absence and presence of the different foreign interferents, respectively. To determine the selectivity of the optode membrane, the membrane was tested for the determination of 40 ppm of Bi3 ions in the presence of some metal ions including Pb2, Ca2, Mn2, Ni2, Cu2, K, Na, Cr3, V3, Ba2, Cd2, Mo(VI), Fe3, Al3, Tl, Sn2, Hg2, ZrO2, and some anions. The results of selectivity studies are summarized in Table 1. As can be seen, the relative error of common ions such as that of alkali metals (Fe3, Al3, Mn2, S2O32, Br, I, PO43, NO2, Ba2, Mo(VI), Cd2, Sn2, Tl except Cu2 and Pb2) were less than 5%, which is tolerated. Thus, this sensor exhibited excellent selectivity toward Bi(III) with respect to other coexisting interferences, which make it feasible for practical applications.

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Reversibility, Reproducibility, and Lifetime It would be desirable for a sensor to have good reversibility and reproducibility. For evaluating these parameters, the membrane was exposed repeatedly to 1 M HCl solution, 12.3 ppm Bi3 ions solution, and 52.7 ppm Bi3 ions solution. The mean absorbance values with the standard deviation were found to be 0.331 0.006 (1 M HCl solution, n 9) and 0.423 0.005 (12.3 ppm Bi3, n 9) and 1.257 0.004 (52.7 ppm Bi3, n 9). Thus it can be concluded that the sensor performance is completed and shows good reproducibility. The results are shown in Fig. 6. To study of stability and lifetime of the proposed sensor, the absorption signal of the optical membrane in contact with the bismuth(III) in solution was recorded. After washing by 1 M HCl, which regenerated the membrane, it was kept unused over a period of 3 months. The membrane exhibited good stability with a deviation of less than 1.3% when bismuth(III) ion solutions were measured. Then, over a period of 6 months, using the optode in contact with bismuth(III) solution (12.3 ppm) for 1 h per day, the absorbance signal of the optical membrane changed no more than 4% during the measurement of sample solution over this period.

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Table 1. Effect of different interferents on the absorbance signal of optical sensor (40 ppm bismuth) Interferent Mn2 Ca2 K Na Ni2 Cr3 V3 Hg2 ZrO2 Mo(VI) Fe3 Al3 NH4 Ba2 Cd2 Sn2 Tl Cu2 Pb2 SCN PO43 NO2 HCO3 S2O32 SO42 Br I Concentration (mol L1) 1.0 101 1.0 101 1.0 101 1.0 101 1.0 102 5.0 102 5.0 102 5.0 102 5.0 102 5.0 102 5.0 102 5.0 102 5.0 102 5.0 102 5.0 102 5.0 102 5.0 102 5.0 102 5.0 102 1.0 101 1.0 101 1.0 101 1.0 101 1.0 101 1.0 101 1.0 101 1.0 101 Relative error [(A A0)=A0] 100 1.45 1.56 1.14 1.21 2.13 2.14 2.08 2.56 1.07 1.69 3.12 3.56 1.11 1.39 2.21 2.14 1.24 5.32 5.87 1.20 1.15 0.55 0.46 0.78 0.65 0.55 0.50

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Response Time From the literature and preliminary experiments, the amounts of PVC and plasticizer can influence the response time of the membrane. The response time of the present optical sensor is controlled by the time of required for the analyte to diffuse from the bulk of the solution toward the membrane interface to associate with the ligand. The results revealed that the membranes containing 80 mg PVC and 120 mg plasticizer gave the shortest response time. The data show that the response time of membrane can reach to 95% of its final (steady state) value in a time of less than 20 s.

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Figure 6. Absorption response vs. time at 318 nm after several repeated concentration changes between (a) 1.0 M HCl solution (0.331 0.006), (b) 12.3 ppm Bi3 (0.423 0.005), and (c) 52.7 ppm Bi3 (1.257 0.004) in HCl solution of pH 0.0.

Table 2. Recovery of bismuth in different water samples Sample Sea watera Seawater Seawater Tap water Tap water Tap water Mineral waterb Mineral water Mineral water River waterc River water River water Added (ppm) 12.50 16.70 12.50 16.70 12.50 16.70 12.50 16.70 Found (ppm) <Detection limit 12.43 0.05 16.43 0.05 <Detection limit 12.34 0.04 16.76 0.07 <Detection limit 12.96 0.07 17.41 0.05 <Detection limit 12.82 0.07 16.98 0.08 Recovery (%) 99.4 98.4 98.7 100.4 103.7 104.2 102.6 101.7

a Obtained from Khazar Lake (Anzali, Iran); numbers in the parentheses show the standard deviations for five replicates. b The water obtained from Damash Spring (Rudbar, Iran). c The water sample obtained from Sefidrud River (Emamzadeh Hashem, Iran).

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Analytical Application As the system has been optimized with laboratory prepared sample, the final test on the efficacy of the sensor as an environmental monitoring device is to run real water samples. The known amounts of Bi(III) were added into them, and the recovery of spiked Bi(III) in these samples was studied with the proposed optical sensor. The results are given in Table 2. The standard deviations of the analyses and the recoveries of the added bismuth to the samples show that the proposed method has capability for real sample analysis. CONCLUSIONS In conclusion, we have shown that a (2E,4E)-5-(2,4 dinitrophenyl amino)penta-2,4-dienal ionophore can be used for the development of an optically sensitive sensor for bismuth ions. Furthermore, the proposed optode film was shown to exhibit better bismuth ion selectivity over the cations such as Mn, Ca, Ni, K, Na, Cd, Al, Mo, Fe, Ba, Sn, Tl, Cr, V, and Hg and some of anions. On the basis of the results presented in this work, the proposed bismuth ion-selective optode has many advantages including easy preparation, low cost, fast response time, good dynamic range, and reproducibility. The sensor can be regenerated readily with HCl solution. It is fully reversible and has long a lifetime. REFERENCES
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