ISSN 1070-4272, Russian Journal of Applied Chemistry, 2007, Vol. 80, No. 5, pp. 799!804. + Pleiades Publishing, Ltd.

, 2007. Original Russian Text + D.O. Kirsanov, A.V. Legin, A.P. Kulikova, E.N. Polshin, Yu.G. Vlasov, 2007, published in Zhurnal Prikladnoi Khimii, 2007, Vol. 80, No. 5, pp. 821!826.

MACROMOLECULAR CHEMISTRY AND POLYMERIC MATERIALS

Polymeric Sensors for Determination of Anions of Organic Acids

D. O. Kirsanov, A. V. Legin, A. P. Kulikova, E. N. Polshin, and Yu. G. Vlasov
St. Petersburg State University, St. Petersburg, Russia
Received March 13, 2007

Abstract New polymeric electrochemical sensors based on various neutral and charged organic ionophores were suggested. The new sensors have a high sensitivity to anions of various organic acids (acetic, oxalic, lactic, malic, succinic, tartaric, and citric) in a wide concentration range. The selectivity and the detection limit of the developed sensors with respect to anions of the acids were studied. DOI: 10.1134/S1070427207050205

Rapid development of such branches as pharmaceutics, food-processing industry, and various biotechnological productions both in Russia and abroad pose a number of new problems in the fields of industrial and environmental analytical chemistry. One of the most important tasks is the development of fast, convenient, and reliable methods of monitoring industrial processes on-line and of monitoring various industrial emissions. The problem of the determination of organic components of various solutions and mixtures, in particular, organic acids is of prime importance. Available methods of the determination of these organic compounds, such as high-performance liquid chromatography, some kinds of ionic chromatography, etc., are characterized by high prices of equipment, complexity of the analyses, and are insufficiently quick. An attractive solution of the problem is the use of chemical sensors, for example, ion-selective electrodes and(or) arrays of selective and nonselective chemical sensors ([electronic tongue]), measurements with which are simple and fast, do not require complicated equipment and highly skilled staff, and can be readily automated. This brings up a problem of searching for new active components of sensory membranes which would ensure a high reproducible sensitivity to various organic acids and selectivity in the presence of inorganic and organic anions. Published compositions of polymeric sensory membranes for the determination of anions of organic acids are limited in number. The majority of the studies are devoted to the determination of salicylate, benzoate, and citrate anions. Metal porphyrins with
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various central atoms were used as membrane-active compounds in sensors for salicylate ions [1, 2]. To determine benzoate ions, sensors based on derivatives of trifluoroacetylbenzoic acid were applied [3]. Citrate ions in aqueous solutions were determined using sensors with membranes containing various dibenzyltin derivatives [4]. Sensors with membranes containing phenylporphyrins and uranyl salophen complexes were used as acetate-sensitive electrodes [5, 6]. It should be noted that the determination of salicylate, for example, is of a low practical value, and more often it is used as an illustration of sensitivity and selectivity of sensors to this ion. At the same time, in real media organic acids, as a rule, are present in complicated mixtures both with each other and with inorganic ions. The aim of this study was to develop compositions and to study properties, in particular, sensitivity and selectivity, of a wide set of solid-contact potentiometric polymeric anion sensors based on various metal porphyrins, quarternary ammonium bases, and derivatives of trifluoroacetylbenzoic acid for the determination of several practically most important organic acids, namely, acetic, citric, oxalic, lactic, malic, succinic, and tartaric, which in various combinations and proportions are contained in the overwhelming majority of drinks, foodstuffs, process liquids of food and pharmaceutical productions, and other important real objects. As the organic acids under study dissociate in aqueous solutions, at least partially, for the determination of organic residues of these acids in liquids it is appropriate to develop and study potentiometric chemical sensors sensitive to anions.

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The final aim of such studies is the development of not one, but a number of chemical sensors with reproducible sensitivity to several organic acids (cross sensitivity), and also with various selectivity toward anions of organic acids and widespread inorganic anions, such as, e.g., chloride, bromide, and nitrate. Combination and use of such sensors in multisensory systems like [electronic tongue] will make it possible to solve the problem of simultaneous quantitative determination of several organic acids in mixtures and in a number of real media. EXPERIMENTAL All the components for making sensory membranes were purchased from Fluka (Switzerland). We also used Merck (Germany) analytical grade organic acids, chemically pure grade inorganic salts and organic solvents from Reaktiv (St. Petersburg), and doubledistilled water. The polymeric sensory membranes studied (a total of more than 15 different compositions) contained various membrane-active components: metal porphyrins differing in the nature of the central metal atom, quarternary ammonium bases with various length of alkyl radicals, and derivatives of trifluoroacetylbenzoic acid. Seven of them are the most promising for the analysis of anions of organic acids, namely: types 133 based on metal porphyrins with manganese and rhodium central atoms and substituents in the porphyrin ring; types 4 and 5 based on quarternary ammonium salts; types 6 and 7 based on neutral organic complexing agents, structural analogs of trifluoroacetylbenzoic acid. Sensory membranes were prepared by a standard technique. Weighed samples of membrane components were poured over with tetrahydrofuran (THF) and mixed using a magnetic stirrer until the dissolution was complete. The resulting cocktail was poured in a Teflon weighing bottle with a flat bottom and allows to stand until THF evaporated completely (~48 h). Disks 7 mm in diameter were cut out from the resulting membrane, and a solid contact (a composite conducting material) was deposited onto one of disk sides. Depositing the composite material results in the formation on the membrane surface of a layer with a mixed conductivity: ionic due to the membrane composition and electronic due to the composite. A current lead (a copper wire) was immersed into the deposited composition. The structure was allowed to stand until the composite conducting material dried completely; then the membrane was pasted in a plastic

electrode case. We have made at least three sensors with membranes of each type. The numerical characteristics of electrodes given below are averaged values for sensors of the same type. Potentiometric measurements were carried out in the voltaic cell
Cu 9 Ag 9 AgCl, 9Test solution9 Membrane 9 Solid 9 Cu. 9 9 KClsat 9 9 9contact9

Readings were taken using a multichannel electronic digital voltmeter with a high input resistance connected to a personal computer for data collection and processing. An EVL 1M 3.1 silver chloride reference electrode was used. The sensitivity of sensors was studied by the method of calibration measurements in the range of concentrations of organic acids 10!6310!2 M. The slopes of the linear portions of the electrode functions were calculated for the concentration range 10!5310!2 M. The pH values of all the calibrating solutions for all the organic acids were fixed by adding sodium hydroxide to pH 6 to eliminate the effect of acidity variation on the electrode functions. The selectivity coefficients were determined by the method of mixed solutions (MMS). The pH values of solutions were monitored with a standard ESL 43-07 pH glass electrode. To check whether the sensors under study are sensitive to anions of organic acids, we made a series of calibrations with respect to solutions of the following acids: oxalic, acetic, citric, lactic, malic, succinic, and tartaric. The calibrations were carried out over the range of organic acid concentrations 10!6310!2 M at a constant pH 6 in all solutions, which was adjusted with sodium hydroxide solution. A typical shape of calibrating plots for various sensors in tartaric acid solutions is shown in Fig. 1. Experimental data on the slopes of the linear portions of the electrode functions of sensors in solutions of organic acids are given in the table. The above data show that the majority of sensors under study have a high sensitivity to anions of organic acids. The slopes of the electrode functions of the majority of the sensors towards anions of oxalic, succinic, malic, and tartaric acids are in the range 24 + 3 mV decade!1, which agrees well with the theoretical value for double-charged anions. The sensitivity of sensors of types 1 and 2 in solutions of acetic acid also approaches the theoretical value of
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Slope of electrode function for indicated acid Sensor type acetic citric lactic malic oxalic succinic tartaric 1 353 338 333 326 323 326 327 2 353 340 334 328 324 327 328 3 350 339 333 328 324 327 328 323 320 318 320 320 4 331 324 5 332 320 323 320 320 320 321 6 343 325 327 322 321 322 323 7 335 322 325 322 321 322 322
59 mV decade!1 for single-charged anions. As a whole, the sensitivity of the sensors based on metal porphyrins to anions of organic acids is slightly higher as compared to other types of sensors. All the types of sensors under consideration are the least sensitive to oxalic acid anions, which is apparently due to high hydrophilicity of oxalate anions (log Ko/w = 3 0.7). On the whole, sensors of types 4 and 5 based on quarternary ammonium salts of various structures show the lowest electrode sensitivity, as their response is of the ion-exchange nature and is not connected with specific complex formation. The selectivity of sensors was determined by the method of mixed solutions. The results obtained are presented in Fig. 2. The sensors studied show the highest selectivity toward citric acid anions. For all the types of sensors, the values of log Ksel(Acetate/Citrate) are less than 31.0, and in case of sensors of type 6, log Ksel(Acetate/Citrate) = 3 4.3 + 0.1, i.e., sensors of type 6 are capable of determining citrate in the presence of 10 000-fold excess of acetate anions. The selectivity to anions of tartaric and succinic acids in the presence of acetate is also fairly high, and the corresponding values of log Ksel(Acetate/X) lie in the range 0.531. The selectivity of sensors with respect to lactate and oxalate in the presence of acetate is low, and the logarithms of the corresponding selectivity coefficients of the majority of sensors are close to zero. For several structurally related acids, succinic, malic, and tartaric, differing only in the number of hydroxy groups at atoms in the carbon skeleton, we have carried out a special experiment on studying their selectivity. The selectivity coefficients were deRUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 80

Slopes of the electrode functions of sensors in solutions of organic acids. Average error of the determination of the electrode function slope +2 mV

termined by the MMS method at a fixed tartaric acid concentration. The experimental data are given in Fig. 2b. Sensors of types 4 and 5 based on quarternary ammonium bases do not exhibit significant selectivity to any of the three acids. A similar pattern takes place for sensors of type 7 based on a neutral transporting agent. The selectivity of the sensors based on metal porphyrins (types 133) clearly increases as the number of hydroxy groups in the carbon skeleton of an acid molecule decreases. These sensors exhibit the highest selectivity to succinic acid anions, which have no hydroxy groups in the carbon chain; then the selectivity decreases to malate (one hydroxy group in the carbon skeleton) and then to tartaric acid anions (two hydroxy
E, mV

log c(Tartrate) [M]

Fig. 1. Typical shape of calibrating plots for various sensors in tartaric acid solutions (constant pH 6). (E) Potential and (c) concentration. Sensor type: (1) 1, (2) 3, and (3) 7. No. 5 2007

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KIRSANOV et al. (a) Type

Type

Type

Type

Type

log Ksel(Tartrate/X) Type

Type

Type

(b) Type

Type

Type

Type

Fig. 2. Logarithms of selectivity coefficients Ksel of sensors (MMS, constant pH 6). Fixed concentration of (a) acetate, (b) tartrate, (c) chloride, and (d) nitrate. (a) (1) citrate, (2) lactate, (3) oxalate, (4) malate, (5) succinate, and (6) tartrate; (b) (1) malate and (2) succinate; (c, d) (1) acetate, (2) citrate, and (3) oxalate.

groups). Sensors of type 6 based on a neutral complexing agent behave similarly. The membranes containing quarternary ammonium salts show no selectivity to any of structurally related acids. It is known that inorganic anions, in particular, chloride and nitrate, can be present in many real analytical objects in noticeable concentrations along with anions of organic acids. Their influence on the electrode function can hinder the determination of organic acids in real solutions. To estimate this influence, we have carried out a series of experiments on studying the selectivity toward the most wide-spread organic acids (acetic, citric, oxalic) in the presence

of inorganic anions. The data obtained are shown in Figs. 2c and 2d. Sensors based on quarternary ammonium bases and neutral transporting agents (types 437) allow citrate ions to be determined in the presence of a tenfold excess of chloride [log Ksel(Cl! : citrate) ; 31]. In the case of sensors based on metal porphyrins (types 133), chloride ions exert a very strong interfering effect on the determination of organic acids, and the logarithms of the corresponding selectivity coefficients are either positive or close to zero (sensors of types 2 and 3, in a citrate3chloride pair). The interfering effect of nitrate ions (Fig. 2e) is
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Type

Type

Type

log Ksel(NO!/X) 3 Type Type Type

(d) Type

Type

Type

Type

Fig. 2. (Contd.)

stronger than that of chloride ions, which is evidently due to the higher lipophilicity of nitrate. However, the determination of citrate (sensors of types 1, 337) and oxalate (type 6) in the presence of a small (23 3-fold) excess of nitrate ions is possible. It should be particularly noted that essentially different selectivities of sensors with different compositions open prospects for their successful and differentiated analytical applications, and also for effective use of a set of such sensors with different sensitivities and selectivities (cross sensitivity) in the composition of multisensor systems like [electronic tongue.]
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CONCLUSIONS (1) New polymeric sensors based on membraneactive components of various nature have been developed. (2) The new sensors have a high sensitivity to anions of widespread organic acids (acetic, citric, oxalic, lactic, malic, succinic, and tartaric) over a wide concentration range at pH 6. (3) The slope of the linear portion of the electrode function of the sensors, e.g., those based on metal porphyrins, in solutions of singly charged anions, in particular acetate, is 53354 mV decade!1, and for
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anions of dibasic acids it is 24 + 3 mV decade!1 for the majority of sensors. (4) The selectivity of sensors both in solutions of organic acids and in solutions containing inorganic anions (chloride and nitrate) has been studied. The selectivities of sensors of various composition toward the same ion differ essentially (by a factor of more than 100), which opens prospects for their successful analytical application in various conditions, and also for the use of a set of such sensors in the composition of multisensor systems. ACKNOWLEDGMENTS This study was financially supported in part by the Russian Foundation for Basic Research (project no. 05-03-34 824).

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1. Chaniotakis, N.A., Park, S.B., and Meyerhoff, M.E., Anal. Chem., 1989, vol. 61, pp. 556 3570. 2. Li, J.Z., Pang, X.Y., Gao, D., and Yu, R.Q., Talanta, 1994, vol. 41, pp. 8813890. 3. Katsu, T. and Hanada, N., Anal. Chim. Acta, 1996, vol. 321, pp. 21325. 4. DeMuelenaere, R.L., Onsrud, P., and Arnold, M.A., Electroanalysis, 1993, vol. 5, pp. 8333838. 5. Amemiya, S., Buhlmann, P., and Umezawa, Y., Anal. Chem., 1999, vol. 71, pp. 104931054. 6. Antonisse, M.M.G., Snellink-Ruel, B.H.M., Ion, A.C., et al., J. Chem. Soc., Perkin Trans. 2, 1999, pp. 12113 1218.

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