Electrochemistry Communications 13 (2011) 1476–1478

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Electrochemistry Communications
journal homepage: www.elsevier.com/locate/elecom

Electrochemistry of saccharinate anion at liquid interfaces
François Quentel a, Katerina Stankoska b, Orhideja Grupče b, Gligor Jovanovski b, c, Valentin Mirčeski b,⁎
a b c

Laboratoire de Chimie Analytique, UMR-CNRS 6521, Université de Bretagne Occidentale, 6,avenue Victor Le Gorgeu, C.S. 93837, 29238 Brest Cedex 3, France Institute of Chemistry, Faculty of Natural Sciences and Mathematics, “Ss Cyril and Methodius” University, P.O. Box 162, 1000 Skopje, R. Macedonia Macedonian Academy of Sciences and Arts, Bul. Krste Misirkov 2, 1000 Skopje, Macedonia

a r t i c l e

i n f o

a b s t r a c t
Electrochemistry of saccharinate anion (sacc −) is studied at the liquid water|nitrobenzene (w|nb) interface by means of three-phase electrodes. Saccharinate anion can be effectively transferred across w|nb interface driven by the redox transformation of the lutetium bis(tetra-tert-butylphthalocyaninato), with a standard Gibbs energy of transfer from water to nitrobenzene of 20.17 kJ mol−1. The kinetics of transfer is estimated applying the quasireversible maximum. In addition, the influence of sacc− on the thermodynamics and kinetics of the alkali metal cations transfer is discussed. © 2011 Elsevier B.V. All rights reserved.

Article history: Received 19 September 2011 Received in revised form 29 September 2011 Accepted 30 September 2011 Available online 7 October 2011 Keywords: Saccharin Ion transfer Three-phase electrodes

1. Introduction Saccharin is one of the best known artificial sweetening agents [1]. As a non-sugar compound, with a sweetening power more than 550 times that of saccharose, saccharin is an excellent additive for dietetic food products [2]; it doesn't cause glycemic response and goes unmetabolized through the human body. Saccharin chemistry, in particular its interactions with biologically relevant metal cations, attracted a great interest, motivated primarily by the suspected carcinogenicity of this compound. Fortunately, such threat was definitely ruled out [3]. Saccharin exhibits a versatile coordination chemistry [4–6], in particular when acting as saccharinate anion (sacc −), obtained by deprotonation of the NH group (pKa ~ 1.6) [7,8]. Saccharinate anion is a polyfunctional ligand [9], however, it is redox inactive [10,11]. Yet, a few electrochemical studies of saccharin metal complexes have been reported [12–17]. Surprisingly, there are no electrochemical studies of sacc − at liquid interfaces. To the best of our knowledge, there are no data on the lipophilicity of sacc −. Hence, in the present work we study the electrochemistry of sacc − at liquid interfaces, applying three-phase electrodes [18,19]. The three-phase electrode system consists of graphite electrode partly modified with a thin film of nitrobenzene solution (nb) containing lutetium bis(tetratert-butylphthalocyaninato) (Lu[tBu4Pc]2) [20] as a redox probe to

study the thermodynamics and kinetics [21] of saccharinate anion transfer across w|nb interface. 2. Experimental Lu[tBu4Pc]2, was synthesized and purified as described in [22]. Saccharin and sodium saccharinate were products of Fluka. Lu[tBu4Pc]2 was dissolved in water-saturated nitrobenzene (2 mmol/L). A disk electrode of highly oriented pyrolytic graphite has been used. Before modification, the electrode was treated as described in [20]. The nitrobenzene solution (0.2 μL), spreads spontaneously over the electrode surface, covering partly the electrode surface and forming a three-phase electrode with an ultrathin film. Square-wave voltammetry (SWV) and cyclic voltammetry (CV) were conducted at AUTOLAB equipment (Eco-Chemie, Utrecht, Netherlands). A saturated calomel electrode was used as a reference and a platinum wire as an auxiliary electrode. Water (Millipore Q) was saturated with nitrobenzene to prevent dissolution of the film. 3. Results and discussion Typical SW voltammogram recorded in contact with a sodium saccharinate aqueous solution is depicted in Fig. 1. All components of the response are particularly well developed, enabling precise evaluation of voltammetric features. As elaborated in the previous study [20], the responses I and II correspond to the oxidation and reduction of the redox probe to a stable, monovalent and hydrophobic cation and anion, respectively. The oxidation I is accompanied by the sacc − transfer across w|nb interface, driven by the

⁎ Corresponding author. Tel.: + 389 71243380; fax: + 389 2 3226 865. E-mail address: valentin@pmf.ukim.mk (V. Mirčeski). 1388-2481/$ – see front matter © 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.elecom.2011.09.030

SW voltammogram recorded in 0. In a series of previous studies it has been unambiguously confirmed that the redox probe in both neutral and ionic forms exhibits high chemical stability and hydrophobicity. it is useful to stress that the diminishing of the voltammetric response cannot be attributed to the leaching of the redox probe. from the (nb) measurements of the formal potential at different c(sacc−). Increasing the concentration of the sacc − caused the peak I to shift toward more negative potentials. being in agreement with the diagnostic criteria [21]. t Þ c ¼ ks. 1. whereas the peak current ratio is virtually 1. The slope of the dependence Ec ' vs. βit is the transfer coefficient. for both responses I and II. Fig. In this context. The log–log dependence of fmax vs. while the solvation sphere is more ordered in water than in the nitrobenzene solution. In order to estimate the phenomenological standard rate constant. The other conditions are the same as for Fig.270 V).17 kJ mol−1 (partition coefficient is logP = −3. In addition. and a⁎ i(nb) is the bulk activity of the corresponding form of the redox probe. 0. a series of experiments has been conducted by altering the SW frequency and following the methodology of the quasireversible maximum [20. a linear dependence was observed (R = 0. in which the negative charge is located mainly at the thiazole ring. 2. T.999). which might be related with the complex structure of the ion. due to the dissolution of the film. t Þ cRed ð0. being in agreement with the trend predicted by Eq. (3).464 V vs NHE) [20]. Δw ϕiθ is the standard potential of the ion transfer across w|nb interface. cOx(0. backward (Ib) and net (Inet) components.5 (2) and 1 M (3) sodium saccharinate solution. Following the diagnostic criteria for the rate limiting step of the coupled electron– ion transfer reaction at three-phase electrodes [21]. is between that of thiocyanate (Δw ϕθ − = 0.it= 4 × 10−4 cm s−1. The simulations were based on the following equation:       I c ð0. the stannb dard transfer potential is estimated to be Δw ϕθ − = 0.1 (1). . The overall electrochemical reactions proceed as coupled electron–ion transfer processes: Lu½tBu4 PcŠ2 ðnbÞ þ sacc ðwÞ⇆Lu½tBu4 PcŠ2 ðnbÞ þ sacc ðnbÞ þ e Lu½tBu4 PcŠ2 ðnbÞ þ M ðwÞ þ e⇆Lu½tBu4 PcŠ2 ðnbÞ þ M ðnbÞ: þ − þ − þ − ð1Þ ð2Þ At a low SW frequency (f b 20 Hz). Obviously. Quentel et al. log(asacc-(w)) equals −52 mV. the experimental quasireversible maximum was fitted with the theoretical one. (3). βit = 0. t) are the surface concentration of the oxidized and reduced form of the redox ¼ θ EOxðnbÞjRedðnbÞ þ RT nb θ Δw ϕsacc− − ! à   RT aRedðnbÞ ln asacc− ðwÞ þ ln ð3Þ F F 2 θ Ec 0 ¼ θ EOxðnbÞjRedðnbÞ þ nb θ Δw ϕMþ !  RT RT  2 ln aMþ ðwÞ þ ln à : þ F F aOxðnbÞ ð4Þ θ Here EOx(nb)|Red(nb) is the standard potential of the redox couple in nb the organic phase. At higher temperature. from the linear dependence nb θ of Δw Gsacc− vs.223 V (i. Accordsacc ingly. t Þ iðnbÞ ð5Þ where ks. over the temperature interval from 11 to 25 °C. The deviation from the theoretically value of − 59 mV reflects the complexity of the sacc − transfer. 0. it is concluded that the sacc− transfer is the rate limiting step.e. revealing that the process is endothermic. The responses I and II correspond to the transfer of sacc− and Na+ across w|nb interface. one can speculate the ion transfer is also complicated by the adsorption at the liquid interface due to the amphiphilic properties Fig.593). t) and cRed(0. showing forward (If).it is the phenomenological standard rate constant of the ion transfer. defined as [20]: θ0 Ec of the saccharinate anion.5 and D = 5 × 10−6 cm2 s−1. ks.. being confined in the organic phase under most of the experimental conditions [20]. The peak potential separation between the forward and backward components is 17 mV. t Þ −βit c ð0.3 J mol−1 K −1 and the standard enthalpy is 39. For kinetic measurements. / Electrochemistry Communications 13 (2011) 1476–1478 1477 Fig. Thus. experiments with repetitive cycling of the potential in both SWV and CV revealed the response gradually decreases with time of the potential cycling (data not shown).95 kJ mol−1.1 M sodium saccharinate solution. 1. T. 2 depicts quasireversible maxima measured for three concentrations of sacc −. Hence. electrochemical reactions (1) and (2) are reversible electrochemical processes [23]. csacc− is a line (R = 0.F. Recalling the standard potential of the redox couple is ELBPC+ |LBPC(nb) θ = 0. the net SW peak potential is equivalent to the formal potentials of reactions (1) and (2).. The parameters of the potential modulation are: f = 12 Hz. The well developed quasireversible maximum shifts toward higher critical frequencies (i.975). the standard Gibbs energy of the sacc− transfer from water to nb θ nitrobenzene is Δw Gsacc− = 20.165 V) and niSCN nb θ − trate (Δw ϕNO3 = 0. Quasireversible maximum for the transfer of sacc− measured in 0. the response is instable. as preθ dicted by Eq. the lipophilicity of sacc−.5 mV. + redox couple Lu[tBu4Pc]2 (nb)/Lu[tBu4Pc]2(nb).209 V. the frequency associated with the position of the maximum. The inset shows a correlation diagram between experimental and theoretical fmax. and ΔE = 1. Esw = 50 mV.21. the standard entropy of sacc− transfer is estimated to be 67. t Þ FS cRed ð0. t Þ− expð−ϕÞ Ox ðl. with respect to nb the w|nb. fmax) by increasing the sacc− concentration. Analyzing the variation of Ep(I) vs.e.24–26]. Hence. rather than it has to be related with the transferring ion itself. For simulations.it expðβit ϕÞ Ox ciðwÞ ðl. whereas the reduction II includes transfer of Na +(aq) accompanying the turnover of − the couple Lu[tBu4Pc]2(nb)/Lu[tBu4Pc]2 (nb).

Alternative Sweeteners. t) and ci(nb)(l. O.S. M. Lawrence.D. Truong. M. Quentel et al. The effect of saccharin increases in the order K + b Li + b Na +.it = (4 ± 0.S. Langmuir 22 (2006) 3404. 3 represents the effect of saccharin on the SW voltammograms recorded in NaNO3. slope = 1. Interestingly. the added saccharin is practically completely dissociated. Cozien. Prahash. R. G. Wadhawan.C. Acknowledgement The support by the Alexander von Humboldt Foundation (3. A.G. the influence of saccharin on the alkali metal cation transfers has been inspected. M. R. Food Chemistry 120 (2010) 1250. [14] G. M. Journal of Solid State Electrochemistry 15 (2011) 197. L. C. U. Langmuir 26 (2010) 19209. whereas for the solution of cOx(0.J. i. the corresponding peak potential shift being 15. Bulut. S. Baran. Çakir. to obtain the solution for ci(w)(l. Buess-Herman. X.2 mM). Baran. Pondaven. Obviously. A. R. Kaitner. F.1478 F. F. [21] V.  F θ′ In addition. . [10] H. V. Mirčeski.4) × 10 −4 cm s −1. G. N. Jovanovski. Totaro.S. T. S. R. Naumov.. it is unlikely to be related with the alteration of the potential difference at w|nb interface due to partitioning of sacc −. Deng. [18] F. A. E. Theoretical simulations have been performed by varying f. which is difficult to be precisely measured. rather than it is related with modification of the structure of the interface. Naumov. Usman.J. Schröder. [2] W.D. and the recent improved mathematical solution [27].e. The fmax for K + transfer shifts from 170 Hz.C. cRed(0. Yilmaz. [25] R. F. Known. We speculate that the accelerating effect of saccharin is due to its adsorption on the liquid interface and specific electrostatic interactions with alkali metal cations. I. Silva. A.6). C. McClenahan. Solid lines show voltammograms recorded in 0. Finally. Epp. Ivanova. fmax shifts from 50 to 70 Hz for the same concentration of saccharin. The inset of Fig. t) and ci(nb)(l. J. H.T. Croatica Chemica Acta 73 (2000) 843. Chantrapromma. t) are concentrations of the transferring ion at the liquid interface.G. Compton. Lozada-Ascencio. Bicer. A.5 M KNO3) to 200 Hz in the presence of 0. Banks. Fun.J. V. Baran. F. L'Her. ϕ ¼ RT E−Ec is dimensionless potential relative to the formal potential of the electrochemical reaction. 3.-K. Quentel. Scholz. Angewandte Chemie International Edition 44 (2005) 1251. Tomovski. implying a facilitating effect of sacc − (Note. Çakir. M. as discussed in [24]. Journal of Electroanalytical Chemistry 552 (2003) 45. New Journal of Chemistry 16 (1992) 711. and for the Li + transfer. 2nd ed. M. O. V.06).J. [11] V. J. Springer. [20] F. We note that the precision of the method depends slightly on the exact thickness of the thin film. Coordination Chemistry Reviews 250 (2006) 1980. Fig. W. Groutas. Gulaboski. For Na +.M. Gewirth. L'Her. Kuang. 1991. Fig. Pondaven. R. / Electrochemistry Communications 13 (2011) 1476–1478 couple at the electrode surface. t) semiinfinite diffusion of the transferring ion i was considered. The best fit between the experimental and theoretical data was obtained for ks. M. Quentel. Jovanovski.J. [5] G. When saccharin is added to the aqueous electrolyte (0. Mirčeski. G.E. Evans. The Journal of Physical Chemistry. Biological Trace Element Research 37 (1993) 293. 22. the kinetic effect is the most pronounced for K + transfer. Marken. and KCl (c). As the effect is cation specific. Mirčeski. Main Group Metal Chemistry 25 (2002) 175. Seik. Doted lines refer to voltammograms recorded in the corresponding electrolytes containing 0. Quimica Nova 28 (2005) 326. E. L'Her. M. [16] D. Y. which is positioned at the distance l fromthe electrode surface. Wain.J. Gelardi. L-Her. Mirčeski. Mirčeski. Galán-Vidal. Ibrahim.R. t). the response at more negative potentials. R. V. G. B.. L'Her. the maximum is virtually located at the same position (fmax = 35 Hz). Quentel. in the identical manner as in experiments. [7] E. Physical Chemistry Chemical Physics 5 (2003) 4053. Monatshefte fur Chemie 126 (1995) 673. [27] V. [24] F. [4] P. [9] P.S.J. t).C. T. Journal of the Electrochemical Society 154 (2007) D577. References [1] L. E.A. assigned to the transfer of the corresponding metal cation [20]. Rae.4Fokoop-DEU/1128670) and Ministry of Education and Science of Macedonia (Grant 14-2437/1) is gratefully acknowledged. LiCl. E. F. [3] Chemistry in Britain 37 (2001) 18.E. then for Na +. Journal of Electroanalytical Chemistry 586 (2006) 86. Parajón-Costa.N. Álvarez-Romero. Berlin. [19] C. Baran. Electrochemistry Communications 2 (2000) 124. The other conditions are the same as for Fig.A. Jovanovski. Ž. L'Her. The effect of saccharin on the transfer of Na+. Venkataraman. ci(w)(l. [13] S. Riley. Jovanovski. Pereira. [6] P.997. (in 0. Çakir. [17] M. Quentel. E. M. A. O. 1.M. Marcel Dekker Inc. [22] A. diffusion model in a film of thickness l was used [27]. Biçer. and 30 mV.D. respectively. BioChemistry Review 99 (1999) 2573. J. Davies.N. shifts toward less negative potentials. This assumption is further supported by the fact that kinetic measurements also show an obvious facilitating effect in the presence of saccharin. and almost insignificant for Li +. B 109 (2005) 1262. [8] E. Cordeiro. Lovrić. Gulaboski. Li+ and K+. Çakir. there is no correlation between the thermodynamic and kinetic effect. New York.2 mM saccharin. Baran. O. [23] V. Electrochemistry Communications 7 (2005) 1122.J.P. Mirčeski.2 mM saccharin. Current Organic Chemistry 5 (2001) 1059. In the present model adopted for the three-phase electrode.B. which might be of importance for ion transfer processes at cellular membranes.A. 3 shows the correlation between theoretical and experimental fmax (R = 0. [26] H.5 M NaNO3(aq) (a). and KCl aqueous electrolytes. Parajon Costa. Scholz. R. [15] B.A. Analytical Chemistry 77 (2005) 1940. [12] B. A.F. S. J. The mathematical model is developed on the basis of the theory presented in [21].M. LiCl(aq) (b). Huang. Quentel. C. Bioorganic & Medicinal Chemistry 4 (1996) 1393. Wang. as pKa ~ 1. Rodríguez-Ávila. revealing an obvious accelerating effect. Páez-Hernández. Apella. O'Brien Nabors. 2005. Grupče. Monatshefte fur Chemie 126 (1995) 673. Electrochemistry of Immobilized Particles and Droplets. Naumov. Hignett.

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