THE THEORETICAL EVALUATION OF THE

Book of abstracts of III Ukrainian-Polish scientific conference „MEMBRANE AND SORPTION PROCESSES AND TECHNOLOGIES" (DECEMBER 12-14, 2017, KYIV, UKRAINE)

THE THEORETICAL EVALUATION OF THE HYDROGEN PEROXIDE ELECTROCHEMICAL SENSING, BASED ON CoSn(OH)6 V. V. Tkach1,2, Y. G. Ivanushko1, S. Lukanova1, M. V. Kushnir1, N. M. Storoshchuk1, S. C. de 2 1 Oliveira , P. I. Yagodynets' 1

2

Chernivtsi National University, 58012, Kotsyubyns'ky Str., 2, Chernivtsi, Ukraine Universidade Federal de Mato Grosso do Sul, Av. Sen. Felinto. Mailer, 1555, C/P. 549, 79074460, Campo Grande, MS, Brazil E-mail: nightwatcher2401 @ gmail. com

Hydrogen peroxide is the simplest peroxide compound [1 - 4 ] . It is used in synthesis as a reagent with either oxidant or reducing properties. His medical use is based on its antiseptic properties, reason why it's used while the first aid is given [5 - 7]. On the other hand, it the most characteristic of the reacting oxygen species (ROS), abundant in the organism [8 - 11], being capable to diffuse through cell membranes freely [12 - 14]. It's important to maintain the peroxide concentration in appropriate level, for intracellular signaling pathways of normal cells. ROS have been shown to initiate responses to various stresses and disorders [15 - 16]. Moreover, its excess may cause the oxidation stress and also provokes diseases like neurodegeneration, Alzheimer disease, cell injury, cancer and autoimmune disorders [17 18]. The same mechanism is realized during the ionizing irradiation of the human and animal organisms, by lipid and protein peroxidation [19 - 20]. So, the, the rapid, sensitive and precise H2O2 quantification in biological environments is actual task for biomedicine, biology and other fields [21 - 22], and the use of electrochemical methods with chemically modified electrodes would be an interesting solution for it [23 - 30]. The use of cobalt oxides and hydroxide based materials as modifiers for electrochemical analysis is one of the modern trends in modern electroanalytics [31 - 35]. Cobalt (III) oxyhydroxide [31 - 32], cobalt (II) complexes [33 - 34] and cobalt-stannous hydroxide [35], present in the form of cubic nanoparticles. The last material has advantage of the active surface and has been used in nanocapacitors [36], lithium-battery catalysts [37]. Nevertheless, its use in electroanalytics has begun only recently [35] and the use of new electrode-modifying materials may encounter some problems like: the indecision in the modifier mechanism of action in the presence on the analyte; the compatibility of the modifier with the tissue or biological object (some modifiers, used in vitro may be non-compatible with in vivo sensing); the presence of electrochemical instabilities, accompanying the similar processes of cobalt (III) oxyhydroxide [38 - 40] synthesis, and electrochemical oxidation and electrooxidative polymerization of organic molecules [41 - 44]; the possibility of electrochemical stages during the electrochemical process. The mentioned problems may only be solved by means of an analysis of a mathematical model, capable to describe adequately the electroanalytical system. By modeling it is also capable compare the behavior of this system with that for the similar ones without any experimental essay. So, the goal of this work is the mechanistic theoretic analysis of the CoSn(OH)6-assisted hydrogen peroxide electrochemical quantification. In order to achieve it, we realize the specific eoals:


suggestion of the mechanism of the chemical and electroanalytical reaction consequence, leading to the appearance of analytical signal; development of the balance equation mathematical model, correspondent to the electroanalytical system; analysis and interpretation of the model in terms of the electroanalytical use of the system; the seek for the possibility of electrochemical instabilities and for the factor, causing them; the comparison of the mentioned system's behavior with the similar ones [45 - 47]. To simplify the interpretation of the CoSn(OH) 6 , we will describe its formula like Co(OH)2*Sn(OH)4. Hydrogen peroxide in this system is reduced to form water. Bivalent cobalt hydroxide is thus oxidized in neutral solution to form cobalt (III) species. 2CoSn(OH) 6 + H 2 0 2 ~> 2CoSnO(OH) 5 +2H 2 0 (1) The substance is then reduced on cathode to form the initial composite. CoSnO(OH)5 + H 2 0 + e' CoSn(OH) 6 + OH" (2) Hydroxyl-ion is often formed during hydrogen peroxide reduction. The presence of tin (IV) stabilizes the cobalt compound, so the pH growth won't affect its stability in significant manner. Thus, to describe its electrochemical behavior with H2O2 in the neutral solution we introduce a classic bivariant equation set, from the analysis of which it is possible to conclude that: CoSn(OH)6 is really an excellent candidate for modifier for hydrogen peroxide quantification. The stable steady-state is maintained easily, and the system is electroanalytically efficient; The process is mostly diffusion-controlled; The oscillatory behavior in this system is caused not only by DEL influences of the electrochemical process, but also by possible autocatalytic influences of H2O2 reaction. Nevertheless, the coaction of the mentioned factors doesn't lead to the oscillatory behavior. Each factor is acting separately; The monotonic instability in this system is also possible, being caused by the equality of the destabilizing influences in DEL to the stabilizing ones; REFERENCES 1. B.C. Nyamunda, F. Chigondo, M. Moyo et. al., J. Atoms. Mol., 3(2013), 23 2. B. Puertolas, A. Hill, T. Garcia et. al, Catal. Today., 248(2015), 115 3. M. L. Kuznetsov, B.R. Rocha, A.J.L. Pombeiro, G.B. Shulpin, ACS Catal., 5(2015), 3823 4. J. Mlochowski, H. Wojtowicz-Mlochowska, Molecules, 20(2015), 10205 5. G. McDonell, A.D. Russell, Clin. Microbiol. Rev., 12(1999), 147 6. A.K. Saha, M.F. Haque, S. Karmaker, M.K. Mohanta, J. Life Earth Sci. 3 - 4(2009), 19 7. http://www.firstaidweb.com/cut.html, access at 10th of December 2016 8. P.D. Ray, B.W.Huang, Y. Tsuji, Cell Sign., 24(2012), 981 9. M.P. Murphy, 417(2009), 1 10. G.-Y. Liou, P. Storz, Free Rad. Res., 44(2010), https://dx.doi.org/10.3109%2F10715761003667554 11. P. Sharma, A. B. Jha, R. S. Dubey, M. Pessarakli, J. Bot., 2012(2012), ID: 217037, 26 pages, http://dx.doi.org/10.1155/2012/217037 12. G.P. Bienert, J. Schjoerring, Th. P. Jahn, 1758(2006), 994 13. G.P. Bienert, F. Chaumont, Biochim. Biophys. Acta, 1840(2014), 1596


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