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Reaction Kinetics, Mechanisms and Catalysis

, Volume 127, Issue 2, pp 543–559 | Cite as

Modelling competition of the enzyme-catalysed glucose oxidation and redox reactions in scanning electrochemical microscopy

  • Raimondas Čiegis
  • Pranas KatauskisEmail author
  • Vladas Skakauskas
Article
  • 51 Downloads

Abstract

Kinetics of the glucose oxidation catalysed with immobilized enzyme (glucose oxidase) and redox reactions that compete for dissolved oxygen in an electrochemical cell is studied numerically by employing a mean-field model of a scanning electrochemical microscopy. The model accounts for: the bulk diffusion of glucose and dissolved oxygen towards the ultramicroelectrode (UME) and catalyst (enzyme-modified surface) and the products (gluconolactone and hydrogen peroxide) bulk one from the catalyst surface into the same cell, adsorption on and desorption from the catalyst surface of particles of both reactants. We have modified the known similar model and included into it two important processes: the surface diffusion of the adsorbed particles and intermediate reaction products, and a possibility to simulate the oxygen flux on the UME surface. The full mathematical model is described by a coupled system of nonlinear partial differential equations. It is approximated by using the finite volume method in space and the alternating direction implicit finite difference technique for integration in time. The influence of the immobilized enzyme concentration, distance between the catalyst surface and the UME, surface diffusivity of all intermediate reaction products, reaction rate constants, and bulk diffusivity of reactants on the evolution of the oxygen reduction current into water at the UME is studied. In particular it is found that the surface diffusion of the intermediate reaction products decreases the oxygen reduction current while the reverse reaction between the oxidized enzyme and hydrogen peroxide increases it. The mechanism of these effects is investigated.

Keywords

Glucose oxidase Enzyme-catalyzed Adsorption Desorption Modelling 

Notes

Acknowledgements

The last two authors of this research were supported by the Research Council of Lithuania (Project No. S-MIP-17-65).

References

  1. 1.
    Gibson QH, Swoboda BEP, Massey V (1964) Kinetics and mechanism of action of glucose oxidase. J Biol Chem 239:3927–3934Google Scholar
  2. 2.
    Bright HJ, Gibson QH (1967) The oxidation of 1-deuterated glucose by glucose oxidase. J Biol Chem 242:994–1003Google Scholar
  3. 3.
    Bateman RC Jr, Evans JA (1995) Using the glucose oxidase/peroxidase system in enzyme kinetics. J Chem Educ 72:A240–A241CrossRefGoogle Scholar
  4. 4.
    Bare WD, Pham CV, Cuber M, Demas JN (2007) An improved method fof studying the enzyme-catalyzed oxidation of glucose using luminescent probes. J Chem Educ 84:1511–1514CrossRefGoogle Scholar
  5. 5.
    Tao Z, Raffel RA, Souid AK, Goodisman J (2009) Kinetic studies enzyme-catalyzed reactions: oxidation of glucose, decomposition of hydrogen peroxide and their combination. Biophys J 96:2977–2988CrossRefGoogle Scholar
  6. 6.
    Bard AJ, Fan FRF, Kwak J, Lev O (1989) Scanning electrochemical microscopy: introduction and principles. Anal Chem 61:132–138CrossRefGoogle Scholar
  7. 7.
    Pierce DT, Unwin PR, Bard AJ (1992) Scanning electrochemical microscopy 17. Studies of enzyme-mediator kinetics for membrane- and surface-immobilized glucose oxidas. Anal Chem 64:1795–1804CrossRefGoogle Scholar
  8. 8.
    Wilhelm T, Wittstock G (2003) Analysis of interaction in patterned multienzyme layers by using scanning electrochemical microscopy. Angew Chem Int Ed Engl 42:2248–2250CrossRefGoogle Scholar
  9. 9.
    Evans SAG, Brakha K, Billon M, Mailey P, Denuault G (2005) Scanning electrochemical microscopy (SECM): localized glucose oxidase immobilization via the direct electrochemical microspotting of polypyrrole-botin films. Electrochem Commun 7:135–140CrossRefGoogle Scholar
  10. 10.
    Lei R, Stratmann L, Schafer D, Erichsen T, Neugebauer S, Li N, Schuhmann W (2009) Imaging biocatalytic activity of enzyme-polymer spots by means of combined scanning electrochemical microscopy/electrogenerated chemiluminescence. Anal Chem 81:5070–5074CrossRefGoogle Scholar
  11. 11.
    Morkvenaite-Vilkonciene I, Ramanaviciene A, Ramanavicius A (2014) Redox competition and generation-collection modes based scanning electrochemical microscopy for the evolution of immobilizedglucose oxidase-catalysed reactions. RSC Adv 4:1998–2002CrossRefGoogle Scholar
  12. 12.
    Morkvenaite-Vilkonciene I, Genys P, Ramanaviciene A, Ramanavicius A (2015) Scanning electrochemical impedance microscopy for investigation of glucose oxidase catalyzed reactions. Colloids Surf B 126:598–602CrossRefGoogle Scholar
  13. 13.
    Echard K, Chen X, Turcu F, Schuhmann W (2006) Redox competition mode of scanning electrochemical microscopy (RC-SECM) for visualization of local catalytic activity. Phys Chem Chem Phys 8:1277–1284Google Scholar
  14. 14.
    Mirkin MV, Bard AJ (1992) Multidimensional integral equations: a new approach to solving microelectrode diffusion problems: part 2. Applications to microband electrodes and the scanning electrochemical microscope. J Elecroanal Chem 323:29–51CrossRefGoogle Scholar
  15. 15.
    Sklyar O, Wittstock G (2002) Numerical simulations of complex nonsymmetrical 3D systems for scanning electrochemical microscopy using the boundary element method. J Phys Chem B 106:7499–7508CrossRefGoogle Scholar
  16. 16.
    Sklyar O, Kueng A, Kranz C, Mizaikoff B, Lugstein A, Bertagnolli E, Wittstock G (2005) Numerical simulation of scanning electrochemical microscopy experiments with frame-shaped integrated atomic force microscopy-SECM probes using the boundary element method. Anal Chem 77:764–771CrossRefGoogle Scholar
  17. 17.
    Sklyar O, Traube M, Zhao C, Wittstock G (2006) Modelling steady-state experiments with a scanning electrochemical microscope involving several independent diffusing species using the boundary element method. J Phys Chem B 110:15869–15877CrossRefGoogle Scholar
  18. 18.
    Nann T, Heinze J (1999) Simulation in electrochemistry using the finite element method: part 1: the algorithm. Electrochem Commun 1:289–294CrossRefGoogle Scholar
  19. 19.
    Ivanauskas F, Morkvenaite-Vilkonciene I, Astrauskas R, Ramanavicius A (2016) Modelling of scanning electrochemical microscopy at redox competition mode using diffusion and reaction equations. Electrochim Acta 222:347–354CrossRefGoogle Scholar
  20. 20.
    Gorban AN, Sargsyan HP, Wahab HA (2011) Quasichemical models of multicomponent nonlinear diffusion. Math Model Nat Phenom 6:184–262CrossRefGoogle Scholar
  21. 21.
    Skakauskas V, Katauskis P (2016) Numerical study of CO oxidation by N2O reaction over supported catalysts. J Math Chem 54:1306–1320CrossRefGoogle Scholar
  22. 22.
    Skakauskas V, Katauskis P, Čiegis R (2018) Modelling of the NO + CO reaction over inhomogeneous surfaces. J Math Chem 56:2626–2646CrossRefGoogle Scholar
  23. 23.
    Leskovac V, Trivic S, Wohlfahrt G, Kandrac J, Pericin D (2005) Glucose oxidase from Aspergilus niger: the mechanism of action with molecular oxygen, quinones, and one electron acceptors. Int J Biochem Cell Biol 37:731–750CrossRefGoogle Scholar
  24. 24.
    Jamnongwong M, Loubiere K, Dietrich N, Hebrard G (2010) Experimental study of oxygen diffusion coefficients in clean water containing salt, glucose of surfactant: consequences on the liquid-side mass transfer coefficients. Chem Eng J 165:758–768CrossRefGoogle Scholar
  25. 25.
    Samarskii AA (2001) The theory of difference schemes. Marcel Dekker, New YorkCrossRefGoogle Scholar
  26. 26.
    Hundsdorfer W, Verwer JG (2003) Numerical solution of time-dependent advection-diffusion-reaction equations. Springer series in computational mathematics. Springer, BerlinCrossRefGoogle Scholar
  27. 27.
    Čiegis R, Katauskis P, Skakauskas V (2018) The robust finite volume schemes for modelling non-classical surface reactions. Nonlinear Anal Model Control 23:234–250CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2019

Authors and Affiliations

  • Raimondas Čiegis
    • 1
  • Pranas Katauskis
    • 2
    Email author
  • Vladas Skakauskas
    • 2
  1. 1.Vilnius Gediminas technical universityVilniusLithuania
  2. 2.Faculty of Mathematics and InformaticsVilnius UniversityVilniusLithuania

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