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Abstract:

The homogeneous reaction between glucose oxidase and osmium bipyridine-pyridine carboxylic acid in the presence of glucose has been studied in detail by cyclic voltammetry and digital simulation. Combination of the analytical equations that describe the dependence of the amperometric response on enzyme, substrate and co-substrate concentrations for the limiting cases with digital simulation of the coupled enzyme reaction diffusion problem allows us to extract kinetic parameters for the substrate-enzyme reaction: KMS = 10.8 mM, kcat = 254 s- 1 and for the redox mediator-enzyme reaction, k = 2.2 × 105 M- 1 s- 1. The accurate determination of the kinetic parameters at low substrate concentrations (< 7 mM) is limited by depletion of the substrate close to the electrode surface. At high substrate concentrations (> 20 mM) inactivation of the reduced form of glucose oxidase in the bulk solution must be taken into account in the analysis of the results. © 2008 Elsevier B.V. All rights reserved.

Registro:

Documento: Artículo
Título:Extracting kinetic parameters for homogeneous [Os(bpy)2ClPyCOOH]+ mediated enzyme reactions from cyclic voltammetry and simulations
Autor:Flexer, V.; Ielmini, M.V.; Calvo, E.J.; Bartlett, P.N.
Filiación:INQUIMAE, Departamento de Quimica Inorganica, Analitica y Quimica Fisica, Facultad de Ciencias Exactas y Naturales, C1428EHA, Argentina
School of Chemistry, University of Southampton, Southampton, SO17 1BJ, United Kingdom
Palabras clave:Enzyme electrode; Glucose oxidase; Kinetics; Mediator; Osmium bipyridine; Acids; Carboxylic acids; Digital arithmetic; Electrolysis; Enzymes; Glucose; Glucose oxidase; Glucose sensors; Kinetic parameters; Organic acids; Osmium; Substrates; Voltammetry; Accurate; Amperometric responses; Analytical equations; Bipyridine; Bulk solutions; Digital simulations; Electrode surfaces; Enzyme electrode; Enzyme reactions; Homogeneous reactions; Limiting cases; Mediator; Pyridine carboxylic acids; Redox mediators; Reduced forms; Substrate concentrations; Cyclic voltammetry; carboxylic acid; glucose oxidase; osmium; pyridine; amperometry; article; catalysis; chemical structure; cyclic potentiometry; diffusion; electrochemistry; electrode; enzyme inactivation; enzyme kinetics; enzyme mechanism; enzyme substrate; oxidation reduction reaction; simulation; Electrochemistry; Enzyme Activation; Glucose Oxidase; Kinetics; Organometallic Compounds; Osmium; Oxidation-Reduction
Año:2008
Volumen:74
Número:1
Página de inicio:201
Página de fin:209
DOI: http://dx.doi.org/10.1016/j.bioelechem.2008.08.001
Título revista:Bioelectrochemistry
Título revista abreviado:Bioelectrochemistry
ISSN:15675394
CODEN:BIOEF
CAS:glucose oxidase, 9001-37-0; osmium, 7440-04-2; pyridine, 110-86-1; Glucose Oxidase, EC 1.1.3.4; Organometallic Compounds; Osmium, 7440-04-2
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_15675394_v74_n1_p201_Flexer

Referencias:

  • Bartlett, P.N., Pratt, K.F.E., A study of the kinetics of the reaction between ferrocene monocarboxylic acid and glucose oxidase using the rotating-disc electrode (1995) J. Electroanal. Chem, 397, pp. 53-60
  • Flexer, V., Forzani, E.S., Calvo, E.J., Luduena, S.J., Pietrasanta, L.I., Structure and thickness dependence of "molecular wiring" in nanostructured enzyme multilayers (2006) Anal. Chem., 78, pp. 399-407
  • Forrow, N.J., Sanghera, G.S., Walters, S.J., The influence of structure in the reaction of electrochemically generated ferrocenium derivatives with reduced glucose oxidase (2002) J. Chem. Soc., Dalton Trans, pp. 3187-3194
  • Albery, W.J., Bartlett, P.N., Driscoll, B.J., Lennox, R.B., Amperometric enzyme electrodes. 5. The homogeneous mediated mechanism (1992) J. Electroanal. Chem, 323, pp. 77-102
  • Bartlett, P.N., Pratt, K.F.E., Modeling of processes in enzyme electrodes (1993) Biosensors & Bioelectronics, 8, pp. 451-462
  • Cass, A.E.G., Davis, G., Francis, G.D., Hill, H.A.O., Aston, W.J., Higgins, I.J., Plotkin, E.V., Turner, A.P.F., Ferrocene-mediated enzyme electrode for amperometric determination of glucose (1984) Anal. Chem, 56, pp. 667-671
  • Green, M.J., Hill, H.A.O., Amperometric enzyme electrodes (1986) J. Chem. Soc., Faraday Trans. I, 82, pp. 1237-1243
  • Liaudet, E., Battaglini, F., Calvo, E.J., Electrochemical study of sulphonated ferrocenes as redox mediators in enzyme electrodes (1990) J. Electroanal. Chem, 293, p. 68
  • Rusling, J.F., Ito, K., Voltammetric determination of electron-transfer rate between an enzyme and a mediator (1991) Anal. Chim. Acta, 252, pp. 23-27
  • Frede, M., Steckhan, E., Continuous electrochemical activation of flavoenzymes using polyethyleneglycol-bound ferrocenes as mediators-a model for the application of oxidoreductases as oxidation catalysts in organic-synthesis (1991) Tet. Lett, 32, pp. 5063-5066
  • Bourdillon, C., Demaille, C., Moiroux, J., Saveant, J.M., New insights into the enzymatic catalysis of the oxidation of glucose by native and recombinant glucose oxidase mediated by electrochemically generated one-electron redox cosubstrates (1993) J. Am. Chem. Soc, 115, pp. 2-10
  • Battaglini, F., Calvo, E.J., Digital-simulation of homogeneous enzyme-kinetics for amperometric redox-enzyme electrodes (1992) Anal. Chim. Acta, 258, pp. 151-160
  • Dequaire, M., Limoges, B., Moiroux, J., Saveant, J.M., Mediated electrochemistry of horseradish peroxidase. Catalysis and inhibition (2002) J. Amer. Chem. Soc, 124, pp. 240-253
  • Bourdillon, C., Thomas, V., Thomas, D., Electrochemical study of d-glucose oxidase auto-inactivation (1982) Enzyme and Microbial Technology, 4, pp. 175-180
  • Bourdillon, C., Hervagault, C., Thomas, D., Increase in operational stability of immobilized glucose oxidase by the use of an artificial cosubstrate (1985) Biotechnology and Bioengineering, 27, pp. 1619-1622
  • Bourdillon, C., Demaille, C., Moiroux, J., Saveant, J.M., Analyzing product inhibition and pH gradients in immobilized enzyme films as illustrated experimentally by immunologically bound glucose oxidase electrode coatings (1999) J. Phys. Chem. B, 103, pp. 8532-8537
  • Greenfield, P.F., Kittrell, J.R., Lawrence, R.L., Inactivation of immobilized glucose oxidase by hydrogen peroxide (1975) Anal. Biochem, 65, pp. 109-124
  • Kepple, K., The effect of hydrogen peroxide on glucose oxidase from Aspergillus niger (1966) Biochemistry, 5, pp. 139-143
  • Kulys, J.J., Cenas, N.K., Oxidation of glucose oxidase from Penicillium vitale by one-electron and 2-electron acceptors (1983) Biochimi. Biophys. Acta, 744, pp. 57-63
  • Miron, J., Gonzalez, M.P., Vazquez, J.A., Pastrana, L., Murado, M.A., A mathematical model for glucose oxidase kinetics, including inhibitory, deactivation and diffusional effects, and their interactions (2004) Enzyme and Microbial Technology, 34, pp. 513-522
  • Razumas, V., Kulys, J., Knichel, M., Wiemhofer, H.D., Gopel, W., Monoalkylferrocene-mediated amperometric enzyme electrodes for glucose determination (1993) Electroanalysis, 5, pp. 399-404
  • Laemmli, U.K., Cleavege of structural protein during the assembly of the head of bacteriophage T4 (1970) Nature, 227, pp. 680-685
  • Danilowicz, C., Corton, E., Battaglini, F., Osmium complexes bearing functional groups: building blocks for integrated chemical systems (1998) J. Electroanal. Chem, 445, pp. 89-94
  • K. F. E. Pratt, PhD Thesis, University of Southampton (1994); Britz, D., (1988) Digital Simulation in Electrochemistry, , Springer-Verlag, Heidelberg
  • Feldberg, S.W., Digital Simulation: A General Method for Solving Electrochemical Diffusion-Kinetic Problems (1969) Electroanalytical Chemistry 3, , Bard A.J. (Ed), Marcel Dekker, New York
  • Bard, A.J., Faulkner, L.R., (2001) Electrochemical Methods: Fundamentals and Applications, , John Wiley & Sons, New York
  • Nelson, D.L., Cox, M.M., Lehninger Principles of Biochemistry (2000) Worth, , New York
  • Weibel, M.K., Bright, H.J., The glucose oxidase mechanism. Interpretation of the pH dependence. (1971) J. Biol. Chem, 246, pp. 2734-2744
  • Wilson, R., Turner, A.P.F., Glucose oxidase-an ideal enzyme (1992) Biosensors & Bioelectronics, 7, pp. 165-185
  • Ahmad, A., Akhtar, M.S., Bhakuni, V., Monovalent cation-induced conformational change in glucose oxidase leading to stabilization of the enzyme (2001) Biochemistry, 40, pp. 1945-1955
  • Yokoyama, K., Kayanuma, Y., Cyclic voltammetric simulation for electrochemically mediated enzyme reaction and determination of enzyme kinetic constants (1998) Anal. Chem, 70, pp. 3368-3376
  • Limoges, B., Moiroux, J., Saveant, J.M., Kinetic control by the substrate and/or the cosubstrate in electrochemically monitored redox enzymatic homogeneous systems. Catalytic responses in cyclic voltammetry (2002) J. Electroanal. Chem, 521, pp. 1-7
  • Gibson, Q.H., Swoboda, B.E., Massey, V., Kinetics and mechanism of action of glucose oxidase (1964) J. Biol. Chem, 239, pp. 3927-3934
  • Swodoba, B.E.P., Massey, V., Purification and properties of the glucose oxidase from Aspergillus niger (1965) J. Biol. Chem, 240, pp. 2209-2215
  • Bright, H.J., Appleby, M., The pH dependence of the individual steps in the glucose oxidase reaction (1969) J. Biol. Chem, 244, pp. 3625-3634
  • Nakamura, S., Ogura, Y., Action mechanism of glucose oxidase of Aspergillus niger (1968) J. Biochem, 63, pp. 308-316
  • Duke, F.R., Weibel, M., Page, D.S., Bulgrin, V.G., Luthy, J., The glucose oxidase mechanism. Enzyme activation by substrate (1969) J. Am. Chem. Soc, 91, pp. 3904-3909
  • Bourdillon, C., Demaille, C., Moiroux, J., Saveant, J.M., New insights into the enzymic catalysis of the oxidation of glucose by native and recombinant glucose oxidase mediated by electrochemically generated one-electron redox cosubstrates (1993) J. Am. Chem. Soc, 115, pp. 2-10
  • Anicet, N., Bourdillon, C., Demaille, C., Moiroux, J., Saveant, J.M., Catalysis of the electrochemical oxidation of glucose by glucose oxidase and a single electron cosubstrate: kinetics in viscous solutions (1996) J. Electroanal. Chem., 410, pp. 199-202

Citas:

---------- APA ----------
Flexer, V., Ielmini, M.V., Calvo, E.J. & Bartlett, P.N. (2008) . Extracting kinetic parameters for homogeneous [Os(bpy)2ClPyCOOH]+ mediated enzyme reactions from cyclic voltammetry and simulations. Bioelectrochemistry, 74(1), 201-209.
http://dx.doi.org/10.1016/j.bioelechem.2008.08.001
---------- CHICAGO ----------
Flexer, V., Ielmini, M.V., Calvo, E.J., Bartlett, P.N. "Extracting kinetic parameters for homogeneous [Os(bpy)2ClPyCOOH]+ mediated enzyme reactions from cyclic voltammetry and simulations" . Bioelectrochemistry 74, no. 1 (2008) : 201-209.
http://dx.doi.org/10.1016/j.bioelechem.2008.08.001
---------- MLA ----------
Flexer, V., Ielmini, M.V., Calvo, E.J., Bartlett, P.N. "Extracting kinetic parameters for homogeneous [Os(bpy)2ClPyCOOH]+ mediated enzyme reactions from cyclic voltammetry and simulations" . Bioelectrochemistry, vol. 74, no. 1, 2008, pp. 201-209.
http://dx.doi.org/10.1016/j.bioelechem.2008.08.001
---------- VANCOUVER ----------
Flexer, V., Ielmini, M.V., Calvo, E.J., Bartlett, P.N. Extracting kinetic parameters for homogeneous [Os(bpy)2ClPyCOOH]+ mediated enzyme reactions from cyclic voltammetry and simulations. Bioelectrochemistry. 2008;74(1):201-209.
http://dx.doi.org/10.1016/j.bioelechem.2008.08.001