Voltammetric biosensors for the determination of formate and glucose-6-phosphate based on the measurement of dehydrogenase-generated NADH and NADPH.

This paper describes the development of a modified electrode for the electrocatalytic oxidation of beta-nicotinamide adenine dinucleotide (beta-NADH) and beta-nicotinamide adenine dinucleotide phosphate (beta-NADPH) using electropolymerised 3,4-dihydroxybenzaldehyde (3,4-DHB). Two voltammetric biosensors using enzyme-immobilised membranes were constructed for the determination of formic acid and glucose-6-phosphate (G6P), respectively. The formic acid biosensor based on the combination of formate dehydrogenase (FDH)-modified membrane with 3,4-DHB-coated glassy carbon electrode is one to two orders more sensitive (LOD, 5.0x10(-5) M) than previously reported electrochemical biosensors. Similarly, lower detection limit (4.0x10(-5) M) for the measurement of G6P was achieved using glucose-6-phosphate dehydrogenase (G6PDH) in the presence of beta-NADP(+). The interference of uric acid and ascorbate was minimised by incorporating an additional membrane modified with uricase and ascorbate oxidase, respectively. The biosensing scheme developed in this study can be adopted universally with a number of dehydrogenases for the detection of different substrates.

[1]  A. Sols,et al.  Apparent unbalance between the activities of 6-phosphogluconate and glucose-6-phosphate dehydrogenases in rat liver. , 1973, Biochemical and biophysical research communications.

[2]  P. Tuñón,et al.  Electrocatalytic detection of nicotinamide coenzymes by poly(o-aminophenol)- and poly(o-phenylenediamine)-modified carbon paste electrodes , 1996 .

[3]  X. Correig,et al.  Reagentless carbon paste phosphate biosensors: preliminary studies , 1998 .

[4]  Wolfgang Schuhmann,et al.  Electrocatalytic oxidation of reduced nicotinamide coenzymes at gold and platinum electrode surfaces modified with a monolayer of pyrroloquinoline quinone. Effect of Ca2+ cations , 1994 .

[5]  Stefan Dipl.-Ing. Schuster,et al.  Regulatory O2 tensions for the synthesis of fermentation products in Escherichia coli and relation to aerobic respiration , 1997, Archives of Microbiology.

[6]  S. Kuwabata,et al.  PREPARATION AND PROPERTIES OF AMPEROMETRIC URIC ACID SENSORS , 1998 .

[7]  G. Gaetani,et al.  Regulation of glucose-6-phosphate dehydrogenase in human erythrocytes. , 1986, The Journal of biological chemistry.

[8]  H. Abruña,et al.  Aldehyde Biosensor Based on the Determination of NADH Enzymically Generated by Aldehyde Dehydrogenase , 1995 .

[9]  Yong J. Yuan,et al.  Effect of an intermediate on the amperometric response of a polypyrrole-based formate biosensing membrane , 2000 .

[10]  C. Cai,et al.  Electrocatalysis of NADH oxidation with electropolymerized films of azure I , 1997 .

[11]  L. Miller,et al.  Electrochemical oxidation of NADH: Kinetic control by product inhibition and surface coating , 1984 .

[12]  H. Abruña,et al.  Electrodeposition of Redox-Active Films of Dihydroxybenzaldehydes and Related Analogs and Their Electrocatalytic Activity toward NADH Oxidation , 1996 .

[13]  L. Gorton,et al.  A comparative study of some 3,7-diaminophenoxazine derivatives and related compounds for electrocatalytic oxidation of NADH , 1990 .

[14]  Zhou Dong-mei,et al.  The electrochemical polymerization of methylene green and its electrocatalysis for the oxidation of NADH , 1996 .

[15]  Joseph Wang,et al.  Electrocatalysis and measurements of hydrazine compounds at glassy carbon electrodes coated with electropolymerized 3,4-dihydroxybenzaldehyde films , 1996 .

[16]  C. Cai,et al.  Electrochemical polymerization of toluidine blue o and its electrocatalytic activity toward NADH oxidation. , 1998, Talanta.

[17]  H. Miwa,et al.  high-performance liquid chromatography of short-and long-chain fatty acids as 2-nitrophenylhydrazides , 1985 .

[18]  R. Conrad,et al.  Transient Production of Formate During Chemolithotrophic Growth of Anaerobic Microorganisms on Hydrogen , 1999, Current Microbiology.

[19]  P. Elving,et al.  Optimization of the analytical oxidation of dihydronicotinamide adenine dinucleotide at carbon and platinum electrodes , 1979 .

[20]  L. Gorton,et al.  Amperometric biosensors based on electrocatalytic regeneration of NAD+ at redox polymer-modified electrodes , 1993 .

[21]  Arne Torstensson,et al.  Electrocatalytic oxidation of reduced nicotinamide coenzymes by graphite electrodes modified with an adsorbed phenoxazinium salt, meldola blue , 1984 .

[22]  R. Parkes,et al.  Analysis of volatile fatty acids by ion-exclusion chromatography, with special reference to marine pore water , 1983 .

[23]  Franco Mazzei,et al.  Acid phosphatase/glucose oxidase-based biosensors for the determination of pesticides , 1996 .

[24]  J. Kulys,et al.  NADH oxidation by quinone electron acceptors. , 1984, Biochimica et biophysica acta.

[25]  Miguel Ángel López,et al.  Amperometric immunosensors and enzyme electrodes for environmental applications , 1998 .

[26]  A. Bassi,et al.  Mediated, amperometric biosensor for glucose-6-phosphate monitoring based on entrapped glucose-6-phosphate dehydrogenase, Mg2+ ions, tetracyanoquinodimethane, and nicotinamide adenine dinucleotide phosphate in carbon paste. , 1999, Analytical biochemistry.

[27]  William R. Heineman,et al.  Chemical Cross-Linking of a Redox Mediator Thionin for Electrocatalytic Oxidation of Reduced β-Nicotinamide Adenine Dinucleotide , 1991 .

[28]  C. Cai,et al.  Electrocatalysis of NADH oxidation with electropolymerized films of nile blue A , 1997 .

[29]  P. Elving,et al.  Effects of adsorption, electrode material, and operational variables on the oxidation of dihydronicotinamide adenine dinucleotide at carbon electrodes , 1978 .

[30]  M. Barcelona.  Dissolved organic carbon and volatile fatty acids in marine sediment pore waters , 1980 .

[31]  P. Elving,et al.  Mechanistic aspects of the electrochemical oxidation of dihydronicotinamide adenine dinucleotide (NADH) , 1980 .

[32]  H. Zare,et al.  Electrocatalytic oxidation of reduced nicotinamide adenine dinucleotide (NADH) at a chlorogenic acid modified glassy carbon electrode , 1999 .

[33]  M. Porter,et al.  Electrochemical oxidation of amine-containing compounds. A route to the surface modification of glassy carbon electrodes , 1994 .

[34]  Wolfgang Schuhmann,et al.  Electropolymerized Azines: Part II. In a Search of the Best Electrocatalyst of NADH Oxidation , 1999 .

[35]  Jose A. Romagnoli,et al.  Data acquisition, signal processing and modelling: a study of a conducting polypyrrole formate biosensor Part 1: Batch experiment , 1996 .

[36]  J. Kulys,et al.  Electrocatalytic oxidation of NADH on carbon black electrodes , 1985 .

[37]  K. Mopper,et al.  Determination of nanomolar levels of formate in natural waters based on a luminescence enzymatic assay , 1990 .

[38]  Wolfgang Schuhmann,et al.  Electrocatalytic properties of polypyrrole in amperometric electrodes , 1991 .

[39]  H. Abruña,et al.  Mechanistic Studies of the Electrocatalytic Oxidation of NADH and Ascorbate at Glassy Carbon Electrodes Modified with Electrodeposited Films Derived from 3,4-Dihydroxybenzaldehyde. , 1997, Analytical chemistry.

[40]  A. Karyakin,et al.  Electropolymerized Azines: A New Group of Electroactive Polymers , 1999 .

[41]  Héctor D. Abruña,et al.  Electrocatalysis of NADH Oxidation with Electropolymerized Films of 3,4-Dihydroxybenzaldehyde , 1994 .

[42]  L. Gorton,et al.  Catalytic oxidation of NADH by surface-modified graphite electrodes , 1981 .

[43]  P. Elving,et al.  Theoretical analysis of eletrochemical reactions involving two successive one-electron transfers with dimerization of intermediate-applicaiton to NAD+/NADH redox couple , 1982 .