Electropolymerized flavin adenine dinucleotide as an advanced NADH transducer.
Electropolymerizing the prosthetic group (flavin adenine dinucleotide, FAD) responsible in the active sites of dehydrogenases for NAD(+)|NADH regeneration, we succeeded in mimicking enzyme activity. Poly(FAD) characterized by an additional polymer-type redox reaction has been discovered as a highly effective electrocatalyst for NADH oxidation: operating at the lowest potentials reported for NADH transducers (0.00 V, pH 7.4), poly(FAD) is characterized by the electrochemical rate constant of 1.8 +/- 0.6 x 10(-3) cm s(-1), which is at the level of the NADH mass-transfer constant. Flow injection analysis of NADH with the poly(FAD)-modified wall-jet electrode as a detector has been characterized by a linear calibration range prolonged down to 5 x 10(-7) M and a sensitivity of 0.08 A M(-1) cm(-2), which taking into account the dispersion coefficient ( approximately 3), is at the diffusion-limiting value. In contrast to the low molecular weight mediators able to exhibit similar electrocatalytic properties, poly(FAD)-modified electrodes are characterized by the dramatically improved stability and, thus, can be considered as the most advantageous NADH transducers for analytical chemistry.
Karyakin
Arkady A
AA
Faculty of Chemistry, M.V. Lomonosov Moscow State University, 119992 Moscow, Russia. karyakin@chem.msu.ru
Ivanova
Yulia N
YN
Revunova
Ksenia V
KV
Karyakina
Elena E
EE
D001665:Binding Sites; D001704:Biopolymers / Q000737:chemistry* / Q000378:metabolism; D004563:Electrochemistry; D005182:Flavin-Adenine Dinucleotide / Q000031:analogs & derivatives / Q000737:chemistry* / Q000378:metabolism; D009243:NAD / Q000737:chemistry*; D010084:Oxidation-Reduction
D001704:Biopolymers; D009243:NAD; D005182:Flavin-Adenine Dinucleotide