Analytical Sciences

Evaluation of Osmium(II) Complexes as Electron Transfer Mediators Accessible for Amperometric Glucose Sensors

Yasuo NAKABAYASHI,*  Atsushi OMAYU,* Shiro YAGI,* Kazuyo NAKAMURA,* and Junko MOTONAKA**

*Unit of Chemistry, Faculty of Engineering, Kansai University, 3-3-35 Yamate, Suita, Osaka 564-8680, Japan
**Department of Chemical Science and Technology, Faculty of Engineering, The University of Tokushima, 2-1 Minami-josanjima, Tokushima 770-8506, Japan

In order to lower the redox potentials of Os(III/II) complexes, the mixed ligand complexes of Os(II) were synthesized. The redox potentials of Os(III/II) complexes could be lowered by the use of 4,4'-dimethyl-2,2'-bipyridine (dmbpy), imidazole (Him) or its derivatives, and chloride ion as ligands, e.g., values of the redox (formal) potentials of 628 mV vs. Ag/AgCl for [Os(bpy)₃]^3+/2+ (bpy: 2,2'-bipyridine) and -6 mV for [OsCl(Him)(dmbpy)₂]^2+/+ were given in deaerated 0.1 mol dm^-3 phosphate buffer (pH 7.0). The evaluation of Os(II) complexes as electron transfer mediators accessible for amperometric glucose sensors was examined according to the determination of the redox potentials of Os(III/II) complexes and the second-order rate constants for electron transfer between glucose oxidase (GOx) in reduced form and the Os(III) complex. Although the Os(II) complexes with lower redox potentials tended to decrease the second-order rate constants k_s, the k_s values for the majority of Os(II) complexes synthesized in this study were greater than that for ferrocenecarboxylic acid. Acceleration of the electron-transfer reaction is attributable to the hydrogen bonding and/or the electrostatic interaction between the Os(II) complexes and GOx. It may be consequently concluded that the mixed ligand complexes of Os(II) with bpy (dmbpy), Him (its derivatives), and Cl^- can act as more efficient electron transfer mediators for the fabrication of amperometric glucose sensors.

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