Evaluation of Osmium(II) Complexes as Electron Transfer Mediators Accessible for Amperometric Glucose Sensors
Evaluation of Osmium(II) Complexes as Electron Transfer Mediators Accessible for Amperometric Glucose Sensors
复制标题
锇(II)络合物作为电流型葡萄糖传感器可使用的电子转移介体的评估
作者：
Y. Nakabayashi;Atsushi Omayu;Shiro Yagi;Kazuyo Nakamura;J. Motonaka
为了降低Os(III/II)配合物的氧化还原电位，合成了Os(II)的混合配体配合物。使用4,4'-二甲基-2,2'-联吡啶(dmbpy)、咪唑(Him)或其衍生物和氯离子作为配体可以降低Os(III/II)配合物的氧化还原电位，例如，氧化还原(形式)电位值为628 mV vs . [Os(bpy)_3]^3+/2+ (bpy: 2,2′-联吡啶) 的 Ag/AgCl 和 [OsCl(Him)(dmbpy)_2]^2+/+ 的 –6 mV 在脱气的 0.1 mol dm^–3 磷酸盐缓冲液 (pH 7.0) 中给出。根据 Os(III/II) 复合物氧化还原电位的测定以及还原型葡萄糖氧化酶 (GOx) 和 Os(III) 复合物之间电子转移的二阶速率常数，对 Os(II) 复合物作为安培葡萄糖传感器可使用的电子转移介体进行了评估。尽管氧化还原电位较低的 Os(II) 配合物往往会降低二阶速率常数 k _s，但本研究中合成的大多数 Os(II) 配合物的 k _s 值均大于二茂铁甲酸的 k _s 值。电子转移反应的加速归因于 Os(II) 配合物和 GOx 之间的氢键和/或静电相互作用。因此可以得出结论，Os(II) 与 bpy (dmbpy)、Him（其衍生物）和 Cl^– 的混合配体配合物可以作为制造电流型葡萄糖传感器的更有效的电子转移介体。
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.
影响因子：
7.4
作者：
OHARA, TJ;RAJAGOPALAN, R;HELLER, A
通讯作者：
HELLER, A