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多同位素效应作为6-磷酸葡萄糖酸脱氢酶反应中质子和氢化物转移的探针。

Multiple isotope effects as a probe of proton and hydride transfer in the 6-phosphogluconate dehydrogenase reaction.

作者信息

Hwang C C, Cook P F

机构信息

Department of Chemistry and Biochemistry, University of Oklahoma, Norman 73019, USA.

出版信息

Biochemistry. 1998 Nov 10;37(45):15698-702. doi: 10.1021/bi981288w.

Abstract

Primary solvent deuterium, primary substrate deuterium, multiple solvent deuterium/substrate deuterium, and multiple solvent deuterium/13C isotope effects on V/K6PG have been measured for the Candida utilis and sheep liver 6-phosphogluconate dehydrogenases (6PGDH). Proton inventory data suggest the presence of a significant medium effect in a step preceding hydride transfer and the presence of a kinetic solvent deuterium isotope effect on hydride transfer. Multiple isotope effect data confirm the presence of multiple solvent deuterium sensitive steps, likely including a conformational change preceding hydride transfer, hydride transfer, and decarboxylation.

摘要

已针对产朊假丝酵母和羊肝6-磷酸葡萄糖酸脱氢酶(6PGDH)测定了初级溶剂氘、初级底物氘、多重溶剂氘/底物氘以及多重溶剂氘/13C对V/K6PG的同位素效应。质子累积数据表明,在氢化物转移之前的步骤中存在显著的介质效应,并且在氢化物转移过程中存在动力学溶剂氘同位素效应。多重同位素效应数据证实存在多个对溶剂氘敏感的步骤,可能包括氢化物转移之前的构象变化、氢化物转移和脱羧反应。

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