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Evidence for Environmentally Coupled Hydrogen Tunneling during Dihydrofolate Reductase Catalysis

Allemann, Rudolf Konrad and Maglia, Giovanni 2003. Evidence for Environmentally Coupled Hydrogen Tunneling during Dihydrofolate Reductase Catalysis. Journal of the American Chemical Society 125 (44) , pp. 13372-13373. 10.1021/ja035692g

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Abstract

Hydride transfer during catalysis by dihydrofolate reductase from Thermotoga maritima has been studied by stopped flow spectroscopy. The reduction of dihydrofolate by NADPH showed a biphasic temperature dependence of the deuterium kinetic isotope effect. At temperatures above 25 °C the KIE was temperature independent, while the reaction rates were strongly temperature dependent. Below 25 °C the KIE becomes dependent on temperature, and the ratio of the preexponential factors is inverse, suggesting a greater role for active dynamics that modulate the tunneling distance.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Cardiff Catalysis Institute (CCI)
Chemistry
Subjects: Q Science > QD Chemistry
Publisher: American Chemical Society
ISSN: 0002-7863
Last Modified: 04 Jun 2017 01:39
URI: http://orca.cf.ac.uk/id/eprint/1376

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