Evidence for Environmentally Coupled Hydrogen Tunneling during Dihydrofolate Reductase Catalysis

Allemann, Rudolf Konrad ORCID: https://orcid.org/0000-0002-1323-8830 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:	17 Oct 2022 08:53
URI:	https://orca.cardiff.ac.uk/id/eprint/1376

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