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Secondary Kinetic Isotope Effects as Probes of Environmentally‐Coupled Enzymatic Hydrogen Tunneling Reactions
Author(s) -
Hay Sam,
Pang Jiayun,
Monaghan Phillip J.,
Wang Xi,
Evans Rhian M.,
Sutcliffe Michael J.,
Allemann Rudolf K.,
Scrutton Nigel S.
Publication year - 2008
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200800291
Subject(s) - kinetic isotope effect , dihydrofolate reductase , quantum tunnelling , chemistry , hydride , kinetic energy , isotope , hydrogen , catalysis , chemical physics , active site , computational chemistry , enzyme , stereochemistry , combinatorial chemistry , deuterium , organic chemistry , physics , atomic physics , quantum mechanics
The secondary kinetic isotope effect for hydride transfer from NADPH to dihydrofolate catalyzed by dihydrofolate reductase (see traces) is neither temperature dependent nor exalted. In environmentally coupled models of H‐tunneling, the secondary isotope effects do not report on promoting motions, but reflect the active site geometry attained immediately prior to H transfer (i.e. the ‘tunnelling ready configuration′).