Secondary kinetic isotope effects as probes of environmentally-coupled enzymatic hydrogen tunneling reactions

Sam Hay; Jiayun Pang; Phillip J. Monaghan; Xi Wang; Rhiannon M. Evans; Michael J. Sutcliffe; Rudolf K. Allemann; Nigel S. Scrutton

doi:10.1002/cphc.200800291

Secondary kinetic isotope effects as probes of environmentally-coupled enzymatic hydrogen tunneling reactions

Sam Hay, Jiayun Pang, Phillip J. Monaghan, Xi Wang, Rhiannon M. Evans, Michael J. Sutcliffe, Rudolf K. Allemann, Nigel S. Scrutton

Research output: Contribution to journal › Article › peer-review

Abstract

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'). (Graph Presented). © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

Original language	English
Pages (from-to)	1536-1539
Number of pages	3
Journal	ChemPhysChem
Volume	9
Issue number	11
DOIs	https://doi.org/10.1002/cphc.200800291
Publication status	Published - 4 Aug 2008

Keywords

Catalysis
Enzyme
Kinetic isotope effects
Quantum chemistry
Reaction mechanisms

Access to Document

10.1002/cphc.200800291

Cite this

@article{f4613203d4054df49ff9cb95a8dfa6d5,

title = "Secondary kinetic isotope effects as probes of environmentally-coupled enzymatic hydrogen tunneling reactions",

abstract = "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'). (Graph Presented). {\textcopyright} 2008 Wiley-VCH Verlag GmbH & Co. KGaA.",

keywords = "Catalysis, Enzyme, Kinetic isotope effects, Quantum chemistry, Reaction mechanisms",

author = "Sam Hay and Jiayun Pang and Monaghan, {Phillip J.} and Xi Wang and Evans, {Rhiannon M.} and Sutcliffe, {Michael J.} and Allemann, {Rudolf K.} and Scrutton, {Nigel S.}",

note = ", Biotechnology and Biological Sciences Research Council, United Kingdom",

year = "2008",

month = aug,

day = "4",

doi = "10.1002/cphc.200800291",

language = "English",

volume = "9",

pages = "1536--1539",

journal = "ChemPhysChem",

issn = "1439-7641",

publisher = "John Wiley & Sons Ltd",

number = "11",

}

TY - JOUR

T1 - Secondary kinetic isotope effects as probes of environmentally-coupled enzymatic hydrogen tunneling reactions

AU - Hay, Sam

AU - Pang, Jiayun

AU - Monaghan, Phillip J.

AU - Wang, Xi

AU - Evans, Rhiannon M.

AU - Sutcliffe, Michael J.

AU - Allemann, Rudolf K.

AU - Scrutton, Nigel S.

N1 - , Biotechnology and Biological Sciences Research Council, United Kingdom

PY - 2008/8/4

Y1 - 2008/8/4

N2 - 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'). (Graph Presented). © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

AB - 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'). (Graph Presented). © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

KW - Catalysis

KW - Enzyme

KW - Kinetic isotope effects

KW - Quantum chemistry

KW - Reaction mechanisms

U2 - 10.1002/cphc.200800291

DO - 10.1002/cphc.200800291

M3 - Article

C2 - 18613201

SN - 1439-7641

VL - 9

SP - 1536

EP - 1539

JO - ChemPhysChem

JF - ChemPhysChem

IS - 11

ER -

Secondary kinetic isotope effects as probes of environmentally-coupled enzymatic hydrogen tunneling reactions

Abstract

Keywords

Access to Document

Fingerprint

Cite this