Article
Extremely elevated room-temperature kinetic isotope effects quantify the critical role of barrier width in enzymatic C-H activation.
Journal of the American Chemical Society - 11 Jun 2014
Hu Shenshen, Sharma Sudhir C, Scouras Alexander D, Soudackov Alexander V, Carr Cody A Marcus, Hammes-Schiffer Sharon, Alber Tom, Klinman Judith P
Abstract excerpt
The enzyme soybean lipoxygenase (SLO) has served as a prototype for hydrogen-tunneling reactions, as a result of its unusual kinetic isotope effects (KIEs) and their temperature dependencies. Using a synergy of kinetic, structural, and theoretical studies, we show how the interplay between donor-acceptor distance and active-site flexibility leads to catalytic behavior previously predicted by quantum tunneling...
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