Journal of the American Chemical Society p. 7629 - 7631 (1983)
Update date:2022-08-04
Topics:
Ostovic, Drazen
Roberts, Roger M. G.
Kreevoy, Mourice M.
Primary kinetic hydrogen isotope effects (KIE's) for hydride transfer between NAD+ analogues are between 6 and 4, for reactions with equilibrium constants ranging from 0.7 to 1016.There is no sign of the sharp change in KIE which would signal the change of a rate-limiting step in a multistep mechanism, and other evidence also indicates a one-step mechanism. 2 The secondary KIE produced by changing the hydrogen already attached at the acceptor site from H to D is about 10percent smaller when the transferred atom is D than when it is H.These results, combined with the values of the primary KIE's, strongly suggest some nuclear tunneling in the reaction coordinate.
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