Abstract
A product isotope effect (PIE) of 1.0 was obtained from the ratio of the yields of [6-1H]-uridine 5′-monophosphate (50%) and [6-2H]-uridine 5′-monophosphate (50%) from the decarboxylation of orotidine 5′-monophosphate (OMP) in 50/50 (v/v) H2O/D2O catalyzed by orotidine 5′-monophosphate decarboxylase. This unitary product isotope effect eliminates a proposed mechanism for enzyme-catalyzed decarboxylation in which proton transfer from Lys-93 to C-6 of OMP provides electrophilic push to the loss of CO2 in a concerted reaction. The complete lack of selectivity for the reaction of solvent H and D that is implied by the value of PIE = 1.0 may be enforced by restricted motion of the NL3+ group of the side-chain of Lys-93 that has been proposed to protonate a vinyl carbanion intermediate.
Original language | English (US) |
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Pages (from-to) | 12946-12947 |
Number of pages | 2 |
Journal | Journal of the American Chemical Society |
Volume | 129 |
Issue number | 43 |
DOIs | |
State | Published - Oct 31 2007 |
ASJC Scopus subject areas
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry