scholarly journals Deuterium isotope effects on the product partitioning of fluoromethylglyoxal by glyoxalase I. Proof of a proton transfer mechanism.

1981 ◽  
Vol 256 (19) ◽  
pp. 9785-9788
Author(s):  
R.V. Chari ◽  
J.W. Kozarich
Keyword(s):  
Proton Transfer ◽  
Isotope Effects ◽  
Transfer Mechanism ◽  
Glyoxalase I ◽  
Deuterium Isotope Effects

Model calculations of isotope effects. VII. Deprotonation of 2-nitropropane by oxy anion bases

1983 ◽  
Vol 36 (8) ◽  
pp. 1503
Author(s):  
DJ McLennan
Keyword(s):  
Proton Transfer ◽  
Transition State ◽  
Isotope Effects ◽  
Experimental Results ◽  
Electron Delocalization ◽  
Model Calculations ◽  
Charge Delocalization ◽  
Successful Model ◽  
Deuterium Isotope Effects ◽  
State Models

Model calculations of primary and secondary deuterium isotope effects for the hydroxide-induced deprotonation of 2-nitropropane are reported. Various transition-state models have been examined in an effort to reproduce experimental results. A purely pyramidal transition state in which proton transfer has run far ahead of carbon rehybridization and charge delocalization is a successful model as far as isotope effects are concerned, but may fail on other counts. Three incipient trigonal models for the transition state have been tested, and, although none can be firmly eliminated by the resultant isotope effects, those involving the proton transfer's running ahead of electron delocalization and perhaps carbon rehybridization are favoured.

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