Examining the Relative Timing of Hydrogen Abstraction Steps during NAD+-Dependent Oxidation of Secondary Alcohols Catalyzed by Long-Chaind-Mannitol Dehydrogenase fromPseudomonas fluorescensUsing pH and Kinetic Isotope Effects†

Biochemistry ◽  
2002 ◽  
Vol 41 (31) ◽  
pp. 10158-10165 ◽  
Author(s):  
Mario Klimacek ◽  
Bernd Nidetzky
Keyword(s):  
Isotope Effects ◽  
Hydrogen Abstraction ◽  
Kinetic Isotope Effects ◽  
Secondary Alcohols ◽  
Relative Timing ◽  
Mannitol Dehydrogenase ◽  
Kinetic Isotope

Hydrogen abstraction from (2H3)methyl acetate by methyl and trifluoromethyl radicals

1981 ◽  
Vol 34 (4) ◽  
pp. 727 ◽  
Author(s):  
NL Arthur ◽  
PJ Newitt
Keyword(s):  
Rate Constants ◽  
Methoxy Group ◽  
Methyl Acetate ◽  
Isotope Effects ◽  
Hydrogen Abstraction ◽  
Kinetic Isotope Effects ◽  
Temperature Range ◽  
Kinetic Isotope ◽  
Acetyl Group

A study of hydrogen abstraction from CH3COOCD3 by CH3 radicals in the temperature range 113-232�, and by CF3 radicals in the range 83-212�, has yielded data on the reactions: CH3+CH3COOCD3 → CH4+CH2COOCD3 (1)CH3+CH3COOCD3 → CH3D+CH3COOCD2 (2) CF3+CH3COOCD3 → CF3H+CH2COOCD2 (3) CF3+CH3COOCD3 → CF3D+CH3COOCD2 (4) The corresponding rate constants, based on the values 1013.34 and 1013.36 cm3 mol-1 s-1 for the recombination of CH3 and CF3 radicals, respectively, are given by (k in cm3 mol-1 s-1 and E in J mol-1): logk1 = (11.31�0.12)-(43500�1030)/19.145T (1) logk1 = (11.31�0.12)-(53460�640)/19.145t (2) logk3 = (11.12�0.06)=(34260�450)/19.145T � (3) logk4 =(10.93�0.12)-(38650�900)/19.145T (4)These results lead to kinetic isotope effects at 400 K for attack on the acetyl group of 11, for the CH3 reaction, and 24, for the CF3 reaction, thus confirming the values we obtained previously. For attack on the methoxy group, the kinetic isotope effects are 8 and 4, for the CH3 and CF3 reactions, respectively.

scholarly journals Kinetic Isotope Effects in the Chromium(VI) Oxidation of Bicyclic Alcohols

1999 ◽  
Vol 23 (2) ◽  
pp. 146-147
Author(s):  
J. Hodge Markgraf ◽  
Jordan S. Dubow ◽  
Jessica A. Charland ◽  
Elliott H. Sohn
Keyword(s):  
Rate Constants ◽  
Acidic Solution ◽  
Isotope Effects ◽  
Activation Parameters ◽  
Kinetic Isotope Effects ◽  
Secondary Alcohols ◽  
First Order ◽  
Chromium Vi ◽  
Kinetic Isotope ◽  
Pseudo First Order

Pseudo first-order rate constants are determined for the oxidation of a series of secondary alcohols and their monodeutero analogues by ammonium chromate in aqueous acidic solution at several temperatures; the relative rates and activation parameters are consistent with a cyclic, symmetrical transition state.

The oxidation of secondary alcohols by dimethyldioxirane: re-examination of kinetic isotope effects

2010 ◽  
Vol 16 (4-6) ◽  
Author(s):  
Alfons L. Baumstark ◽  
Pedro C. Vasquez ◽  
Mark Cunningham ◽  
Pamela M. Leggett-Robinson
Keyword(s):  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Secondary Alcohols ◽  
Kinetic Isotope

scholarly journals Kinetic Isotope Effects in Multipath VTST: Application to a Hydrogen Abstraction Reaction

2015 ◽  
Vol 120 (8) ◽  
pp. 1911-1918 ◽  
Author(s):  
Luis Simón-Carballido ◽  
Tiago Vinicius Alves ◽  
Agnieszka Dybala-Defratyka ◽  
Antonio Fernández-Ramos
Keyword(s):  
Isotope Effects ◽  
Hydrogen Abstraction ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope ◽  
Abstraction Reaction ◽  
Hydrogen Abstraction Reaction

scholarly journals Oxygen-18 Kinetic Isotope Effects of Nonheme Iron Enzymes HEPD and MPnS Support Iron(III) Superoxide as the Hydrogen Abstraction Species

2015 ◽  
Vol 137 (33) ◽  
pp. 10448-10451 ◽  
Author(s):  
Hui Zhu ◽  
Spencer C. Peck ◽  
Florence Bonnot ◽  
Wilfred A. van der Donk ◽  
Judith P. Klinman
Keyword(s):  
Isotope Effects ◽  
Hydrogen Abstraction ◽  
Kinetic Isotope Effects ◽  
Nonheme Iron ◽  
Nonheme Iron Enzymes ◽  
Kinetic Isotope ◽  
Iron Enzymes
Sign in / Sign up

Export Citation Format

Share Document