Intrinsic Primary, Secondary, and Solvent Kinetic Isotope Effects on the Reductive Half-Reaction of D-Amino Acid Oxidase: Evidence against a Concerted Mechanism

Biochemistry ◽  
1994 ◽  
Vol 33 (13) ◽  
pp. 4001-4007 ◽  
Author(s):  
John M. Denu ◽  
Paul F. Fitzpatrick
Keyword(s):  
Amino Acid ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Acid Oxidase ◽  
Amino Acid Oxidase ◽  
Concerted Mechanism ◽  
Kinetic Isotope

scholarly journals pH and kinetic isotope effects in d -amino acid oxidase catalysis.

2001 ◽  
Vol 268 (21) ◽  
pp. 5504-5520 ◽  
Author(s):  
Christopher M. Harris ◽  
Loredano Pollegioni ◽  
Sandro Ghisla
Keyword(s):  
Amino Acid ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Acid Oxidase ◽  
Amino Acid Oxidase ◽  
Kinetic Isotope

Kinetics and Mechanism of the Aminolysis of S-Aryl O-Ethyl Dithiocarbonates in Acetonitrile

2004 ◽  
Vol 69 (12) ◽  
pp. 2174-2182 ◽  
Author(s):  
Hyuck Keun Oh ◽  
Ji Young Oh ◽  
Dae Dong Sung ◽  
Ikchoon Lee
Keyword(s):  
Transition State ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Interaction Constant ◽  
Kinetics And Mechanism ◽  
Cyclic Structure ◽  
Concerted Mechanism ◽  
Tetrahedral Intermediate ◽  
Kinetic Isotope ◽  
Hydrogen Bonded

The aminolysis of S-aryl O-ethyl dithiocarbonates with benzylamines are studied in acetonitrile at -25.0 °C. The βX (βnuc) values are in the range 0.67-0.77 with a negative cross-interaction constant, ρXZ = -0.24, which are interpreted to indicate a concerted mechanism. The kinetic isotope effects involving deuterated benzylamine nucleophiles (XC6H4CH2ND2) are large, kH/kD = 1.41-1.97, suggesting that the N-H(D) bond is partially broken in the transition state by forming a hydrogen-bonded four-center cyclic structure. The concerted mechanism is enforced by the strong push provided by the EtO group which enhances the nucleofugalities of both benzylamine and arenethiolate from the putative zwitterionic tetrahedral intermediate.

scholarly journals Kinetic isotope effect on the reaction of D-Amino-acid oxidase

FEBS Letters ◽  
1970 ◽  
Vol 6 (1) ◽  
pp. 22-24 ◽  
Author(s):  
Kunio Yagi ◽  
Morimitsu Nishikimi ◽  
Nobuko Ohishi ◽  
Akiko Takai
Keyword(s):  
Amino Acid ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Acid Oxidase ◽  
Amino Acid Oxidase ◽  
Kinetic Isotope

Nitrogen Isotope Effects As Probes of the Mechanism ofd-Amino Acid Oxidase

2000 ◽  
Vol 122 (51) ◽  
pp. 12896-12897 ◽  
Author(s):  
Kevin A. Kurtz ◽  
Mark A. Rishavy ◽  
W. W. Cleland ◽  
Paul F. Fitzpatrick
Keyword(s):  
Amino Acid ◽  
Isotope Effects ◽  
Nitrogen Isotope ◽  
Acid Oxidase ◽  
Amino Acid Oxidase
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