The experimental secondary kinetic isotope effects for an ADH model reaction were replicated computationally using a motion related H-tunneling model. The model reaction was a hydride-transfer reaction from an alcohol to four carbocations which are analogous to NAD+ cofactor in ADH. These four carbocations have different steric hindrance effect due to the various chemical groups attached to the reaction centers. The steric hindrance effect on primary isotope dependence of 2° KIE was studied via computation. Computational findings suggest that Marcus-like H-tunneling model is able to interpret and predict the abnormal 2o KIEs which are not explainable by semi-classical and 1°/2° coupled-motions model.
|Commitee:||Lu, Yun, Shabestary, Nahid, Wei, Chin-Chuan|
|School:||Southern Illinois University at Edwardsville|
|School Location:||United States -- Illinois|
|Source:||MAI 53/06M(E), Masters Abstracts International|
|Keywords:||Alcohol dehydrogenase, Computational chemistry, Enzyme, Hydrogen tunneling, Secondary kinetic isotope effect|
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