Analysis of Kinetic Isotope Effects in Enzymatic Carbon–Hydrogen Cleavage Reactions

نویسندگان
چکیده

برای دانلود باید عضویت طلایی داشته باشید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

Enzymatic single-molecule kinetic isotope effects.

Ensemble-based measurements of kinetic isotope effects (KIEs) have advanced physical understanding of enzyme-catalyzed reactions, but controversies remain. KIEs are used as reporters of rate-limiting H-transfer steps, quantum mechanical tunnelling, dynamics and multiple reactive states. Single molecule (SM) enzymatic KIEs could provide new information on the physical basis of enzyme catalysis. ...

متن کامل

Analysis of kinetic isotope effects for nonadiabatic reactions.

Factors influencing the rates of quantum mechanical particle transfer reactions in many-body systems are discussed. The investigations are carried out on a simple model for a proton transfer reaction that captures generic features seen in more realistic models of condensed phase systems. The model involves a bistable quantum oscillator coupled to a one-dimensional double-well reaction coordinat...

متن کامل

Isotope effects on enzymatic and nonenzymatic reactions of phosphorothioates

O-phosphorothioate analogs of phosphate monoesters have long been used to probe kinetic and stereochemical aspects of phosphoryl transfer. Both uncatalyzed reactions in solution and enzymatic reactions have been studied, the latter most notably with alkaline phosphatase. Large thio effects, defined as the ratio of the reaction rate with a phosphate substrate over that of the corresponding phosp...

متن کامل

Deuterium kinetic isotope effects in microsolvated gas-phase E2 reactions.

This work describes the first experimental studies of deuterium kinetic isotope effects (KIEs) for the gas-phase E2 reactions of microsolvated systems. The reactions of F(-)(H(2)O)(n) and OH(-)(H(2)O)(n), where n = 0, 1, with (CH(3))(3)CX (X = Cl, Br), as well as the deuterated analogs of the ionic and neutral reactants, were studied utilizing the flowing afterglow-selected ion flow tube techni...

متن کامل

Enzymatic Kinetic Isotope Effects from First-Principles Path Sampling Calculations.

In this study, we develop and test a method to determine the rate of particle transfer and kinetic isotope effects in enzymatic reactions, specifically yeast alcohol dehydrogenase (YADH), from first-principles. Transition path sampling (TPS) and normal mode centroid dynamics (CMD) are used to simulate these enzymatic reactions without knowledge of their reaction coordinates and with the inclusi...

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

ژورنال

عنوان ژورنال: The Journal of Physical Chemistry B

سال: 2011

ISSN: 1520-6106,1520-5207

DOI: 10.1021/jp2022117