Kinetic Isotope Effects as Tools To Reveal Solvation Changes Accompanying a Proton Transfer. A Canonical Unified Statistical Theory Calculation

1996 ◽  
Vol 100 (50) ◽  
pp. 19389-19397 ◽  
Author(s):  
Jordi Villà ◽  
Angels González-Lafont ◽  
José M. Lluch
Keyword(s):  
Statistical Theory ◽  
Proton Transfer ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope ◽  
Theory Calculation

scholarly journals Heavy-Enzyme Kinetic Isotope Effects on Proton Transfer in Alanine Racemase

2013 ◽  
Vol 135 (7) ◽  
pp. 2509-2511 ◽  
Author(s):  
Michael D. Toney ◽  
Joan Nieto Castro ◽  
Trevor A. Addington
Keyword(s):  
Proton Transfer ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Alanine Racemase ◽  
Enzyme Kinetic ◽  
Kinetic Isotope

Kinetic Isotope Effects in Multiple Proton Transfer

2005 ◽  
pp. 521-548 ◽  
Author(s):  
Willem Siebrand ◽  
Zorka Smedarchina ◽  
Antonio Fernández-Ramos
Keyword(s):  
Proton Transfer ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope

Kinetic isotope effects of proton transfer in aqueous and methanol containing solutions, and in gramicidin A channels

2003 ◽  
Vol 103 (2) ◽  
pp. 179-190 ◽  
Author(s):  
Anatoly Chernyshev ◽  
Régis Pomès ◽  
Samuel Cukierman
Keyword(s):  
Proton Transfer ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Gramicidin A ◽  
Kinetic Isotope

Asymmetric Double Proton Transfer of Excited 1:1 7-Azaindole/Alcohol Complexes with Anomalously Large and Temperature-Independent Kinetic Isotope Effects

2004 ◽  
Vol 43 (43) ◽  
pp. 5792-5796 ◽  
Author(s):  
Oh-Hoon Kwon ◽  
Young-Shin Lee ◽  
Han Jung Park ◽  
Yongho Kim ◽  
Du-Jeon Jang
Keyword(s):  
Proton Transfer ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Double Proton Transfer ◽  
Kinetic Isotope

Theoretical simulation of Brønsted correlations for proton transfer and methyl transfer: the significance of the Brønsted coefficient β

1999 ◽  
Vol 77 (5-6) ◽  
pp. 830-841 ◽  
Author(s):  
Ian H Williams ◽  
Paul A Austin
Keyword(s):  
Proton Transfer ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Molecular Orbital Calculations ◽  
Theoretical Simulation ◽  
Kinetic Isotope ◽  
Methyl Transfer ◽  
Equilibrium Relationship ◽  
Substituted Pyridines ◽  
Very High

Brønsted correlations for proton transfer and methyl transfer between pairs of mimicked 4-substituted pyridines have been simulated by means of AM1 molecular orbital calculations. The enthalpies of activation and of reaction are well correlated by the Marcus relation. The Brønsted correlation is markedly curved for proton transfer for which the Marcus intrinsic barrier is very low (~ 5 kJ mol-1). Conversely, the Brønsted correlation is almost imperceptibly curved for methyl transfer for which the Marcus intrinsic barrier is very high (~ 152 kJ mol-1). The slope of the Brønsted correlation provides an approximate measure of the position of the transition structure along the reaction coordinate between the reactant and product encounter complexes. Primary kinetic isotope effects for proton transfer show a broad maximum, centered on ΔHrxn = 0, when plotted against reaction exo/endothermicity only if computed with respect to isolated acids and bases, but intracomplex kinetic isotope effects show a maximum displaced significantly towards the endothermic proton transfers.Key words: Brønsted correlation, rate-equilibrium relationship, transition state, isotope effect.

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