Role of Solvent Dynamics in Stabilizing the Transition State of RNA Hydrolysis by Hairpin Ribozyme

2006 ◽  
Vol 2 (3) ◽  
pp. 858-862 ◽  
Author(s):  
Hwangseo Park ◽  
Sangyoub Lee
1971 ◽  
Vol 49 (23) ◽  
pp. 3856-3865 ◽  
Author(s):  
Carol A. Pollock ◽  
P. J. Smith

The role of solvent and base on the nature of the transition state for the concerted one-step carbonyl elimination reaction of benzyl nitrate has been examined using rate and kinetic isotope effect techniques. The primary hydrogen–deuterium isotope effect was found to increase with increasing strength of the abstracting base, kH/kD = 5.94 and 6.41 at 30° for reaction with EtO−/EtOH and t-BuO−/t-BuOH, respectively. The nitrogen isotope effect decreased with increasing strength of the abstracting base, 2.07, 1.82, and 1.54% for reaction with OH−/40 vol % EtOH–H2O, EtO−/EtOH, and t-BuO−/t-BuOH, respectively. The conclusion is reached that an increase in the strength of the abstracting base leads to a more reactant-like transition state with decreased rupture of both the C—H and O—N bonds. The role of solvent on the nature of the transition state was examined by determining rates and nitrogen isotope effects for reaction in various ethanol–water and ethanol–dimethyl sulfoxide mixtures. The nitrogen effect was found to remain essentially constant in solvent mixtures ranging from 65 vol % EtOH–H2O on the one hand to 80 vol% EtOH–DMSO on the other hand where the rate constants differed by a factor of 100 fold. It is concluded that solvent plays only a very minor role in determining transition state structure for the concerted elimination reaction of a neutral substrate with base.


1989 ◽  
Vol 260 (1) ◽  
pp. 15-24 ◽  
Author(s):  
Roger M. Nielson ◽  
Michael J. Weaver

1992 ◽  
Vol 114 (9) ◽  
pp. 3564-3565 ◽  
Author(s):  
Jeffrey M. Zaleski ◽  
Chi K. Chang ◽  
George E. Leroi ◽  
Robert I. Cukier ◽  
Daniel G. Nocera

2013 ◽  
Vol 25 (18) ◽  
pp. 10499-10503 ◽  
Author(s):  
Ziya Ahmad Khan ◽  
Abdullah S. Al-Bogami
Keyword(s):  

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