Catalytic specificity of yeast inorganic pyrophosphatase for magnesium ion as cofactor. An analysis of divalent metal ion and solvent isotope effects on enzyme function

Biochemistry ◽  
1983 ◽  
Vol 22 (9) ◽  
pp. 2243-2248 ◽  
Author(s):  
Katherine M. Welsh ◽  
Andrew Jacobyansky ◽  
Bleecker Springs ◽  
Barry S. Cooperman
Biochemistry ◽  
1981 ◽  
Vol 20 (21) ◽  
pp. 6051-6060 ◽  
Author(s):  
Barry S. Cooperman ◽  
Anna Panackal ◽  
Bleecker Springs ◽  
Donald J. Hamm

2021 ◽  
Vol 22 (14) ◽  
pp. 7394
Author(s):  
Kyoung Ho Park ◽  
Mi Hye Seong ◽  
Jin Burm Kyong ◽  
Dennis N. Kevill

A study was carried out on the solvolysis of 1-adamantyl chlorothioformate (1-AdSCOCl, 1) in hydroxylic solvents. The rate constants of the solvolysis of 1 were well correlated using the Grunwald–Winstein equation in all of the 20 solvents (R = 0.985). The solvolyses of 1 were analyzed as the following two competing reactions: the solvolysis ionization pathway through the intermediate (1-AdSCO)+ (carboxylium ion) stabilized by the loss of chloride ions due to nucleophilic solvation and the solvolysis–decomposition pathway through the intermediate 1-Ad+Cl− ion pairs (carbocation) with the loss of carbonyl sulfide. In addition, the rate constants (kexp) for the solvolysis of 1 were separated into k1-Ad+Cl− and k1-AdSCO+Cl− through a product study and applied to the Grunwald–Winstein equation to obtain the sensitivity (m-value) to change in solvent ionizing power. For binary hydroxylic solvents, the selectivities (S) for the formation of solvolysis products were very similar to those of the 1-adamantyl derivatives discussed previously. The kinetic solvent isotope effects (KSIEs), salt effects and activation parameters for the solvolyses of 1 were also determined. These observations are compared with those previously reported for the solvolyses of 1-adamantyl chloroformate (1-AdOCOCl, 2). The reasons for change in reaction channels are discussed in terms of the gas-phase stabilities of acylium ions calculated using Gaussian 03.


2021 ◽  
pp. 131291
Author(s):  
Ahmed S. Faihan ◽  
Mohammad R. Hatshan ◽  
Ali S. Alqahtani ◽  
Fahd A. Nasr ◽  
Subhi A. Al-Jibori ◽  
...  

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