scholarly journals Global analysis of the thermal and chemical denaturation of the N-terminal domain of the ribosomal protein L9 in H2O and D2O. Determination of the thermodynamic parameters, ΔH°, ΔS°, and ΔC°p, and evaluation of solvent isotope effects

1998 ◽  
Vol 7 (11) ◽  
pp. 2405-2412 ◽  
Author(s):  
Brian Kuhlman ◽  
Daniel P. Raleigh
Keyword(s):  
Ribosomal Protein ◽  
Thermodynamic Parameters ◽  
Global Analysis ◽  
Isotope Effects ◽  
Chemical Denaturation ◽  
Terminal Domain ◽  
Ribosomal Protein L9 ◽  
Solvent Isotope ◽  
Solvent Isotope Effects

The Hydrolysis of Disubstituted Alkyl Phosphorochloridates and N,N,N′,N′-Tetra-stibstituted Phosphorodiamidic Chlorides in Water and Deuterium Oxide: Heat Capacity of Activation and Kinetic Solvent Isotope Effects

1973 ◽  
Vol 51 (4) ◽  
pp. 597-603 ◽  
Author(s):  
E. C. F. Ko ◽  
R. E. Robertson
Keyword(s):  
Heat Capacity ◽  
Thermodynamic Parameters ◽  
Alkyl Group ◽  
Deuterium Oxide ◽  
Isotope Effects ◽  
Potential Relationship ◽  
Mechanism Of Reaction ◽  
Solvent Isotope ◽  
Hydrolysis Of ◽  
Solvent Isotope Effects

The pseudo-thermodynamic parameters, ΔH≠, ΔS≠, and ΔCp≠ and the kinetic solvent isotope effects have been determined for the three alkyl-phosphorochloridates, where the alkyl group is ethylisopropyl and n-propyl; for tetra-methyl and tetra-ethyl phosphorodiamidic chlorides; the di-n-propyl and di-isopropyl analog, the di(isopropylmethylcarbinyl)phosphorochloridate and the tetra-ethylthiophosphorodiamidic chloride. These compounds have a potential relationship to compounds used as insecticides and as polymers. The mechanism of reaction is discussed on the basis of these data.

scholarly journals Determination of the Contributions of Concurrent Acetal and Vinyl Ether Hydrolyses on the Basis of the Different Solvent Isotope Effects in These Reactions.

1969 ◽  
Vol 23 ◽  
pp. 1465-1470 ◽  
Author(s):  
Alpo Kankaanperä ◽  
Kari Miikki ◽  
Ch. Larsen ◽  
P. H. Nielsen ◽  
Per-Erik Werner ◽  
...  
Keyword(s):  
Vinyl Ether ◽  
Isotope Effects ◽  
Solvent Isotope ◽  
Solvent Isotope Effects

scholarly journals Rate and Product Studies with 1-Adamantyl Chlorothioformate under Solvolytic Conditions

2021 ◽  
Vol 22 (14) ◽  
pp. 7394
Author(s):  
Kyoung Ho Park ◽  
Mi Hye Seong ◽  
Jin Burm Kyong ◽  
Dennis N. Kevill
Keyword(s):  
Rate Constants ◽  
Isotope Effects ◽  
Ion Pairs ◽  
Carbonyl Sulfide ◽  
Activation Parameters ◽  
Chloride Ions ◽  
Reaction Channels ◽  
Decomposition Pathway ◽  
Solvent Isotope ◽  
Solvent Isotope Effects

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.

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