Dynamic Solvent Effects on Equilibrium Isomerization: Kramers Theory Revisited with 2DIR Chemical Exchange

2010 ◽  
Author(s):  
Jessica M. Anna ◽  
Kevin J. Kubarych
Keyword(s):  
Solvent Effects ◽  
Chemical Exchange

The Photochemically Produced Ketyl of Perfluorobenzophenone: Electron Spin Resonance Studies of Solvent Effects

1973 ◽  
Vol 51 (19) ◽  
pp. 3211-3216 ◽  
Author(s):  
Frederick Peter Sargent ◽  
Marshall Grant Bailey
Keyword(s):  
Electron Spin Resonance ◽  
Equilibrium Constant ◽  
Mole Fraction ◽  
Electron Spin ◽  
Solvent Effects ◽  
Chemical Exchange ◽  
Solvent Molecule ◽  
Solvent Mixtures ◽  
Ketyl Radical ◽  
Spin Resonance

The ketyl radical is formed when solutions of perfluorobenzophenone are photolyzed with u.v. light. The radical was identified by electron spin resonance (e.s.r.) studies of the effects of solvent, temperature, chemical exchange, and deuteration on the spectra. Solvent mixtures of cyclohexane and ethanol gave spectra which were very sensitive to the mole fraction of alcohol in the range 0–1%. An equilibrium constant for solvent molecule exchange has been deduced.

Solvent Effects on Chemical Exchange in a Push–Pull Ethylene as Studied by NMR and Electronic Structure Calculations

2011 ◽  
Vol 115 (26) ◽  
pp. 7531-7537 ◽  
Author(s):  
Maysoon Ababneh-Khasawneh ◽  
Blythe E. Fortier-McGill ◽  
Marzia E. Occhionorelli ◽  
Alex D. Bain
Keyword(s):  
Electronic Structure ◽  
Solvent Effects ◽  
Chemical Exchange ◽  
Electronic Structure Calculations ◽  
Structure Calculations

Kinetic Solvent Effects in Organic Reactions

2017 ◽  
Author(s):  
Belinda Slakman ◽  
Richard West
Keyword(s):  
Solvent Effect ◽  
Reaction Kinetics ◽  
Computational Methods ◽  
High Throughput ◽  
Kinetic Modeling ◽  
Solvent Effects ◽  
Reaction Rates ◽  
Prior Work ◽  
Solvent Phase ◽  
High Throughput Manner

<div> <div> <div> <p>This article reviews prior work studying reaction kinetics in solution, with the goal of using this information to improve detailed kinetic modeling in the solvent phase. Both experimental and computational methods for calculating reaction rates in liquids are reviewed. Previous studies, which used such methods to determine solvent effects, are then analyzed based on reaction family. Many of these studies correlate kinetic solvent effect with one or more solvent parameters or properties of reacting species, but it is not always possible, and investigations are usually done on too few reactions and solvents to truly generalize. From these studies, we present suggestions on how best to use data to generalize solvent effects for many different reaction types in a high throughput manner. </p> </div> </div> </div>

Detection of Chemical Exchange in Methyl Groups of Macromolecules

2019 ◽  
Author(s):  
Michelle Gill ◽  
Andrew Hsu ◽  
Arthur G. Palmer, III
Keyword(s):  
Relaxation Rate ◽  
Chemical Exchange ◽  
Double Quantum ◽  
Methyl Groups ◽  
Multiple Quantum ◽  
Relaxation Data ◽  
E Coli ◽  
Methyl Trosy ◽  
Dynamics Simulations ◽  
Exchange Broadening

<div> <div> <div> <p>The zero- and double-quantum methyl TROSY Hahn-echo and the methyl <sup>1</sup>H-<sup>1</sup>H dipole- dipole cross-correlation nuclear magnetic resonance experiments enable estimation of multiple quantum chemical exchange broadening in methyl groups in proteins. The two relaxation rate constants are established to be linearly dependent using molecular dynamics simulations and empirical analysis of experimental data. This relationship allows chemical exchange broadening to be recognized as an increase in the Hahn-echo relaxation rate constant. The approach is illustrated by analyzing relaxation data collected at three temperatures for <i>E. coli </i>ribonuclease HI and by analyzing relaxation data collected for different cofactor and substrate complexes of <i>E. coli </i>AlkB. </p> </div> </div> </div>

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