Electron transfer energies and dipole moments of alkyl halides and amines from an electrostatic model

1981 ◽  
Vol 75 (4) ◽  
pp. 1863-1868 ◽  
Author(s):  
Jon Applequist ◽  
Clifford E. Felder
Keyword(s):  
Electron Transfer ◽  
Dipole Moments ◽  
Alkyl Halides ◽  
Electrostatic Model

Evidence for single electron transfer in the reaction of alkoxides with alkyl halides

1984 ◽  
Vol 25 (45) ◽  
pp. 5107-5110 ◽  
Author(s):  
E.C. Ashby ◽  
Dong-Hak Bae ◽  
Won-Suh Park ◽  
Robert N. Depriest ◽  
Wei-Yang Su
Keyword(s):  
Electron Transfer ◽  
Alkyl Halides ◽  
Single Electron ◽  
Single Electron Transfer

scholarly journals Plausible molecular mechanism for activation by fumarate and electron transfer of the dopamine β-mono-oxygenase reaction

2002 ◽  
Vol 367 (1) ◽  
pp. 77-85 ◽  
Author(s):  
D. Shyamali WIMALASENA ◽  
Samantha P. JAYATILLAKE ◽  
Donovan C. HAINES ◽  
Kandatege WIMALASENA
Keyword(s):  
Electron Transfer ◽  
Molecular Mechanism ◽  
Geometric Isomer ◽  
Enzyme Activation ◽  
Reduced Form ◽  
Electrostatic Model ◽  
Steady State Kinetic ◽  
Low Concentrations ◽  
Substrate Inhibitor ◽  
Inhibition Potency

A series of fumarate analogues has been used to explore the molecular mechanism of the activation of dopamine β-mono-oxygenase by fumarate. Mesaconic acid (MA) and trans-glutaconic acid (TGA) both activate the enzyme at low concentrations, similar to fumarate. However, unlike fumarate, TGA and MA interact effectively with the oxidized enzyme to inhibit it at concentrations of 1—5mM. Monoethylfumarate (EFum) does not activate the enzyme, but inhibits it. In contrast with TGA and MA, however, EFum inhibits the enzyme by interacting with the reduced form. The saturated dicarboxylic acid analogues, the geometric isomer and the diamide of fumaric acid do not either activate or inhibit the enzyme. The phenylethylamine—fumarate conjugate, N-(2-phenylethyl)fumaramide (PEA-Fum), is an 600-fold more potent inhibitor than EFum and behaves as a bi-substrate inhibitor for the reduced enzyme. The amide of PEA-Fum behaves similarly, but with an inhibition potency 20-fold less than that of PEA-Fum. The phenylethylamine conjugates of saturated or geometric isomers of fumarate do not inhibit the enzyme. Based on these findings and on steady-state kinetic analysis, an electrostatic model involving an interaction between the amine group of the enzyme-bound substrate and a carboxylate group of fumarate is proposed to account for enzyme activation by fumarate. Furthermore, in light of the recently proposed model for the similar copper enzyme, peptidylglycine α-hydroxylating mono-oxygenase, the above electrostatic model suggests that fumarate may also play a role in efficient electron transfer between the active-site copper centres of dopamine β-mono-oxygenase.

scholarly journals Ni/Co-Catalyzed Homo-Coupling of Alkyl Tosylates

Molecules ◽  
2019 ◽  
Vol 24 (8) ◽  
pp. 1458 ◽  
Author(s):  
Kimihiro Komeyama ◽  
Ryusuke Tsunemitsu ◽  
Takuya Michiyuki ◽  
Hiroto Yoshida ◽  
Itaru Osaka
Keyword(s):  
Electron Transfer ◽  
Oxidative Addition ◽  
Alkyl Halides ◽  
Cobalt Catalysts ◽  
Single Electron ◽  
Single Electron Transfer ◽  
Mild Conditions

A direct reductive homo-coupling of alkyl tosylates has been developed by employing a combination of nickel and nucleophilic cobalt catalysts. A single-electron-transfer-type oxidative addition is a pivotal process in the well-established nickel-catalyzed coupling of alkyl halides. However, the method cannot be applied to the homo-coupling of ubiquitous alkyl tosylates due to the high-lying σ*(C–O) orbital of the tosylates. This paper describes a Ni/Co-catalyzed protocol for the activation of alkyl tosylates on the construction of alkyl dimers under mild conditions.

Dipole-moment-driven diesel soot oxidation in the presence of alkali metal chlorides

2018 ◽  
Vol 8 (4) ◽  
pp. 970-974 ◽  
Author(s):  
Hui Chen ◽  
Yexin Zhang ◽  
Jian Zhang
Keyword(s):  
Electron Transfer ◽  
Dipole Moment ◽  
Alkali Metal ◽  
Dipole Moments ◽  
Soot Oxidation ◽  
Diesel Soot ◽  
Alkali Metal Chlorides ◽  
Metal Chlorides ◽  
Diesel Soot Oxidation

The dipole moments of alkali metal chlorides drive the oxidation of soot by promoting electron transfer, justifying their excellent activities despite their poor redox abilities.

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