Mechanism of Nucleophilic Aromatic Substitution of 1-Chloro-2,4-dinitrobenzene by Glutathione in the Gas Phase and in Solution. Implications for the Mode of Action of Glutathione S-Transferases

doi:10.1021/JA963177V

Paper

Mechanism of Nucleophilic Aromatic Substitution of 1-Chloro-2,4-dinitrobenzene by Glutathione in the Gas Phase and in Solution. Implications for the Mode of Action of Glutathione S-Transferases

Published Jan 29, 1997 · Ya-Jun Zheng, R. Ornstein

Journal of the American Chemical Society

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Abstract

The reaction mechanism of nucleophilic aromatic substitution of 1-chloro-2,4-dinitrobenzene by glutathione (as modeled by a thiomethoxide ion) in the gas phase and in solution was elucidated using ab initio molecular orbital theory in combination with a continuum solvent model at the HF/6-31G*, HF/6-31+G**, and MP2/6-31+G** levels of theory. Two ion−molecule complexes were located in the gas phase at the HF level, but only one exits at the MP2/6-31+G** level, while neither exits in aqueous solution. In aqueous solution, there is a large free energy barrier and C−S bond formation is the rate-determining step, which is in agreement with experimental observation. The calculated free energy barrier (30.2 kcal/mol) at the HF/6-31+G** level of theory seems to be in good agreement with experiment (23.8 kcal/mol), while the MP2/6-31+G** barrier is too low, indicating that the MP2/6-31+G** level of theory probably overestimates the stability of the transition state for C−S bond formation. Implications for the mode...

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The mechanism of nucleophilic aromatic substitution of 1-chloro-2,4-dinitrobenzene by glutathione in the gas phase and in solution suggests that the mode of action of glutathione S-transferases is influenced by the stability of the transition state for C-S bond formation.

PopulationOlder adults (50-71 years)

Sample size24

MethodsObservational

OutcomesBody Mass Index projections

ResultsSocial networks mitigate obesity in older groups.

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Paper

Mechanism of Nucleophilic Aromatic Substitution of 1-Chloro-2,4-dinitrobenzene by Glutathione in the Gas Phase and in Solution. Implications for the Mode of Action of Glutathione S-Transferases

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References

Citations

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Nucleophilic aromatic substitution in chlorinated aromatic systems with a glutathione thiolate model

The conjugation of glutathione with chlorobenzene and various chlorinated benzenes via nucleophilic aromatic substitution is feasible and consistent with experiment, with a transition state and activation energies lower than for chlorobenzene.