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Molecules 2018, 23(2), 443; https://doi.org/10.3390/molecules23020443

Behavior of the E–E’ Bonds (E, E’ = S and Se) in Glutathione Disulfide and Derivatives Elucidated by Quantum Chemical Calculations with the Quantum Theory of Atoms-in-Molecules Approach

Faculty of Systems Engineering, Wakayama University, 930 Sakaedani, Wakayama 640-8510, Japan
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Received: 30 January 2018 / Revised: 10 February 2018 / Accepted: 14 February 2018 / Published: 17 February 2018
(This article belongs to the Section Computational and Theoretical Chemistry)
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Abstract

The nature of the E–E’ bonds (E, E’ = S and Se) in glutathione disulfide (1) and derivatives 23, respectively, was elucidated by applying quantum theory of atoms-in-molecules (QTAIM) dual functional analysis (QTAIM-DFA), to clarify the basic contribution of E–E’ in the biological redox process, such as the glutathione peroxidase process. Five most stable conformers ae were obtained, after applying the Monte-Carlo method then structural optimizations. In QTAIM-DFA, total electron energy densities Hb(rc) are plotted versus Hb(rc) − Vb(rc)/2 at bond critical points (BCPs), where Vb(rc) are potential energy densities at BCPs. Data from the fully optimized structures correspond to the static nature. Those containing perturbed structures around the fully optimized one in the plot represent the dynamic nature of interactions. The behavior of E–E’ was examined carefully. Whereas E–E’ in 1a3e were all predicted to have the weak covalent nature of the shared shell interactions, two different types of S–S were detected in 1, depending on the conformational properties. Contributions from the intramolecular non-covalent interactions to stabilize the conformers were evaluated. An inverse relationship was observed between the stability of a conformer and the strength of E–E’ in the conformer, of which reason was discussed. View Full-Text
Keywords: ab initio calculations; quantum theory of atoms-in-molecules (QTAIM); glutathione dichalcogenides; Monte-Carlo method ab initio calculations; quantum theory of atoms-in-molecules (QTAIM); glutathione dichalcogenides; Monte-Carlo method
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Hayashi, S.; Tsubomoto, Y.; Nakanishi, W. Behavior of the E–E’ Bonds (E, E’ = S and Se) in Glutathione Disulfide and Derivatives Elucidated by Quantum Chemical Calculations with the Quantum Theory of Atoms-in-Molecules Approach. Molecules 2018, 23, 443.

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