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

Abstract

The nature of the E–E’ bonds (E, E’ = S and Se) in glutathione disulfide (1) and derivatives 2–3, 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 a–e 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 1a–3e 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.

Dynamic and Static Nature of Br4σ(4c–6e) and Se2Br5σ(7c–10e) in the Selenanthrene System and Related Species Elucidated by QTAIM Dual Functional Analysis with QC Calculations

“…A E---B E of A E 2 B E 2 σ(4c-6e) has been elucidated [24][25][26][27] using the quantum theory of atoms in molecules (QTAIM) approach, introduced by Bader [28][29][30][31][32][33][34][35][36][37]. e linear interactions of the σ(4c-6e) type will form if B E in A E 2 B E 2 is replaced by X, giving E 2 X 2 σ(4c-6e).…”

Correlation Between Age, Body Mass Index, And Blood Selenium Level with Glutathione Peroxidase Activity Among Elderly in South Jakarta

“…GSSG is radical so it must be reduced to GSH immediately. 9,10,11 Recently, study about selenium in elderly still rarely. Baierle et al 12 in 2015 found negative correlation between GPx activity with plasma carbonyl in elderly population.…”

Behavior of I4σ(4c–6e) in tellurolane system and related species, elucidated by QTAIM dual functional analysis with QC calculations

“…The nature of the B E··· A E and A E– A E in B E··· A E– A E··· B E at naphthalene peri‐positions was elucidated by employing the quantum theory of atoms‐in‐molecules (QTAIM) approach . The nature of the X···E and E–E in X···E–E···X was similarly clarified.…”

“…[11][12][13][14][15][16] The nature of the B E··· A E and A E-A E in B E··· A E-A E··· B E at naphthalene peri-positions was elucidated by employing the quantum theory of atoms-in-molecules (QTAIM) approach. [17][18][19][20] The nature of the X···E and E-E in X···E-E···X was similarly clarified. X 4 σ(4c-6e) of the n p (X-)→σ*(X-X)←np(X) type is also expected to stabilize the linear alignment of four halogen atoms (X) of the σ-type.…”