First principle quantum molecular computations have been carried out at the B3LYP/6-31G(d,p) and G3MP2B3 levels of theory on ethyl mercaptan and diethyl disulfide to study their full conformational space. The consequences of molecular axis chirality for the potential energy hypersurface of diethyl disulfide was fully explored. Thermodynamic functions (U, H, S, and G) have been computed for every conformer of the products as well as the reactants of the redox systems studied. Relative values of the thermodynamic functions were calculated with respect to the reference structures with anti orientation. The energetics of the following Red-Ox reactions Et - SH + HO - OH + HS - Et &rarr: 2H 2O + Et - S - S - Et Et - SH + HO - OCOO (-) + HS - Et → H 2O + Et - S - S - Et + HCO 3 - have been chosen to mimic the biologically important Red-Ox reactions of glutathione G - SH + H 2O 2 + HS - G → 2H 2O + G - S - S - G G - SH + HCO 4 - + HS - G → H 2O + G - S - S - G + HCO 3 - The Red-Ox reaction of Et - SH → Et - S - S - Et was found to be exothermic by first principle molecular computations and the intramolecular interactions, such as the unusual C - H ⋯ H - C noncovalent bondings were studied by Bader's atoms in molecules analysis of the electron density topology. The present paper focuses attention on the thermodynamic aspect of the redox reaction of glutathione. It has been noted previously that on going from a cancerous to a healthy cell, the entropy change is negative, corresponding to information accumulation. Likewise, the dissociation of peptide parallel β-sheets, that dominate the plaques in Alzheimer's Disease, governs negative entropy change. It may be interesting to note, according to the results obtained in the present paper, a negative entropy change, corresponding to information accumulation.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry