Thermodynamic role of glutathione oxidation by peroxide and peroxybicarbonate in the prevention of Alzheimer's disease and cancer

Natalie J. Galant, Hui Wang, DongJin R. Lee, Zoltan Mucsi, David H. Setiadi, B. Viskolcz, I. Csizmadia

Research output: Contribution to journalArticle

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Abstract

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.

Original languageEnglish
Pages (from-to)9138-9149
Number of pages12
JournalJournal of Physical Chemistry A
Volume113
Issue number32
DOIs
Publication statusPublished - Aug 13 2009

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glutathione
Peroxides
peroxides
Glutathione
Entropy
cancer
Thermodynamics
Disulfides
Oxidation
thermodynamics
oxidation
disulfides
entropy
Chirality
Redox reactions
Potential energy
Carrier concentration
Cells
chirality
thiols

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Thermodynamic role of glutathione oxidation by peroxide and peroxybicarbonate in the prevention of Alzheimer's disease and cancer. / Galant, Natalie J.; Wang, Hui; Lee, DongJin R.; Mucsi, Zoltan; Setiadi, David H.; Viskolcz, B.; Csizmadia, I.

In: Journal of Physical Chemistry A, Vol. 113, No. 32, 13.08.2009, p. 9138-9149.

Research output: Contribution to journalArticle

Galant, Natalie J. ; Wang, Hui ; Lee, DongJin R. ; Mucsi, Zoltan ; Setiadi, David H. ; Viskolcz, B. ; Csizmadia, I. / Thermodynamic role of glutathione oxidation by peroxide and peroxybicarbonate in the prevention of Alzheimer's disease and cancer. In: Journal of Physical Chemistry A. 2009 ; Vol. 113, No. 32. pp. 9138-9149.
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AU - Mucsi, Zoltan

AU - Setiadi, David H.

AU - Viskolcz, B.

AU - Csizmadia, I.

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