Species-Specific Thiol–Disulfide Equilibrium Constant: A Tool To Characterize Redox Transitions of Biological Importance

Microscopic redox equilibrium constants, a new species-specific type of physicochemical parameters, were introduced and determined to quantify thiol–disulfide equilibria of biological significance. The thiol–disulfide redox equilibria of glutathione with cysteamine, cysteine, and homocysteine were a...

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Bibliographic Details
Published in:The journal of physical chemistry. B 2015-08, Vol.119 (32), p.10191-10197
Main Authors: Mirzahosseini, Arash, Somlyay, Máté, Noszál, Béla
Format: Article
Language:English
Subjects:
Algorithms
Basicity
Biological
Chemical equilibrium
Constants
Cysteamine
Cysteamine - chemistry
Cysteine
Cysteine - chemistry
Disulfides - chemistry
Glutathione - chemistry
Homocysteine - chemistry
Hydrogen-Ion Concentration
Models, Biological
Models, Chemical
Oxidation-Reduction
Physical chemistry
Proton Magnetic Resonance Spectroscopy
Protons
Reference Values
Solutions - chemistry
Sulfhydryl Compounds - chemistry
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Summary:Microscopic redox equilibrium constants, a new species-specific type of physicochemical parameters, were introduced and determined to quantify thiol–disulfide equilibria of biological significance. The thiol–disulfide redox equilibria of glutathione with cysteamine, cysteine, and homocysteine were approached from both sides, and the equilibrium mixtures were analyzed by quantitative NMR methods to characterize the highly composite, co-dependent acid–base and redox equilibria. The directly obtained, pH-dependent, conditional constants were then decomposed by a new evaluation method, resulting in pH-independent, microscopic redox equilibrium constants for the first time. The 80 different, microscopic redox equilibrium constant values show close correlation with the respective thiolate basicities and provide sound means for the development of potent agents against oxidative stress.
ISSN:1520-6106
1520-5207
DOI:10.1021/acs.jpcb.5b05708