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CHE 211B Non-Equilibrium Thermodynamics and Redox Biochemistry

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Understanding the kinetics of redox elements in biological systems remains a major challenge in the study of redox signals and oxidative stress. Redox central elements include the evolutionarily conserved cysteine and methionine subgroups of proteins, which act as sulfur switches, as well as unstable reactive oxygen species (ROS) and reactive nitrogen species (RNS), which play a role in redox signalling. Sulfur switching is dependent on a redox environment where the rate of oxidation is balanced by the rate of reduction with thioredoxin, glutathione disulfide, and cysteine/cystine redox pairs. These central pairs, which we call redox control nodes, maintain stable but non-equilibrium homeostasis, are regulated largely independently in various sub-cellular compartments, and are quasi-independent of each other within compartments. Destruction of the redox control node can affect sulfur switching in different ways, resulting in different responses to oxidative stress. Systems biology provides solutions to the complex problems associated with these responses. In this review, we have summarized the thiol/disulfide pathway, redox potential, and rate information as a basis for modelling sulfur switch kinetics. The summary highlighted gaps in knowledge, especially those related to redox coupling between compartments, the definition of redox pathways, and differences between types of sulfur switches. The GSH/GSSG Redox Control Kinetic Modeling Formula shows that systems biology can stimulate new therapies to prevent oxidative stress by identifying specific redox-sensitive sites that could be targeted for intervention.

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