Abstract
The imbalance between prooxidants and antioxidants in biological systems, known as oxidative stress, can lead to a disruption of redox signaling by the reactive oxygen/nitrogen species and is related to severe diseases. The most vulnerable moiety targeted by oxidant species in the redox signaling pathways is the thiol (SH) group in the cysteine residues, especially in its deprotonated (S−) form. Cysteine, along with its oxidized, disulfide-containing form, cystine, constitute one of the most abundant low molecular weight biological redox couples, providing a significant contribution to the redox homeostasis in living systems. In this work, NMR spectra from cysteine, cystine, and cysteine-containing small peptides were thoroughly studied at the submolecular level, and through the chemical shift data set of their certain atoms it is possible to estimate either thiolate basicity or the also related standard redox potential. Regression analysis demonstrated a strong linear relationship for chemical shift vs thiolate logK of the cysteine microspecies data. The αCH 13C chemical shift is the most promising estimator of the acid-base and redox character.
Highlights
The imbalance between prooxidants and antioxidant pathways in biological systems, known as oxidative stress, can lead to a disruption of redox signaling by the reactive oxygen/nitrogen species and is related to aging, atherosclerosis, carcinogenesis, diabetes, and neurodegeneration [1, 2]
Project no. 20181.2.1-NKP-2018-00005 has been implemented with the support provided from the National Research, Development and Innovation Fund of Hungary, financed under the 2018-1.2.1-NKP funding scheme
Arash Mirzahosseini is grateful for the Janos Bolyai Research Scholarship of the Hungarian Academy of Sciences
Summary
The imbalance between prooxidants and antioxidant pathways in biological systems, known as oxidative stress, can lead to a disruption of redox signaling by the reactive oxygen/nitrogen species and is related to aging, atherosclerosis, carcinogenesis, diabetes, and neurodegeneration [1, 2]. The abovementioned reactive oxidizing species have some essential role against infectious pathogens and in cellular signaling systems, their effects are favorable only if they are present in low or moderate concentrations and under tight cellular regulation [3]. Lendulet grant from the Hungarian Academy of Sciences is gratefully acknowledged. This work was completed in the ELTE Thematic Excellence Programme supported by the Hungarian Ministry for Innovation and Technology. Arash Mirzahosseini is grateful for the Janos Bolyai Research Scholarship of the Hungarian Academy of Sciences. The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript
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