Cyclic Disulfide-Bridged Dinitroxide Biradical for Measuring Thiol Redox Status by Electron Paramagnetic Resonance.
| Autor: | Woodcock LB; Department of Chemistry and Biochemistry, University of Denver, Denver, Colorado 80208, United States., Legenzov EA; Center for Biomedical Engineering & Technology, and Department of Physiology, University of Maryland School of Medicine, Baltimore, Maryland 21201, United States., Dirda NDA; Center for Biomedical Engineering & Technology, and Department of Physiology, University of Maryland School of Medicine, Baltimore, Maryland 21201, United States., Kao JPY; Center for Biomedical Engineering & Technology, and Department of Physiology, University of Maryland School of Medicine, Baltimore, Maryland 21201, United States., Eaton GR; Department of Chemistry and Biochemistry, University of Denver, Denver, Colorado 80208, United States., Eaton SS; Department of Chemistry and Biochemistry, University of Denver, Denver, Colorado 80208, United States. |
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| Jazyk: | angličtina |
| Zdroj: | The journal of physical chemistry. B [J Phys Chem B] 2023 Oct 19; Vol. 127 (41), pp. 8762-8768. Date of Electronic Publication: 2023 Oct 09. |
| DOI: | 10.1021/acs.jpcb.3c03387 |
| Abstrakt: | Among low-molecular-weight thiols, glutathione (GSH) is the main antioxidant in the cell, and its concentration is an indicator of the redox status. A cyclic disulfide-linked dinitroxide was designed for monitoring GSH by electron-paramagnetic resonance (EPR) spectroscopy. Reaction of the disulfide with GSH and three other thiols was measured at 9.6 GHz (X-band) and shown to be of first order in thiols. It is proposed that the reaction of the disulfide with 1 equiv of thiolate produced a short-lived intermediate that reacts with 1 equiv of thiolate to produce the cleavage product. The equilibrium ratio of the cleaved and intact disulfide is a measure of the redox state. Since the long-term goal is to use the disulfide to probe physiology in vivo, the feasibility of EPR spectroscopy and imaging of the disulfide and its cleavage product was demonstrated at 1 GHz (L-band). |
| Databáze: | MEDLINE |
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