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Published on: February 16, 2022
One-electron reduction of S-nitrosothiols in aqueous medium
V M Manoj1, H Mohan, U K Aravind
1School of Chemical Sciences, Mahatma Gandhi University, Kottayam 686560, Kerala, India.
One-electron reduction of S-nitrosothiols (RSNO) by hydrated electrons releases nitric oxide (NO) and thiols. This reaction, crucial in biological systems, proceeds via a radical anion intermediate, not a thiyl radical.
Area of Science:
- Biochemistry
- Physical Chemistry
- Radiochemistry
Background:
- S-nitrosothiols (RSNO) are important signaling molecules involved in various physiological processes.
- Understanding the redox chemistry of RSNOs is crucial for elucidating their biological functions.
Purpose of the Study:
- To investigate the one-electron reduction of various S-nitrosothiols (RSNOs) using hydrated electrons (e(aq)(-)).
- To determine the kinetics and mechanism of RSNO decomposition upon reduction.
Main Methods:
- Pulse radiolysis technique to generate hydrated electrons (e(aq)(-)) and study reaction kinetics.
- High-performance liquid chromatography (HPLC), fluorimetry, and mass spectrometry (MS) for product analysis.
Main Results:
- The reaction rate constants for e(aq)(-) with RSNOs were diffusion-controlled at neutral pH (approx. 10(10) dm(3) mol(-1) s(-1)).
- Major products identified were thiol (RSH) and nitric oxide (NO).
- A radical anion intermediate (RSN(*)O(-)) was proposed, with no evidence for thiyl radical formation.
Conclusions:
- One-electron reduction of RSNOs leads to the direct liberation of nitric oxide (NO).
- The proposed mechanism involves RSNO radical anion formation, distinct from oxidation pathways.
- This study provides insights into the reductive decomposition of RSNOs relevant to biological redox processes.
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