Redox Transformations of the OX063 Radical in Biological Media: Oxidative Decay of Initial Trityl with Further Formation of Structurally-Modified TAM.

Autor: Ovcherenko SS; N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, 9 Akad. Lavrentiev Avenue, Novosibirsk, 630090, Russian Federation.; Novosibirsk State University, 2 Pirogova Street, Novosibirsk, 630090, Russian Federation., Raizvich AE; N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, 9 Akad. Lavrentiev Avenue, Novosibirsk, 630090, Russian Federation.; Novosibirsk State University, 2 Pirogova Street, Novosibirsk, 630090, Russian Federation., Rogozhnikova OY; N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, 9 Akad. Lavrentiev Avenue, Novosibirsk, 630090, Russian Federation., Tormyshev VM; N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, 9 Akad. Lavrentiev Avenue, Novosibirsk, 630090, Russian Federation., Trukhin DV; N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, 9 Akad. Lavrentiev Avenue, Novosibirsk, 630090, Russian Federation., Koval VV; Institute of Chemical Biology and Fundamental Medicine SB RAS, 8 Akad. Lavrentiev Avenue, Novosibirsk, 630090, Russian Federation., Salnikov GE; N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, 9 Akad. Lavrentiev Avenue, Novosibirsk, 630090, Russian Federation., Genaev AM; N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, 9 Akad. Lavrentiev Avenue, Novosibirsk, 630090, Russian Federation., Shernyukov AV; N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, 9 Akad. Lavrentiev Avenue, Novosibirsk, 630090, Russian Federation., Bagryanskaya EG; N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, 9 Akad. Lavrentiev Avenue, Novosibirsk, 630090, Russian Federation.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Sep 16; Vol. 30 (52), pp. e202400718. Date of Electronic Publication: 2024 Sep 03.
DOI: 10.1002/chem.202400718
Abstrakt: Being a low-toxic and hydrophilic representative of TAM, OX063 has shown its suitability for in-vivo and in-cell EPR experiments and design of spin labels. Using 13 C labeling, we investigated the course of oxidative degradation of OX063 into quinone-methide (QM) under the influence of superoxide as well as further thiol-promoted reduction of QM into TAM radical, which formally corresponds to substitution of a carboxyl function by a hydroxyl group. We found these transformations being quantitative in model reactions mimicking specific features of biological media and confirmed the presence of these reactions in the blood and liver homogenate of mice in vitro. The emergence of the trityl with the hydroxyl group can be masked by an initial TAM in EPR spectra and may introduce distortions into EPR-derived oximetry data if they have been obtained for objects under hypoxia. 13 C labeling allows one to detect its presence, considering its different hyperfine splitting constant on 13 C 1 (2.04 mT) as compared to OX063 (2.30 mT). The potential involvement of these reactions should be considered when using TAM in spin-labeling of biopolymers intended for subsequent EPR experiments, as well as in the successful application of TAM in experiments in vivo and in cell.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE
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