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- Title
Marcus Cross-Relationship Probed by Time-Resolved CIDNP.
- Authors
Geniman, Maksim P.; Morozova, Olga B.; Lukzen, Nikita N.; Grampp, Günter; Yurkovskaya, Alexandra V.
- Abstract
The time-resolved CIDNP method can provide information about degenerate exchange reactions (DEEs) involving short-lived radicals. In the temperature range from 8 to 65 °C, the DEE reactions of the guanosine-5′-monophosphate anion GMP(-H)− with the neutral radical GMP(-H)•, of the N-acetyl tyrosine anion N-AcTyrO− with a neutral radical N-AcTyrO•, and of the tyrosine anion TyrO− with a neutral radical TyrO• were studied. In all the studied cases, the radicals were formed in the reaction of quenching triplet 2,2′-dipyridyl. The reorganization energies were obtained from Arrhenius plots. The rate constant of the reductive electron transfer reaction in the pair GMP(-H)•/TyrO− was determined at T = 25 °C. Rate constants of the GMP(-H)• radical reduction reactions with TyrO− and N-AcTyrO− anions calculated by the Marcus cross-relation differ from the experimental ones by two orders of magnitude. The rate constants of several other electron transfer reactions involving GMP(-H)−/GMP(-H)•, N-AcTyrO−/N-AcTyrO•, and TyrO−/TyrO• pairs calculated by cross-relation agree well with the experimental values. The rate of nuclear paramagnetic relaxation was found for the 3,5 and β-protons of TyrO• and N-AcTyrO•, the 8-proton of GMP(-H)•, and the 3,4-protons of DPH• at each temperature. In all cases, the dependences of the rate of nuclear paramagnetic relaxation on temperature are described by the Arrhenius dependence.
- Subjects
OXIDATION-reduction reaction; RADICALS (Chemistry); EXCHANGE reactions; REORGANIZATION energy; POLARIZATION (Nuclear physics)
- Publication
International Journal of Molecular Sciences, 2023, Vol 24, Issue 18, p13860
- ISSN
1661-6596
- Publication type
Article
- DOI
10.3390/ijms241813860