Photo- and Chemiluminescence Processes in Alkaline DMSO. Salient Facets
Yurii B. Tsaplev1, Olga I. Yablonskaya1, Vladimir V. Naumov1, Galina F. Fedorova1, Timur L. Veprintsev,1 Aleksei V. Trofimov1; 1Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, Moscow, Russia
Abstract
Dimethyl sulfoxide (DMSO) is a very important polar aprotic solvent which dissolves both polar and nonpolar compounds and is miscible with a wide range of organic solvents and water. These properties define its utility for mechanistic studies. In the context of our work, the properties of DMSO in the presence of bases are of particular importance. Most prominently, its ability to create superbasic conditions upon addition of strong bases is noteworthy. Such kind of superbasic environment facilitates reactions that are otherwise difficult to perform. The ground-state chemistry under superbasic conditions is marked by striking and unexpected results of both mechanistic and synthetic value. As distinct from that, in our resent works [1-9] we have studied for the first time the peculiarities of the processes occurring in a superbasic environment involving electronic excitation, the latter refers to both photo- [1-4,8,9] and chemiluminescence [5-7] processes. Our model studies pertain to a detailed investigation of the environmental effects and the influence of the specific interactions on the spectral and photochemical properties of the pertinent luminophores (curcumin, its derivatives and methylene blue) in alkaline DMSO, as well as on the chemiluminescence of luminol under the same conditions. Deprotonation of luminol is an important step in its chemiluminescence pathway, and a superbasic medium (e.g., alkaline DMSO) is necessary to convert luminol into a doubly deprotonated form. Using alkaline DMSO enabled us to determine the conditions and ways for inhibiting, quenching and subsequent reactivation of the luminol chemiluminescence using hydrogen peroxide and, for the first time, to establish a detailed mechanism of such a process, whose key stage pertains to the electron transfer from luminol dianion to oxygen during autoxidation.
(1) Yu.B. Tsaplev, V.A. Lapina, A.V. Trofimov, Dyes Pigm. 2020, 177, 108327.
(2) Yu.B. Tsaplev, V.A. Lapina, A.V. Trofimov, J. Photochem. Photobiol. A: Chem. 2021, 405, 112967.
(3) Yu.B. Tsaplev, A.V. Trofimov, Spectrochim. Acta A: Mol. Biomol. Spectrosc., 2021, 251, 119425.
(4) Yu.B. Tsaplev, N.A. Kostin, A.V. Trofimov, Dyes Pigm. 2025, 237, 112692.
(5) Yu.B. Tsaplev, A.V. Trofimov, Russ. J. Phys. Chem. A 2020, 94, 2369-2374.
(6) Yu.B. Tsaplev, A.V. Trofimov, Russ. J. Phys. Chem. A 2022, 96, 1099-1105.
(7) Yu.B. Tsaplev, A.V. Trofimov, Photochem. Photobiol. 2024, 100, 1803-1812.
(8) Yu.B. Tsaplev, A.V. Trofimov, Dyes Pigm. 2026, 248, 113549.
(9) Yu.B. Tsaplev, V.V. Maksimenko, I.G. Plaschina, A.V. Trofimov, Spectrochim. A: Mol. Biomol. Spectrosc. 2026, 358, 127889.
Speaker
Aleksei V. Trofimov
Emanuel Institute of Biochemical Physics RAS
Russian Federation
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