Effect of micelle polarity on kinetics and efficiency of peroxyoxalate chemiluminescent reaction

Fomin, E.O.; Iakimov, N.P.; Budynina, E.M.; Plutalova, A.V.; Chernikova, E.V.; Grozdova, I.D.; Melik-Nubarov, N.S.

Авторы: Fomin Evgenii O., Iakimov Nikolai P., Budynina Ekaterina M., Plutalova Anna V., Chernikova Elena V., Grozdova Irina D., Melik-Nubarov Nikolay S.
Журнал: Journal of Photochemistry and Photobiology A: Chemistry
Том: 477
Год издания: 2026
Издательство: Elsevier BV
Местоположение издательства: Netherlands
Номер статьи: 117147
DOI: 10.1016/j.jphotochem.2026.117147
Аннотация: The peroxyoxalate chemiluminescent reaction (PO-CL reaction) is particularly significant among energy sources for chemiexcited photodynamic therapy, owing to its high quantum yield. Nevertheless, when conducted in an aqueous medium, PO-CL reaction often encounters side reactions, such as oxalate hydrolysis, which considerably diminish the quantum yield. To mitigate the impact of side processes, hydrophobic nanoreactors are utilized. Our research represents the first investigation of the relationship between the polarity of micellar nanoreactors and the kinetics and efficiency of PO-CL reaction. Block copolymers composed of monomethoxy-poly(ethylene glycol), mPEG, and poly(l-lactide) (PLLA) or poly(ɛ-caprolactone) (PCL) were synthesized and used for preparation of micellar nanoreactors. Micelle polarity estimated by the position of the absorption band ET30 was recognized to be an important factor determining performance of PO-CL reaction. A decrease in nanoreactor polarity caused a reduction of hydrolysis rate constant and a growth of the efficiency of PO-CL reaction. The latter effect appeared to be due to the enhancement of the efficiency of activator excitation step of PO-CL reaction. The results obtained herein open the way to rational design of functioning nanoreactors for chemiexcited-PDT.
Добавил в систему: Фомин Евгений Олегович

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