Photoinduced energy and electron transfer in Zn(II) carborane phthalocyanine and its complex with albumin explored from femto- to milliseconds

Nekipelova, T.D.; Wöhrle, D.; Burtsev, I.D.; Druzina, A.A.; Egorov, A.E.; Kostyukov, A.A.; Bregadze, V.I.; Shelaev, I.V.; Nadtochenko, V.A.; Kuzmin, V.A.

Авторы: Nekipelova Tatiana D., Wöhrle Dieter, Burtsev Ivan D., Druzina Anna A., Egorov Anton E., Kostyukov Alexey A., Bregadze Vladimir I., Shelaev Ivan V., Nadtochenko Victor A., Kuzmin Vladimir A.
Журнал: Journal of Photochemistry and Photobiology A: Chemistry
Том: 477
Год издания: 2026
Издательство: Elsevier BV
Местоположение издательства: Netherlands
Номер статьи: 117129
DOI: 10.1016/j.jphotochem.2026.117129
Аннотация: The photophysical and photochemical properties of carborane-substituted zinc(II) phthalocyanine (ZnBPc) and its noncovalent complexes with albumin were studied to elucidate the reactivity triplet-state and photoinduced electron transfer pathways relevant to photodynamic therapy (PDT). The binding constant of the ZnBPc–BSA complex (1.5 × 106 M􀀀 1) indicates strong affinity facilitating its efficient delivery to malignant cells. Steady-stateand time-resolved spectroscopy, including nanosecond transient absorption and femtosecond pump–probe techniques showed that ZnBPc in both free and albumin-bound forms efficiently populates a long-lived triplet state capable of generating singlet oxygen (ΦΔ = 0.54), comparable to unsubstituted ZnPc. Quenching the triplet state with molecular oxygen and ascorbic acid demonstrated that BSA complexation introduces steric hindrance decreasing bimolecular quenching rate constants relative to free ZnBPc. Photoinduced electron transfer from ascorbic acid to the triplet state yielded ZnBPc radical anions, characterized by absorption at 550–630 nm and second-order decay kinetics due to dark back electron transfer. In aqueous HSA-containing systems, femtosecondexperiments provided direct evidence for ultrafast (0.5 ps) electron transfer from aromatic amino acid residues to ZnBPc, generating an excited singlet radical–ion pair 1[HSA(Tyr•+)-ZnBPc•–]. The decay kinetics of the radicalions pair occurs via back fast electron transfer (50 ps) limiting superoxide generation via this pathway. These results indicate that the albumin–ZnBPc complex maintains the high reactivity of the triplet state toward oxygenby modulating the electron transfer and energy transfer dynamics, which opens the potential for selective photochemical action in PDT applications involving superoxide and singlet oxygen.
Добавил в систему: Бурцев Иван Дмитриевич

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Photoinduced energy and electron transfer in Zn(II) carborane phthalocyanine and its complex with albumin explored from femto- to millisecondsстатья

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