Game of ligands: tuning the photodynamic activity of P(V) porphyrins in aqueous mediaстатья
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Дата последнего поиска статьи во внешних источниках: 16 июля 2025 г.
Аннотация:For developing novel photosensitizers (PS), a three series of phosphorus (V) tetra-meso-aryl-substituted porphyrins, bearing varying number of pyridyl groups (0 to 2) and different axial ligands (-OH, -OEt, -OPrOH) were obtained. All complexes exhibit fluorescence in EtOH with moderate quantum yields (0.10-0.15) and singlet oxygen (SO) generation with high quantum yields (0.58-0.87). Photostability, fluorescence, and SO generation quantum yields increase with a reduction of the number of pyridyl groups. Moreover, on the example of P(V) mono-pyridyl-substituted porphyrins, it was demonstrated that the photostability and SO generation depend on the nature of the axial ligands, with an increase observed in the following series: -OH < -OPrOH < -OEt. Interestingly, P(V) porphyrins with axial -OH ligands are subject to intracellular dephosphorylation and accumulation in human carcinoma cell organelles (apparently in lysosomes), whereas complexes with axial -OEt groups remain in the initial state and are diffusely distributed throughout the cytoplasm. Remarkably, P(V) complexes exhibit high photoinduced cytotoxicity against human breast adenocarcinoma MCF-7 and human lung adenocarcinoma A-549 cells, with IC50 values reaching the nanomolar range. Mono-pyridyl-three-phenyl and tetraphenyl- complexes bearing -OEt axial ligands are the most promising photosensitizing agents with the highest light cytotoxicity (IC₅₀ =2.0 and 5.7 M for A-549 and 8.9 and 14 nM for MCF-7 cells correspondingly). The dose-dependent effect has also been demonstrated, confirming a light-induced mechanism of cell death