TY - JOUR

T1 - Synthesis, Photophysical Properties, and Toxicity of o-Xylene-Bridged Porphyrin Dimers

AU - Zhdanova, Kseniya A.

AU - Zaytsev, Andrey A.

AU - Gradova, Margarita A.

AU - Gradov, Oleg V.

AU - Lobanov, Anton V.

AU - Novikov, Alexander S.

AU - Bragina, Natal’ya A.

PY - 2023/10/19

Y1 - 2023/10/19

N2 - In this work, a number of new porphyrin dimers coupled with spacers based on α,α’-dibromo-o-xylene were synthesized and characterized by 1H, 13C NMR, 1H-1H COSY NMR, UV-vis-spectroscopy, and MALDI-TOF mass spectrometry. The initial A3B-type hydroxy-substituted porphyrins form dimer structures with high yields of 80–85%, while the use of amino-substituted porphyrins as starting compounds leads to the heterocyclization and formation of N-heterocycle fused porphyrins. For porphyrin dimers, photophysical properties and quantum yields of singlet oxygen were investigated. The peripheral alkoxy-substituents increase fluorescence quantum yield in comparison with the unsubstituted compounds. Also, it was found that dimers are characterized by lower singlet oxygen quantum yields compared to the corresponding monomers. Model aggregation experiments in micellar systems demonstrate stabilization of the photoactive monomolecular form of all the porphyrins, using nonionic surfactant Triton X-100. Cytotoxicity of received dimers shows high inhibition against HEK293T cells in the absence of light.

AB - In this work, a number of new porphyrin dimers coupled with spacers based on α,α’-dibromo-o-xylene were synthesized and characterized by 1H, 13C NMR, 1H-1H COSY NMR, UV-vis-spectroscopy, and MALDI-TOF mass spectrometry. The initial A3B-type hydroxy-substituted porphyrins form dimer structures with high yields of 80–85%, while the use of amino-substituted porphyrins as starting compounds leads to the heterocyclization and formation of N-heterocycle fused porphyrins. For porphyrin dimers, photophysical properties and quantum yields of singlet oxygen were investigated. The peripheral alkoxy-substituents increase fluorescence quantum yield in comparison with the unsubstituted compounds. Also, it was found that dimers are characterized by lower singlet oxygen quantum yields compared to the corresponding monomers. Model aggregation experiments in micellar systems demonstrate stabilization of the photoactive monomolecular form of all the porphyrins, using nonionic surfactant Triton X-100. Cytotoxicity of received dimers shows high inhibition against HEK293T cells in the absence of light.

KW - aggregation

KW - dark toxicity

KW - meso-arylporphyrins

KW - porphyrin dimers

KW - singlet oxygen

KW - solubilization

KW - synthesis

UR - https://www.mendeley.com/catalogue/ff86f024-f566-372a-a227-f27b346ddc48/

U2 - 10.3390/inorganics11100415

DO - 10.3390/inorganics11100415

M3 - Article

VL - 11

JO - Inorganics

JF - Inorganics

SN - 2304-6740

IS - 10

M1 - 415

ER -