Low-symmetry A 3 B-type 6H-1,4-diazepinoporphyrazines with anti-Kasha effect as promising photosensitizers.

Autor: Tarakanov PA; Institute of Physiologically Active Compounds at Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences (IPAC RAS), Chernogolovka, Russia., Neganova ME; Institute of Physiologically Active Compounds at Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences (IPAC RAS), Chernogolovka, Russia., Mishchenko DV; Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences (FRC PCPMC RAS), Chernogolovka, Russia.; Scientific and Educational Center in Chernogolovka of Moscow Region State University, Mytishchi, Russia.; Department of Fundamental Physical and Chemical Engineering, Lomonosov Moscow State University, Moscow, Russia., Bondarenko SD; Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences (FRC PCPMC RAS), Chernogolovka, Russia.; Department of Fundamental Physical and Chemical Engineering, Lomonosov Moscow State University, Moscow, Russia., Sergeeva IA; Department of Physics, Lomonosov Moscow State University, Moscow, Russia., Krot AR; Department of Physics, Lomonosov Moscow State University, Moscow, Russia., Goryachev NS; Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences (FRC PCPMC RAS), Chernogolovka, Russia., Simakov AO; Institute of Physiologically Active Compounds at Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences (IPAC RAS), Chernogolovka, Russia., Kukharsky MS; Institute of Physiologically Active Compounds at Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences (IPAC RAS), Chernogolovka, Russia., Pukhov SA; Institute of Physiologically Active Compounds at Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences (IPAC RAS), Chernogolovka, Russia., Pushkarev VE; Institute of Physiologically Active Compounds at Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences (IPAC RAS), Chernogolovka, Russia.
Jazyk: angličtina
Zdroj: Photochemistry and photobiology [Photochem Photobiol] 2024 Jan 02. Date of Electronic Publication: 2024 Jan 02.
DOI: 10.1111/php.13898
Abstrakt: A series of tribenzo[g,l,q]-6H-1,4-diazepino[2,3-b]porphyrazines has been synthesized. A temperature-dependent steric effect was applied in the mixed Linstead macrocyclization of phthalonitrile and 5,7-bis(2'-arylethenyl)-6-propyl-6H-1,4-diazepine-2,3-dicarbonitrile to achieve high yield of low-symmetry A 3 B-type Mg(II) tribenzo[g,l,q]-6H-1,4-diazepino[2,3-b]porphyrazinate. The analysis of photophysical and photochemical properties of the obtained complexes showed the anti-Kasha effect: the ultrafast spin changes successfully compete with the IC. TD-DFT calculations showed that the presence of 1,4-diazepine heterocycle in the porphyrazine structure leads to the formation of additional charge-transfer triplet state T 2 . We propose, it could participate in the pumping of T 1x state alongside with T 1y state (these states are degenerate in D 4h symmetry) and, therefore, increase singlet oxygen ( 1 Δ g ) generation. Stable micellar nanoparticles have been obtained based on the tribenzo[g,l,q]-6H-1,4-diazepino[2,3-b]porphyrazine Mg(II) and Zn(II) complexes using polyvinylpyrrolidone. The nanoparticles effectively interact with model biological structures (FBS and brain homogenate), leading to disaggregation of the macrocycles. They also exhibit pronounced phototoxic effects in MCF-7 cells upon red light irradiation. We propose that enhancement in PDT activity could be explained by their increased resistance to aggregation due to the presence of n-propyl substituent directly attached to the C6 position of the 1,4-diazepine moiety. The demonstrated results show the promising potential of tribenzo-6H-1,4-diazepinoporphyrazines as heavy atom-free photosensitizers.
(© 2023 American Society for Photobiology.)
Databáze: MEDLINE
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