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Heterogeneous Photocatalytic Systems Based on Fluorinated Tetraphenylporphyrin Supported on Polysaccharide Aerogels

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Abstract

Solid-phase photosensitizing systems active in the generation of singlet oxygen (1O2) are obtained from fluorinated tetraphenylporphyrin (FTPP) immobilized on polysaccharide aerogels (chitosan and calcium alginate). Immobilization is carried out in a supercritical carbon dioxide (SC–CO2), or by planting FTPP on an aerogel (AEG) from a solution in chloroform. The kinetic parameters of the oxidation of tryptophan in an aqueous medium and anthracene in SC–CO2 are found using these photocatalytic systems. It is shown that the immobilization of porphyrin on a chitosan aerogel does not affect the effective rate constant of photooxidation. Active photocatalytic systems for FTPP immobilized on AG of calcium alginate are obtained only by impregnating the polymer with FTPP molecules in SC–CO2. It is found that FTPP immobilized on both chitosan and calcium alginate aerogels retains its functional activity for 3–4 cycles in model photooxidation processes. Differential thermal analysis is used to explain the differences between the photocatalytic activity of solid-phase aerogel systems containing porphyrin photosensitizers. Treatment with chloroform in particular has almost no effect on the thermooxidative destruction of the FTPP–chitosan aerogel system. A change in the thermooxidative destruction of the catalyst after treating the FTPP–AG system of calcium alginate with chloroform testifies to a change in structure of the system. It is concluded that photostable photosensitizing systems based on aerogels of calcium alginate or chitosan containing fluorinated tetraphenylporphyrins can be used for the photooxidation of organic substrates in both aqueous solutions and a supercritical medium.

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Funding

This work was supported by the Russian Foundation for Basic Research, project no. 18-29-06019 (preparation of photoactive systems based on polysaccharide aerogels). It was performed as part of State Task no. 0082-2019-0012 (analysis of the structure of polymer carriers after SC-impregnation with functionally active compounds).

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Authors and Affiliations

  1. Semenov Federal Research Center of Chemical Physics, Russian Academy of Sciences, 119991, Moscow, Russia

    A. S. Kopylov, N. A. Aksenova, M. A. Savko, I. V. Shershnev, T. S. Zarkhina, A. V. Cherkasova, P. S. Timashev & A. B. Solovieva

  2. Institute of Fine Chemical Technologies, Russian Technological University, 119571, Moscow, Russia

    A. S. Kopylov

  3. Institute of Regenerative Medicine, First Moscow State Medical University, 119435, Moscow, Russia

    N. A. Aksenova & P. S. Timashev

  4. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, 119991, Moscow, Russia

    A. V. Krivandin & O. V. Shatalova

  5. Department of Chemistry, Moscow State University, 119234, Moscow, Russia

    P. S. Timashev

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  1. A. S. Kopylov
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  2. N. A. Aksenova
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  3. M. A. Savko
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  4. I. V. Shershnev
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  5. T. S. Zarkhina
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  6. A. V. Krivandin
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  7. O. V. Shatalova
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  8. A. V. Cherkasova
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  9. P. S. Timashev
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  10. A. B. Solovieva
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Correspondence to A. S. Kopylov.

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Translated by A. Tulyabaev

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Kopylov, A.S., Aksenova, N.A., Savko, M.A. et al. Heterogeneous Photocatalytic Systems Based on Fluorinated Tetraphenylporphyrin Supported on Polysaccharide Aerogels. Russ. J. Phys. Chem. 96, 444–449 (2022). https://doi.org/10.1134/S0036024422020133

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  • DOI: https://doi.org/10.1134/S0036024422020133

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