Features of the supercritical CO2-assisted immobilization of fluorinated tetraphenylporphyrins into tetrafluoroethylene copolymers
- Authors: Shershnev I.V.1, Cherkasova A.V.1, Kopylov A.S.1, Glagolev N.N.1, Bragina N.A.2, Solov’eva A.B.1
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Affiliations:
- Semenov Institute of Chemical Physics
- Moscow Technological University
- Issue: Vol 91, No 7 (2017)
- Pages: 1324-1331
- Section: Physical Chemistry of Surface Phenomena
- URL: https://journals.rcsi.science/0036-0244/article/view/169624
- DOI: https://doi.org/10.1134/S0036024417070275
- ID: 169624
Cite item
Abstract
The immobilization of fluorinated tetraphenylporphyrins (FTPPs) into tetrafluoroethylene copolymers (fluoroplast F-42 and MF-4SK, a perfluorinated sulfonic acid cation exchanger in H+-form) is conducted in supercritical CO2 (scCO2). The effects the conditions of immobilization (the temperature and pressure of scCO2, reaction time, and the addition of cosolvents) and the structure of the carrier polymer have on the content of porphyrin in these polymers is studied. The porphyrin-loaded polymer systems are shown to exhibit photosensitizing activity in anthracene and cholesterol oxidation in scCO2. Under conditions of photocatalysis, chemical and functional stability is a feature of only MF-4SK polymer systems; this is attributed to the formation of protonated forms of the porphyrins and their interaction with SO3−-groups of the polymer (an ion exchange process), which prevents leaching of the FTPP from the polymer matrix. The photocatalytic process actually occurs inside the matrix of the perfluorinated copolymer, with the protonated form of the porphyrin acting as a photosensitizer. The rate constant of anthracene photooxidation in the presence of FTPP-loaded MF-4SK films in scCO2 is found to pass through a maximum as a function of the porphyrin content and the polymer film thickness. The use of such catalytic systems for cholesterol photooxidation in scCO2 is shown to produce a virtual monoproduct (yield, ~10%): 6-formyl-B-norcholestane-3,5-diol, a compound with high biological activity.
About the authors
I. V. Shershnev
Semenov Institute of Chemical Physics
Author for correspondence.
Email: shershnev.ilya@gmail.com
Russian Federation, Moscow, 1199911
A. V. Cherkasova
Semenov Institute of Chemical Physics
Email: shershnev.ilya@gmail.com
Russian Federation, Moscow, 1199911
A. S. Kopylov
Semenov Institute of Chemical Physics
Email: shershnev.ilya@gmail.com
Russian Federation, Moscow, 1199911
N. N. Glagolev
Semenov Institute of Chemical Physics
Email: shershnev.ilya@gmail.com
Russian Federation, Moscow, 1199911
N. A. Bragina
Moscow Technological University
Email: shershnev.ilya@gmail.com
Russian Federation, Moscow, 119454
A. B. Solov’eva
Semenov Institute of Chemical Physics
Email: shershnev.ilya@gmail.com
Russian Federation, Moscow, 1199911