Catalysis science and technology p. 1260 - 1272 (2019)
Update date:2022-08-17
Topics:
Nasrollahi, Rahele
Heydari-Turkmani, Akram
Zakavi, Saeed
In continuation of our studies on the photocatalytic performance of porphyrin diacids, the kinetics and mechanisms of the photooxidation of para-substituted phenyl methyl sulfides (para X = H, CH3, OCH3, Cl, and F) catalyzed by a series of meso-tetra(aryl)porphyrins (aryl = phenyl, 2-chlorophenyl, 2-methylphenyl, 4-chlorophenyl, 4-methylphenyl and 4-methoxyphenyl) immobilized on Amberlyst 15 nanostructures (nanoAmb), H2T(2 or 4-X)PP@nanoAmb, are reported. The immobilization of porphyrins on the polymer was confirmed by diffuse reflectance UV-vis spectroscopy and EDX analysis. While little or no catalyst degradation was observed for a reaction time of ca. 3 h, the electron-deficient porphyrins (pseudo-first-order rate constants, kobs = 0.0049-0.012 min-1) showed faster second-order kinetics than the electron-rich ones (kobs = 2.30 × 10-5-9.92 × 10-4 min-1). The order of photocatalytic activity of the porphyrins approximately correlates with the singlet oxygen quantum yield (φΔ) of the photosensitizers. Diffuse reflectance UV-vis spectra of the immobilized porphyrins demonstrated a large red shift of the Soret and Q bands of the porphyrins which was more dominant in the case of H2T(4-OMe)PP. The weak overlap between the emission spectrum of the light source and the absorption spectrum of the latter was used to explain the low photocatalytic activity of H2T(4-OMe)PP@nanoAmb. The observation of a slope (ρ) of -2.80 for the oxidation of methyl phenyl sulfide and para-substituted phenyl methyl sulfides is in accord with the involvement of an electrophilic oxidation mechanism mediated by singlet oxygen species. H2TPP@naoAmb was recovered and reused at least five times without significant loss of the catalytic activity and detectable catalyst degradation, giving a turnover number of 5 × 5000 for five successive reactions. The catalyst was successfully used for large-scale (up to 6.6 mmol of sulfide per batch, in a 1:10000 catalyst-to-sulfide molar ratio) photooxidation of a wide range of sulfides to the corresponding sulfoxide in a water/acetonitrile solvent mixture.
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Doi:10.1016/j.ijpharm.2019.118655
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