In this work, we report the use of oxovanadium phosphate as support of the 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin iron (III) chloride (Fe(TDCPP)Cl) and of the 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin manganese (III) chloride (Mn(TDCPP)Cl) catalysts for cyclohexane and cyclooctene oxidations by iodosylbenzene. The catalytic results have shown that oxovanadium phosphate support is suitable for metalloporphyrin catalysts leading to an efficient system for the cyclooctene epoxidation and very selective for cyclohexane hydroxylation.
The aim of this work was to evaluate whether metalloporphyrin models could mimic the action of cytochrome P-450 in the oxidation of atrazine, a herbicide. The commercially available second-generation metalloporphyrins 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin metal(III) chloride [M(TDCPP)Cl] and 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin metal(III) chloride [M(TFPP)Cl] (metal = Fe or Mn) and the oxidants iodosylbenzene and metachloroperbenzoic acid were employed in this study. Results showed that the metalloporphyrins used here can oxidize atrazine. Yields as high as 32% were obtained for the Mn(TFPP)Cl/PhIO system, which shows that these catalysts can mimic both the in vivo and the in vitro action of cytochrome P-450, with formation of the metabolites DEA and DIA. The formation of five other unknown products was also detected, but only one of them could be identified, since the other four were present in very low concentrations. The compound COA, identified by mass spectrometry, was the main product in most of the oxidation reactions.
The porphyrin 5,10,15,20-tetrakis[4-(1,4,7,10,13-pentaoxacyclopentadecane-2-aminomethyl)2,3,5,6-tetrafluorophenyl]porphyrin,T15C5P, was synthesized by the reaction of 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin with the crown ether 2-aminomethyl-(15-crown-5). The crowned porphyrin showed a distinct spectroscopic behavior in the presence of sodium and potassium ions. Dimerization studies based on absorption measurements clearly indicate that T15C5P aggregates in the presence of potassium ions in chloroform/methanol medium (1.0 × 10−5 mol.L −1 or 1.0 × 10−4 mol.L −1), with a dimerization constant ( K D ) of 2.14 × 10−5 and 2.23 × 10−5, respectively. The same formalism applied to the T15C5P in the presence of sodium ions indicated absence of the aggregation process. The ionic radius of Na + is suitable to fit well into the cavity of 15-crown-5 moieties, leading to intramolecular complexes only. Potassium ion is too large to lie in the hole of the crown ether entities and is probably located between two porphyrin molecules, promoting 2:1 aggregated complexes through it's sandwiching, as is observed for phthalocyanines.
In this study, we evaluated the photophysical properties of 5,10,15,20-tetrakis[4-(1,4,7,10,13-pentaoxacyclopentadecane-2-aminomethyl)2,3,5,6-(tetrafluoro)-phenyl]-porphyrin (H2C4P) and Zn(II)5,10,15,20-tetrakis[4-(1,4,7,10,13-pentaoxacyclopenta-decane-2-aminomethyl)2,3,5,6-(tetrafluoro)-phenyl]-porphyrinate (ZnC4P). We observed that these porphyrins have unique properties when compared with classical porphyrins. The porphyrins H2C4P and ZnC4P showed efficient transfer energy S1 to T1 by intersystem crossing with high and reasonable yields of triplet excited state and singlet oxygen production. These amphiphilic structures of these porphyrins could improve its localization in the tumor cells due to the presence of the crown ether in its framework. We also believed that the crown ether could modulate the change in ion homeostase (Ca(+2), K+, Na+) as already described by some new phthalocyanine dye. This fact makes us believe that it could be reasonably used as a photosensitizer for PDT purposes.
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