- Significant role of high-valent iron-oxo species in the degradation and detoxification of indomethacine
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A novel high-valent iron-oxo species (Fe(IV) = O) generated from Iron hexadecachlorophthalocyanine (FePcCl16)-mediated peroxymonosulfate (PMS) activation under visible light illumination for the degradation of a special group of compounds, indomethacine (IDM), containing methoxy, carboxyl, chloro, and amide groups was investigated. The experimental results indicate that Fe(IV) = O was able to selectively attack the carbonyl C–N bond on twisted amide groups, which exerts a strong toxic effect, and could therefore, effectively degrade and detoxify IDM and its byproducts. Twelve byproducts were identified by HPLC/MS/MS and calculation of frontier electron densities (FEDs), with all amide-group breakage products detected, and the possible pathways were deduced, which mainly consisted of Fe(IV) = O-induced cleavage of amide groups and radicals-induced reactions. Ecological risk assessment further confirmed a decrease in toxicity towards IDM degradation, which provides a promising Fe(IV) = O species for selective oxidation and detoxification of destabilized ground-state amides in drinking-water and wastewater treatment.
- Chen, Han,Lin, Tao,Chen, Wei,Xu, Hang,Tao, Hui
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- Perchlorinated phthalocyanines: Spectroscopic properties and surface electrochemistry
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The electronic spectroscopic data for zinc, cobalt, and iron perchlorinated phthalocyanines in several oxidation states are discussed. The magnetic properties of the iron(II) and cobalt(II) derivatives from ambient temperature to 5 K are reported. The electrochemical behavior of these three species is reported in solution and as surfaces on highly oriented pyrolytic graphite. The pH dependence of the surface data is analyzed in detail. The first clearly defined reduction process corresponds with MI[Cl16Pc(-2)]-/MI[Cl 16Pc(-3)]2- for M = Co and Fe. The iron and cobalt species' MIIPc(-2)/[MIPc(-2)]- redox process are broad or ill-defined on the surface and absent from solution. The FeIII[Cl16Pc(-2)]+/FeII[Cl 16Pc(-2)] redox process has atypical pH dependence. The data are explained in terms of the acceptor nature of the chlorine substitution. Oxygen reduction data, catalyzed by these species, are also reported.
- Golovin, M. Neal,Seymour, Penny,Jayaraj, Karupiah,Fu, YanSong,Lever
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p. 1719 - 1727
(2008/10/08)
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- Synthesis and properties of substituted (phthalocyaninato)iron and -cobalt compounds and their pyridine adducts
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A direct route to peripherally substituted (phthalocyaninato)metal derivatives RmPcM (R = t-Bu, m = 4, M = Fe, Co; R = CH3O, m = 8, M = Fe, Co; R = NO2, m = 4, M = Co; R = CH3, m = 8, M = Fe; R = Cl, m = 16, M = Fe) is described. Their thermal stabilities, UV/vis and mass spectra, and solubilities are reported. The coordination behavior of these metallomacrocycles to base molecules has been investigated in a model reaction with pyridine. The synthesis of the pyridine adducts RmPcM(py)2 is presented. The new complexes have been characterized by thermal analyses (TG, DTA). The thermal properties of the pyridine adducts, and in the case of the cobalt complexes the coordination number of the central metal atom, are correlated with peripheral substituent effects.
- Metz, Josef,Schneider, Otto,Hanack, Michael
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p. 1065 - 1071
(2008/10/08)
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