Iron(III) complexes with meridional ligands as functional models of intradiol-cleaving catechol dioxygenases.

Six dichloroiron(III) complexes of 1,3-bis(2'-arylimino)isoindoline (BAIH) with various N-donor aryl groups have been characterized by spectroscopy (infrared, UV-vis), electrochemistry (cyclic voltammetry), microanalysis, and in two cases X-ray crystallography. The structurally characterized Fe(III)Cl(2)(L(n)) complexes (n = 3, L(3) = 1,3-bis(2'-thiazolylimino)isoindoline and n = 5, L(5) = 1,3-bis(4-methyl-2'-piridylimino)isoindoline) are five-coordinate, trigonal bipyramidal with the isoindoline ligands occupying the two axial and one equatorial positions meridionally. These compounds served as precursors for catechol dioxygenase models that were formed in solution upon addition of 3,5-di-tert-butylcatechol (H(2)DBC) and excess triethylamine. These adducts react with dioxygen in N,N-dimethylformamide, and the analysis of the products by chromatography and mass spectrometry showed high intradiol over extradiol selectivity (the intradiol/extradiol product ratios varied between 46.5 and 6.5). Kinetic measurements were performed by following the change in the intensity of the catecholate to iron ligand-to-metal charge transfer (LMCT) band, the energy of which is influenced by the isoindolinate-ligand (827-960 nm). In combination with electrochemical investigations the kinetic studies revealed an inverse trend between reaction rates and oxidation potentials associated with the coordinated DBC(2-). On the basis of these results, a substrate activation mechanism is suggested for this system in which the geometry of the peroxide-bridged intermediate may be of key importance in regioselectivity.

Ionizing radiation induced degradation of diuron in dilute aqueous solution.

BACKGROUND: Cutting edge technologies based on Advanced Oxidation Processes (AOP) are under development for the elimination of highly persistent organic molecules (like pesticides) from water matrices. Among them, ionizing radiation treatment represents a promising technology that requires no additives and can be easily adapted to an industrial scale. In these processes several reactive species are produced, mainly powerful oxidizing radicals inducing the degradation. This paper investigates the reactions taking place in dilute aqueous solutions of a hazardous pollutant (diuron) during irradiation. RESULTS: Irradiation of aqueous diuron solutions resulted in effective degradation of the solute mainly due to the reactions of hydroxyl radicals formed in water radiolysis. Hydroxyl radical reacts with diuron with a second order rate constant of (5.8 ± 0.3) × 10(9) mol(-1) dm(3) s(-1). The main reaction is addition to the ring forming hydroxycyclohexadienyl radical. 30 - 50% of hydroxyl radical reactions induce dechlorination. Reactions with the methyl groups or with the α-amino group have low contribution to the transformation. The presence of dissolved oxygen enhances the rate of degradation; one hydroxyl radical on average induces five-electron oxidations. The high oxidation rate is attributed to the reaction of some of the primarily formed organic radicals with dissolved O2 and the subsequent reactions of the peroxy radicals. CONCLUSION: The presence of dissolved oxygen is highly important to achieve efficient ionizing radiation induced degradation of diuron in dilute aqueous solution.

Analytical approaches to the OH radical induced degradation of sulfonamide antibiotics in dilute aqueous solutions.

By combining a large variety of analytical techniques this study aimed at elaborating methods to follow up the degradation of sulfonamides in an advanced oxidation process (AOP): irradiation with ionizing radiation in dilute aqueous solution. In this process, besides other radicals, hydroxyl radicals are produced. As pulse radiolysis experiments show the basic initial reaction is hydroxyl radical addition to the benzene ring, forming cyclohexadienyl radical intermediates. In aerated solutions these radicals transform to peroxy radicals. Among the first formed products aromatic molecules hydroxylated in the benzene rings or in some cases in the heterocyclic rings were observed by LC-MS/MS. Chemical oxygen demand (COD) measurements indicate that at the early reaction period of degradation one hydroxyl radical induces incorporation of 1.5 O atoms into the products. Comparison of the COD and TOC (total organic carbon content) results shows gradual oxidation. Simultaneously with hydroxylation ring opening also takes place. The kinetics of inorganic SO4(2-) and NH4(+) formation, analyzed by ion chromatography, is similar to the kinetics of ring degradation (UV spectroscopy), however, there is a delayed formation of NO3(-). The latter ions may be produced in oxidative degradation of smaller N containing fragments. The S atoms of the sulfonamides remain in the solution (ICP-MS measurements) after degradation, whereas some part of the N atoms leaves the solution probably in the form of N2 (total nitrogen content (TN) measurements). Degradation is accompanied by a high pH drop due to formation of SO4(2-), NO3(-) and smaller organic acids. The degradation goes through many simultaneous and consecutive reactions, and with the applied methods the different stages of degradation can be characterized.

Hydroxyl radical-induced degradation of fenuron in pulse and gamma radiolysis: kinetics and product analysis.

Radiolytic reactions of phenylureas were studied in detail with fenuron model compound in dilute aqueous solutions using pulse radiolysis for detection of the intermediates, gamma radiolysis with UV-Vis and HPLC-MS techniques for analysis of the final products. The kinetics of oxidation was followed by COD, TOC and toxicity measurements. During radiolysis of aerated solutions hydroxyl radical ((•)OH), eaq (-), H(•) and O2 (•-)/HO2 (•) reactive intermediates are produced, the degradation of solute takes place practically entirely through (•)OH reactions. Therefore, the product distribution is similar to the distributions reported in other advanced oxidation processes with (•)OH as main reactant. (•)OH mainly reacts with the aromatic ring, forming cyclohexadienyl radical as an intermediate. This radical in pulse radiolysis has a wide absorption band in the 310-390 nm wavelength range with a maximum at 350 nm. Cyclohexadienyl radical reacts with dissolved O2 with a rate coefficient of ∼ 4 × 10(8) mol(-1) dm(3) s(-1) forming peroxy radical. The latter may eliminate HO2 (•) giving phenols or undergoes fragmentation. The one-electron oxidant (•)OH on average induces more than two-electron oxidations. The toxicity first increases with absorbed dose, then decreases. This increase is partly due to phenols formed during the first degradation period.