Oxidative-degradation system

Azobisnittiles are efficient sources of free radicals for vinyl polymerizations and chain reactions, eg, chlorinations (see Initiators). These compounds decompose in a variety of solvents at nearly first-order rates to give free radicals with no evidence of induced chain decomposition. They can be used in bulk, solution, and suspension polymerizations, and because no oxygenated residues are produced, they are suitable for use in pigmented or dyed systems that may be susceptible to oxidative degradation. 

The oxidative degradation of organic pollutants in water and air streams is considered as one of the so-called advanced oxidation processes. Photocatalytic decomposition of organics found widespread industrial interest for air purification (e.g., decomposition of aldehydes, removal of NO , ), deodorization, sterilization, and disinfection. Domestic applications based on Ti02 photocatalysts such as window self-cleaning, bathroom paints that work under illumination with room light, or filters for air conditioners operating under UV lamp illumination have already been commercialized. Literature-based information on the multidisciplinary field of photocatalytic anti-pollutant systems can be found in a number of publications, such as Bahnemann s [237, 238] (and references therein). 

The decompositions of hydroperoxides (reactions 4 and 5) that occur as a uni-or bimolecular process are the most important reactions leading to the oxidative degradation (reactions 4 and 5). The bimolecular reaction (reaction 5) takes place some time after the unimolecular initiation (reaction 4) provided that a sufficiently high concentration of hydroperoxides accumulates. In the case of oxidation in a condensed system of a solid polymer with restricted diffusional mobility of respective segments, where hydroperoxides are spread around the initial initiation site, the predominating mode of initiation of free radical oxidation is bimolecular decomposition of hydroperoxides. 

Beunink J, Rehm HJ (1990) Coupled reductive and oxidative degradation of 4-chloro-2-nitrophenol by a co-immobilized mixed culture system. Appl Microbiol Biotechnol 34 108-115... 

FIGURE 9 Oxidative degradation of dictyotene by TPPMn/Ph-I==0. Compounds 1-14 are isolated products of an oxidative degradation of dictyotene by a radical pathway induced by the system TPPMn/Ph-I=0. Most of these compounds are present among the oxygenated derivatives of dictyotene from natural sources (cf. Figure 8). 

The oxidative degradations of binuclear azaarenes (quinoline, isoquinoline, and benzodrazines) by hydroxyl and sulfate radicals and halogen radicals have been studied under both photochemical and dark-reaction conditions. A shift from oxidation of the benzene moiety to the pyridine moiety was observed in the quinoline and isoquinoline systems upon changing the reaction from the dark to photochemical conditions. The results were interpreted using frontier-orbital calculations. The reaction of OH with the dye 3,3,6,6-tetramethyl-3,4,6,7,9,10-hexahydro-(l,8)(2//,5//)-acridinedione has been studied, and the transient absorption bands assigned in neutral solution.The redox potential (and also the pA a of the transient species) was determined. Hydroxyl radicals have been found to react with thioanisole via both electron transfer to give radical cations (73%) and OH-adduct formation (23%). The bimolec-ular rate constant was determined (3.5 x lO lmoU s ). " ... 

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