Photooxidative free-radical

Products of photooxidation free radicals, unsaturations, caibonyl groups, Itydroperoxides, chain scissions... 

Fig. 6. The initial degradation pathway for thermooxidation and photooxidation. The free radical X is generated by the effect of heat or light on impurities,...

Polyamides, like other macromolecules, degrade as a result of mechanical stress either in the melt phase, in solution, or in the soHd state (124). Degradation in the fluid state is usually detected via a change in viscosity or molecular weight distribution (125). However, in the soHd state it is possible to observe the free radicals formed as a result of polymer chains breaking under the appHed stress. If the polymer is protected from oxygen, then alkyl radicals can be observed (126). However, if the sample is exposed to air then the radicals react with oxygen in a manner similar to thermo- and photooxidation. These reactions lead to the formation of microcracks, embrittlement, and fracture, which can eventually result in failure of the fiber, film, or plastic article. 

Initiation by light accelerates oxidation due to the photochemical generation of free radicals, which was noticed by Backstrom [16] and repeated by many others [9,11 — 13], The quantum yield (photooxidation products is sufficiently higher than unity. Here are several examples [12]. 

To perform the dissociation of the hydrocarbon to alkyl radicals with C—C bond scission, a hydrocarbon molecule should absorb light with the wavelength 270-370 nm. However, alkanes do not absorb light with such wavelength. Therefore, photosensitizers are used for free radical initiation in hydrocarbons. Mercury vapor has been used as a sensitizer for the generation of free radicals in the oxidized hydrocarbon [206-212], Nalbandyan [212-214] was the first to study the photooxidation of methane, ethane, and propane using Hg vapor as photosensitizer. Hydroperoxide was isolated as the product of propane oxidation at room temperature. The quantum yield of hydroperoxide was found to be >2, that is, oxidation occurs with short chains. The following scheme of propane photoxidation was proposed [117] ... 

Photooxidation of poly(styrene) has been a subject of considerable interest over the past 25 years (14,15). However, the surface photooxidation of poly(styrene), the aspects of which are most pertinent to the proposed photooxidative scheme, has only been examined recently (16,17). Free radical intermediates have been proposed to account for the formation of oxidized groups upon 254 nm irradiation of poly(styrene). 

Photolytic. When synthetic air containing gaseous nitrous acid and 4-methyl-2-pentanone was exposed to artificial sunlight k = 300-450 nm), photooxidation products identified were acetone, peroxyacetal nitrate, and methyl nitrate (Cox et al, 1980). In a subsequent experiment, the OH-initiated photooxidation of 4-methyl-2-pentanone in a smog chamber produced acetone (90% yield) and peroxyacetal nitrate (Cox et al, 1981). Irradiation at 3130 A resulted in the formation of acetone, propyldiene, and free radicals (Calvert and Pitts, 1966). 

A photooxidative reaction in which molecular oxygen is incorporated into the reaction products(s). Three mechanisms appear to be common for such processes (a) reaction of triplet O2 with free radicals that have been generated photochemically (b) reaction of photochemically produced singlet oxygen with a molecular species and (c) the production of superoxide anion which then acts as the reactive species. See also Photooxidation... 

Temperature control has an additional advantage with respect to the problem of chamber contamination. After a smog chamber has been used, some hydrocarbons and nitrogen compounds may remain adsorbed on the chamber walls. These may desorb in subsequent runs and, in some cases (e.g., HCHO), act as free radical sources to accelerate the photooxidation processes. The ability to bake out smog chambers while pumping to low pressures is therefore useful in reducing chamber contamination effects. 

There are a number of reports in the literature on the photochemistry of amides, including the photodegradation of serum albumin,224 and of polypeptides.1 Photodegradation involves reactions of acyl and imine free radicals generated by photolytic scission of the amide group.23 33 The photooxidation of N-pentylhexanamide led to the formation of n-valeraldehyde and valeric acid from the amine part of the molecule... 

This process continually generates lipid free radicals. The formation of nonradical products resulting from the combination of two radical species can terminate this chain reaction or propagation. Alternatively, unsaturated lipids can form hydroperoxides by reacting with singlet oxygen produced by sensitized photooxidation, which is a non-free-radical process. 

Photooxidation of Chlorophyll Generates a Cationic Free Radical... 

Previous work in our laboratory (3) and in others (4) has established that the primary photoprocess in a variety of excited carbanions involves electron ejection. This photooxidation will generate a reactive free radical if recapture of the electron is inhibited. Parallel generation of these same carbon radicals by electrochemical oxidation reveals an irreversible anodic wave, consistent with rapid chemical reaction by the oxidized organic species (5). Little chemical characterization of the products has been attempted, however (6). 

The photoimaging process occurs via a photooxidation process photo-initiated by residual transition metal impurities in the presence of oxygen and terminated by coupling of polymer-bound radicals. Photoinduced cross-linking thus requires generation of a critical, and large, concentration of free radicals. 

The Photo-oxidation of Methoxy Substituted Phenols. As we are now aware of the fact that there are several routes to form phenols in the chemical reactions of lignin, we have looked into the nature of free radical induced photooxidation of phenols (IS). There is no doubt that photolysis of methoxy phenols in solutions or in solid state produces yellow products. Molecular oxygen has often been shown to be a necessary reactant in the oxidation, although the radical nature of the mechanism is not understood (16). 

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