Hydroperoxide groups chemiluminescence

F. Gugumus [21] provides an alternative view of the thermal oxidation reactions in polymers. Various possibilities arising from inter- and intramolecular reactions between hydroperoxide groups, peroxy radicals, and alkoxy radicals are postulated. The author underlines the plausible over-estimation of degradation attributed to -scissions in polypropylene (PP) and offers alternative (non (3-scission) routes that result in formation of 1,2-dioxetane which can account for auto-oxidation, chain scissions and enhanced chemiluminescence of PP oxidation products. An illustration of this proposed scheme is provided in Scheme 6.4. 

The quality of the polymer, its photo-oxidation and thermo-oxidation history expressed in concentration of hydroperoxides, carbonyl groups or of other oxidized structures and terminal groups. The rate of an oxidative attack may then be related to the average molar mass and to its distribution, and to the ratio of amorphous/crystalline structures. Polymers cannot be simply ordered according to the intensity of light emission at a given temperature. The chemiluminescence-time patterns are related with the rate of sample oxidation, but they may differ from one to the next polymer. 

Provided that chemiluminescence intensity Iql is proportional to the rate of peroxyl radicals termination, that is Icl [PO ]2, which is often assumed in the literature, chemiluminescence intensity should achieve some quasi-stationary level when hydroperoxide concentration becomes stationary and its decay should correspond to consumption of oxidizable groups, PH, in a polymer. At the same time, the chemiluminometric curves of type (a), which are typical with an autoaccelerating increase of the light emission (Figure 4) are relevant for... 

The degradation process has a free radical mechanism. It is initiated by free radicals P that appear due to, for example, hydroperoxide decomposition induced thermally or by trace amounts of metal ions present in the polysaccharide. One cannot exclude even direct interaction of the polysaccharide with oxygen in its ground triplet state with biradical character. Hydroperoxidic and/or peracid moieties are easily formed by oxidation of semiacetal chain end groups. The sequence of reactions on carbon 6 of polysaccharide structural unit that ultimately may lead to chemiluminescence is shown in Scheme 11. 

The determination of lipid peroxides in lipids is an important issue, because lipid peroxides indicate that oils and fats can undergo oxidative deterioration. The methods for the determination of hydroperoxides present in lipids are based on the physical properties of the LOOH, for example, conjugated dienes, or on the chemical properties of the peroxide group, for example, PV. However, in some foods, the quantity of fats could be too low to apply the above-mentioned methods with accuracy. Chemiluminescence offers the sensitivity to overcome this problem. 

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