Conjugated chains reaction

In the study of conjugated processes, of special attention are works by Emanuel [5], who has considered conjugated chain reactions to be of great importance and promising directions of radical reactions. Emanuel et al. have implemented detailed studies in this area. In particular, they suggested an effective method of propylene and acetaldehyde conjugated oxidation [6] for a one-stage synthesis of propylene oxide and acetic acid [7],... 

Bleaching and decolorization can occur by destroying one or more of the double bonds in the conjugated chain, by cleaving the conjugated chain, or by oxidation of one of the other moieties in the conjugated chain. The result of any one of the three reactions is an increase in the energy gap between the... 

Addition polymerization requires a chain reaction in which one monomer molecule adds to a second, then a third and so on to form a macromolecule. Addition polymerization monomers are mainly low molecular-weight olefinic compounds (e.g., ethylene or styrene) or conjugated diolefins (e.g., hutadiene or isoprene). 

Synthetic polymers can be classified as either chain-growth polymen or step-growth polymers. Chain-growth polymers are prepared by chain-reaction polymerization of vinyl monomers in the presence of a radical, an anion, or a cation initiator. Radical polymerization is sometimes used, but alkenes such as 2-methylpropene that have electron-donating substituents on the double bond polymerize easily by a cationic route through carbocation intermediates. Similarly, monomers such as methyl -cyanoacrylate that have electron-withdrawing substituents on the double bond polymerize by an anionic, conjugate addition pathway. 

Taking into account that ROS produced by irradiated fullerenes C60 may act only in the radius of their short diffusion existence, one may suppose that cytotoxic effect is determined by the interaction of fullerene C60 with the surface of cells and initiation of chain reactions of free radical peroxidation in membranes. That is why the influence of photoexcited fullerene C60 on the course of LPO process was studied and evaluated by the content of generated primary (diene conjugates) and final (Schiff bases) products. The content of diene conjugates in thymocytes was 17.7 4.2, inEAC cells was 21.1 1.3, andinL1210 was 12.8 3.1 nM/mg protein, and Schiff bases -56 7.9,46.5 4.5, and 36.6 4.6 rel. units/mg protein, respectively, and did not alter during 1 h incubation of the cells. 

Mead s work (M8, P5, M4) with fatty-acids emulsions deserves attention. X rays initiate oxidative chain reactions in these systems as measured spectrophotometrically by the formation of a conjugated double bond. Some antioxidants when added to the system prevent this reaction and are themselves destroyed. 

This unexpected result may be related to the increase in TOC on fraction G3 and may be further evidence of the polymerization phenomenon discussed earlier. However, this hypothesis must be carefully considered because of our limited knowledge of pyrolysis mechanisms. The possibility of phenol formation during the thermal fragmentation process from elimination reactions followed by cycliza-tion of poly conjugated chains has been suggested by Bracewell (22) and should be investigated. 

The cyclopentadienyl radical, C-C5H5, undergoes an isomerization reaction in which the ring is broken, forming the conjugated chain radical (i.e., the reaction C-C5H5 — CH=CHCH=CHCH). 

Haase and Dunkley (1969B) reported that although high concentrations of ascorbic acid in model systems of potassium linoleate were prooxidant, a decrease in the rate of oxidation was observed. Haase and Dunkley (1969C) further noted that certain concentrations of ascorbic acid and copper inhibited the formation of conjugated dienes, but not the oxidation of ascorbic acid, and caused a rapid loss of part of the conjugated dienes already present in the system. They theorized that certain combination concentrations of ascorbic acid and copper inhibit oxidation by the formation of free radical inhibitors which terminate free- radical chain reactions, and that the inhibitors are complexes that include the free radicals. 

Figure 2-17. Lipid peroxidation. A hydroxyl radical abstracts a hydrogen from a fatty acid or lipid molecule. After rearrangement to a conjugated structure, the radical reacts with oxygen to form a peroxyl radical. The newly formed peroxyl radical can initiate a chain reaction whereby new peroxyl radicals are formed.

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