Chain-breaking antioxidant effect

Other Physicochemical Aspects Associated to the Chain-Breaking Antioxidant Effect The Stability of the Polyphenol-Derived Free Radicals... 

It will be noticed that with chain-breaking antioxidants the additive will be consumed whilst if we assume that the AO2H molecule will regenerate A radicals the oxidation retarder is not effectively consumed. The difference between the two is illustrated schematically in Figure 7.4. 

In antioxidants, synergism appears to arise either from one antioxidant effectively regenerating another so that the latter does not become consumed or by the two antioxidants functioning by differing mechanisms. The latter is more important and it is easy to see how effective a combination of peroxide decomposer and chain-breaking antioxidant can be. 

The peroxide decomposer will drastically reduce the number of radicals, which can then be more effectively mopped up by the chain-breaking materials. A widely used combination is 4-methyl-2,6,di-t-butylphenol and dilauryl thiodipropionate. It is possible to envisage most powerful combinations where a chain-breaking antioxidant, a regenerating agent, a peroxide decomposer, a metal deactivator and an ultraviolet absorber are all employed together. 

Synergism can also arise from cooperative effects between mechanistically different classes of antioxidants, e.g., the chain breaking antioxidants and peroxide decomposers (heterosynergism) [42]. For example, the synergism between hindered phenols (CB—D) and phosphites or sulphides (PD) is particularly important in thermal oxidation (Table 2). Similarly, effective synergism is achieved between metal dithiolates (PD) and UV-ab-sorbers (e.g., UV 531), as well as between HALS and UV-absorbers, (Table 3). 

There has been some evidence of a higher antioxidant effect when both flavonoids and a-tocopherol are present in systems like LDL, low-density lipoproteins (Jia et al., 1998 Zhu et al, 1999). LDL will incorporate a-tocopherol, while flavonoids will be present on the outside in the aqueous surroundings. A similar distribution is to be expected for oil-in-water emulsion type foods. In the aqueous environment, the rate of the inhibition reaction for the flavonoid is low due to hydrogen bonding and the flavonoid will not behave as a chain-breaking antioxidant. Likewise, in beer, none of the polyphenols present in barley showed any protective effect on radical processes involved in beer staling, which is an oxidative process (Andersen et al, 2000). The polyphenols have, however, been found to act synergistically... 

In the water-like solvent tert-butyl alcohol, a-tocopherol was found to prevent lipid oxidation, showing a distinct lag-phase for oxygen consumption. This was in contrast to quercetin or epicatechin, which were only weak retarders of lipid oxidation without any clear antioxidative effect. Quercetin or epicatechin, when combined with a-tocopherol, increased the lag-phase for oxygen consumption as seen for a-tocopherol alone. The stoichiometric factor for a-tocopherol, a-TOH, as chain-breaking antioxidant has the value n = 2 according to the well-established mechanism ... 

Flavonoids are chain-breaking antioxidants in lipid-like solvents like chlorobenzene, although the k(inh) is smaller than for a-tocopherol and the lag-phase accordingly less evident. For peroxidating lipids in chlorobenzene the clear lag-phase for a-tocopherol became longer when quercetin or catechin were present. The effect appears to be additive and a regeneration of a-tocopherol by quercetin or catechin in this lipid-like solvent should rather be termed a co-antioxidative effect (Pedrielli and Skibsted, 2002). 

The potency of a chain-breaking antioxidant, which scavenges peroxyl radicals, will decrease as the concentration of lipid peroxides in the LDL particle increases (Scheme 2.2). This is illustrated in the experiment shown in Fig. 2.3 in which the antioxidant potency of a peroxyl radical scavenger (BHT) decreases as a function of added exogenous hpid hydroperoxide. If the endogenous lipid peroxide content of LDL were to vary between individuals, this could explain the observed diferences in the effectiveness of a-tocopherol in suppressing lipid peroxidation promoted by copper. 

Polymer stabilization is another area in which the peroxide-decomposing and chain-breaking antioxidant properties of diorganotellurides has found utUity. Alone or in combination with phenol and phosphate antioxidants, electron-rich dialkylamino-substirnted diaryltellurides and alkylaryltellurides provided greatly enhanced polymer stability for a thermoplastic elastomer and for polypropylene. The effects were unique to the tellurides, with selenides not providing similar protective effects. ... 

Polyphenols could act as effective chain-breaking antioxidants (AH = POH) through the one-electron transfer reactions 4 and 5 if they produce a stable and relatively nonreactive antioxidant radical (A = PO) [Jovanovic et al., 1994], Reactions 4 and 5 can be represented by the reaction 8, where L or LOO represents the oxidant free radical. This reaction can be decomposed in two half-reactions one reduction (reaction 9) and one oxidation (reaction 10) ... 

The lipid-soluble antioxidants present in the LDL particle are responsible for the LDL particle resistance to oxidation [3]. LDL copper-mediated oxidability in vitro, has been used by several researchers to evaluate oxidation resistance of LDL. LDL oxidation is evaluated by following in vitro copper-mediated oxidation of LDL [3,49]. Duration of the lag phase determines the resistance of LDL to oxidation and depends on the content of antioxidants in the LDL molecule. During the lag period, the alpha-tocopherol and other antioxidants are lost from LDLs. The length of the lag phase reflects the protective effects of chain-breaking antioxidants, especially alpha-tocopherol. When LDL particles, isolated from subjects who have consumed vitamin E supplements, or are enriched with vitamin E, the length of lag period is significantly increased [3]. 

The importance of the cyclical regeneration of nitroxide in the aromatic series seems to be therefore questionable N,N -di-substituted PD, most probably not involved in this cycle, are generally more efficient chain-breaking antioxidants than both diphenylamine and N-phenyl-1-naphthylamine, potentially partly involved in the nitoxide cycle. It may, therefore, be supposed that the high antioxidant activity of PD more probably accounts for the positive cooperative effects of PD with its principal oxidative transformation product, BQDI. 

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