Antioxidants discussion

From chemical point of view, efficient free radical scavengers must contain substituents with the very weak C—H, O—H, or S—H bonds, from which reactive free radicals are able to abstract a hydrogen atom. It can be seen that the antioxidants discussed above (ascorbic acid, a-tocopherol, ubihydroquinones, glutathione, etc) fall under this category. However, many other compounds manifest free radical scavenging activity in in vitro and in vivo systems. 

Table 5 shows the maximum levels permitted by the FDA for the four major synthetic antioxidants (BHA, BHT, PG, and TBHQ) in specific applications (51). The regulatory status for these antioxidants in the USA, Canada, and Europe is given in Table 6 Table 7 summarizes their status in other countries for which a listing could be found. In addition to the major synthetic antioxidants discussed above (BHA, BHT, TBHQ, gallates, erythorbic acid, and ascorbyl palmitate), several other... 

As well as being excellent UV stabilisers for several polymer applications, there is ample evidence [31] to suggest that hindred amine light stabilisers can also operate as thermal antioxidants. Discussion of these additives will be undertaken in Chapter 8. 

The amine antioxidants discussed above have the problem that they discolor the rubber products. They are not suitable for products intended to be light colored. With the development of synthetic rubber in the 1930s and 1940s, which was initially white from its polymerization reactors, it became even more desirable to develop non-staining antioxidants [ 1 ]. Substances such as hydroquinone, resorcinol, 1-naphtol, and 2-naphthol had been claimed as antioxidants early in the century [6, 7]. By the 1940s tris(nonyl phenyl)phosphite (Polygard )... 

The exterior durabiHty of relatively stable coatings can be enhanced by use of additives. Ultraviolet absorbers reduce the absorption of uv by the resins and hence decrease the rate of photodegradation. Eurther improvements can be gained by also adding free-radical trap antioxidants (qv) such as hindered phenols and especially hindered amine light stabilizers (HALS). A discussion of various types of additives is available (113). 

Ultraviolet light absorbers will be discussed in more detail under another section. Suffice it to say that their incorporation into a polymer can provide a useful antioxidant function. 

When polyethylene is to be used in long-term applications where a low power factor is to be maintained and/or where it is desired to provide thermal protection during processing, antioxidants are incorporated into the polymers. These were discussed extensively in Chapter 7 but a few particular points with regard to their use in polyethylene should be made. Although amines have been used widely in the past phenols are now used almost exclusively. 

Further variations in the properties of polyethylenes may be achieved by incorporating additives. These include rubber, antioxidants and glass fibres and their effects will be discussed further in Section 11.1.4. 

Factors affecting laboratory polymerisation of the monomer have been discussed" and these indicate that a Ziegler-Natta catalyst system of violet TiCl3 and diethyl aluminium chloride should be used to react the monomer in a hydrocarbon diluent at atmospheric pressure and at 30-60°C. One of the aims is to get a relatively coarse slurry from which may be washed foreign material such as catalyst residues, using for example methyl alcohol. For commercial materials these washed polymers are then dried and compounded with an antioxidant and if required other additives such as pigments. 

Means to minimize processes 1 and 2 have already been discussed. Processes 3-5 can be minimized or at least delayed through the choice of suitable antioxidants. 

It has been proposed that the development of the complications of diabetes mellitus may be linked to oxidative stress and therefore might be attenuated by antioxidants such as vitamin E. Furthermore, it is discussed that glucose-induced vascular dysfunction in diabetes can be reduced by vitamin E treatment due to the inactivation of PKC. Cardiovascular complications are among the leading causes of death in diabetics. In addition, a postulated protective effect of vitamin E (antioxidants) on fasting plasma glucose in type 2 diabetic patients is also mentioned but could not be confirmed in a recently published triple-blind, placebo-controlled clinical trial [3]. To our knowledge, up to now no clinical intervention trials have tested directly whether vitamin E can ameliorate the complication of diabetes. 

In relation to consumer uses of possible concern for this CICAD, data from the Women s Environmental Network indicate that butyltin stabilizers have been detected in the non-woven polypropylene topsheet of babies nappies (diapers). It is possible that this could relate to the last of the three key uses described above, in that the topsheet could be of silicone-grafted polypropylene (or, as discussed below, the butyltin may be present because of its use as a catalyst in the production of an antioxidant in polyolefin films). 

Consequently, the antioxidant activity of GA in biological systems is still an unresolved issue, and therefore it requires a more direct knowledge of the antioxidant capacity of GA that can be obtained by in vitro experiments against different types of oxidant species. The total antioxidant activity of a compound or substance is associated with several processes that include the scavenging of free radical species (eg. HO, ROO ), ability to quench reactive excited states (triplet excited states and/ or oxygen singlet molecular 1O2), and/or sequester of metal ions (Fe2+, Cu2+) to avoid the formation of HO by Fenton type reactions. In the following sections, we will discuss the in vitro antioxidant capacity of GA for some of these processes. 

In addition to phenolic substances, there are other components present in foods which have no antioxidant activity of their own, but which increase that of phenolic antioxidants. They are called synergists, and they should be accounted for in any discussion of antioxidant activity. Polyvalent organic acids, amino acids, phospholipids (lecithin) and various chelating agents belong to this group. Proteins may modify the efficiency of antioxidants as they react with the reaction products of both antioxidants and synergists. 

Natural antioxidants may be classified according to their nutritive value or according to their solubility. The hydrophobic vitamin E and the hydrophilic vitamin C are thus important both as nutrients and as antioxidants. The nonnutritive antioxidants may similarly be divided into lipid-soluble and water-soluble antioxidants, as shown in Fig. 16.3, which will also form the basis for a discussion of exploitation of combinations of anhoxidants in order to improve protective effects. 

Knowledge of the identity of phenolic compounds in food facilitates the analysis and discussion of potential antioxidant effects. Thus studies of phenolic compounds as antioxidants in food should usually by accompanied by the identification and quantification of the phenols. Reversed-phase HPLC combined with UV-VIS or electrochemical detection is the most common method for quantification of individual flavonoids and phenolic acids in foods (Merken and Beecher, 2000 Mattila and Kumpulainen, 2002), whereas HPLC combined with mass spectrometry has been used for identification of phenolic compounds (Justesen et al, 1998). Normal-phase HPLC combined with mass spectrometry has been used to identify monomeric and dimeric proanthocyanidins (Lazarus et al, 1999). Flavonoids are usually quantified as aglycones by HPLC, and samples containing flavonoid glycosides are therefore hydrolysed before analysis (Nuutila et al, 2002). 

The ability of carotenoids to act as antioxidants is closely related to their long-chain conjugated polyene structures (see Section 2.2 in Chapter 2). Two main types of antioxidant actions can be distinguished singlet oxygen quenching and reactions with radicals. The first mechanism occurs in vivo in plants and has been extensively studied in vitro. Reactions with radicals of different types have also been extensively studied in vitro under different conditions but their occurrence in vivo is still a matter of discussion. 

This chapter addresses (1) the mechanisms, antioxidant defences and consequences in relation to free-radical production in the inflamed rheumatoid joint (2) lipid abnormalities in RA (3) the potential contribution of ox-LDL to RA (the role of ox-LDL in coronary heart disease is discussed in Chapters 2 and 3 and will not be fully discussed here) and (4) the therapeutic aspects of chain-breaking antioxidant interventions in RA. 

The efficient removal of O2 and H2O2 vvill diminish OH formation and therefore antioxidant defence systems have evolved to limit their accumulation. Enzymic and low molecular weight antioxidants exist to scavenge free radicals as self-protection mechanisms. Some proteins exhibit antioxidant properties because they chelate transition-metal catalysts. The significance of antioxidants in relation to inflammatory joint disease is discussed below. 

The importance of vitamin E for maintenance of lipid integrity in vivo is emphasized by the fact that it is the only major lipid-soluble chain-breaking antioxidant found within plasma, red cells and tissue cells. Esterbauer etal. (1991) have shown that the oxidation resistance of LDL increases proportionately with a-tocopherol concentration. In patients with RA, synovial fluid concentrations of a-tocopherol are significantly lower relative to paired serum samples (Fairburn et al., 1992). The low level of vitamin E within the inflamed joint implies it is being consumed via its role in terminating lipid peroxidation and this will be discussed further in Section 3.3. 

Esterbauer et al. (1991) have demonstrated that /3-carotene becomes an effective antioxidant after the depletion of vitamin E. Our studies of LDL isolated from matched rheumatoid serum and synovial fluid demonstrate a depletion of /8-carotene (Section 2.2.2.2). Oncley et al. (1952) stated that the progressive changes in the absorption spectra of LDL were correlated with the autooxidation of constituent fatty acids, the auto-oxidation being the most likely cause of carotenoid degradation. The observation that /3-carotene levels in synovial fluid LDL are lower than those of matched plasma LDL (Section 2.2.2) is interesting in that /3-carotene functions as the most effective antioxidant under conditions of low fOi (Burton and Traber, 1990). As discussed above (Section 2.1.3), the rheumatoid joint is both hypoxic and acidotic. We have also found that the concentration of vitamin E is markedly diminished in synovial fluid from inflamed joints when compared to matched plasma samples (Fairburn etal., 1992). This difference could not be accounted for by the lower concentrations of lipids and lipoproteins within synovial fluid. The low levels of both vitamin E and /3-carotene in rheumatoid synovial fluid are consistent with the consumption of lipid-soluble antioxidants within the arthritic joint due to their role in terminating the process of lipid peroxidation (Fairburn et al., 1992). 

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