Antioxidative properties, sulfur

Antioxidative properties, sulfur compounds in foods, 4 Aqueous washing, role in heat-induced changes of sulfhydryl groups of muscle foods, 174,1751... 

Natural rubber (NR) and guttapercha consist essentially of polyisoprene in cis-l, 4 and trans-1,4 isomers, respectively. Commercially produced synthetic polyisoprenes have more or less identical structure but reduced chain regularity, although some may contain certain proportions of 1,2- and 3,4-isomers. Microstructure differences not only cause the polymers to have different physical properties but also affect their response to radiation. The most apparent change in microstructure on irradiation is the decrease in unsaturation. It is further promoted by the addition of thiols and other compounds.130 On the other hand, antioxidants and sulfur were found to reduce the rate of decay of unsaturation.131 A significant loss in unsaturation was found, particularly in polyisoprenes composed primarily of 1,2- and 3,4-isomers.132,133... 

Certain enzymes present in grapes are responsible for wine problems such as clouding, darkening or an oxidized taste. To prevent this, wineries routinely treat must and wines with sulfur dioxide. In addition to its antimicrobial activity, SO2 has an antioxidative property which prevents browning and taste defects. Polyphenoloxidase has detrimental effects on wine quality. However enzymes are also responsable for the formation of certain desir able esters which are essential to the aroma or bouquet of the wine. 

Properties Pale yel. liq. m.w. 634 dens. 0.915 (25/15 C) m.p. 20 C ref. index 1.4985-1.5025 flash pt. (COC) 430 F Toxicoiogy TSCA listed Precaution Combustible Uses StabiIizer for polymers esp. polyolefins lubricant chemical intermediate antioxidant and sulfur deactivator in lubricants improves antiwear and antifriction props. 

Antioxidative Properties. When cooked meat is refrigerated, a rancid or stale flavor usually develops within 48 hrs. This character has been termed warmed-over flavor (WOF) and is generally attributed to the oxidation of lipids. Various synthetic and natural antioxidants have been used to reduce the development of WOF. Among the natural antioxidants used are the sulfur containing amino acid cysteine, and various Maillard reaction products. Eiserich and Shibamoto (Chapter 20) found that certain volatile sulfur heterocycles derived from Maillard reaction systems can function as antioxidants. 

These additional forms represent bound sulfur dioxide, or bound SO2 as it is defined in enology. The sum of free SO2 plus bound SO2 is equal to total SO2. With respect to free SO2, bound SO2 has much less significant (even insignificant), antiseptic and antioxidant properties (Section 8.6). 

Sulfur dioxide and ascorbic acid therefore have different antioxidant properties. The first has a delayed, but stable, effect which continues over time even in the presence of a subsequent oxygenation. It cannot prevent iron casse, which rapidly appears after an aeration. The second has an immediate effect it can instantaneously compensate the damage of an abrupt and intense aeration (iron casse), but it acts only as long as the wine is not in permanent contact with air. 

More recendy, molecular molybdenum-sulfur complexes and clusters have been used as soluble precursors for M0S2 in the formulation of lubricating oils for a variety of appHcations (70). Presumably, the oil-soluble molybdenum—sulfur-containing precursors decompose under shear, pressure, or temperature stress at the wear surface to give beneficial coatings. In several cases it has been shown that the soluble precursors are trifunctional in that they not only display antifriction properties, but have antiwear and antioxidant characteristics as weU. In most cases, the ligands for the Mo are of the 1,1-dithiolate type, including dithiocarbamates, dithiophosphates, and xanthates (55,71). 

Rubber. The mbber industry consumes finely ground metallic selenium and Selenac (selenium diethyl dithiocarbamate, R. T. Vanderbilt). Both are used with natural mbber and styrene—butadiene mbber (SBR) to increase the rate of vulcanization and improve the aging and mechanical properties of sulfudess and low sulfur stocks. Selenac is also used as an accelerator in butyl mbber and as an activator for other types of accelerators, eg, thiazoles (see Rubber chemicals). Selenium compounds are useflil as antioxidants (qv), uv stabilizers, (qv), bonding agents, carbon black activators, and polymerization additives. Selenac improves the adhesion of polyester fibers to mbber. 

This combination of monomers is unique in that the two are very different chemically, and in thek character in a polymer. Polybutadiene homopolymer has a low glass-transition temperature, remaining mbbery as low as —85° C, and is a very nonpolar substance with Htde resistance to hydrocarbon fluids such as oil or gasoline. Polyacrylonitrile, on the other hand, has a glass temperature of about 110°C, and is very polar and resistant to hydrocarbon fluids (see Acrylonitrile polymers). As a result, copolymerization of the two monomers at different ratios provides a wide choice of combinations of properties. In addition to providing the mbbery nature to the copolymer, butadiene also provides residual unsaturation, both in the main chain in the case of 1,4, or in a side chain in the case of 1,2 polymerization. This residual unsaturation is useful as a cure site for vulcanization by sulfur or by peroxides, but is also a weak point for chemical attack, such as oxidation, especially at elevated temperatures. As a result, all commercial NBR products contain small amounts ( 0.5-2.5%) of antioxidant to protect the polymer during its manufacture, storage, and use. 

Increase the rate of the cross-linking action with sulfur considerably allow for lower sulfur content to achieve optimum vulcanisate properties. Organic accelerators (e.g. thiuram, dithiocarbamate, etc.) are of major importance. In some cases it is necessary to retard the onset of vulcanisation to assure sufficient processing safety. The antioxidant 2-mercaptobenzimidazole (MBI) acts as a retarder for most accelerators. 

Garlic has been reported to have lipid- and blood-pressure-lowering properties, as well as antiplatelet, antioxidant, and fibrinolytic effects. In animal models and human cell cultures, it has been shown to have antiatherosclerotic activity (see Chapter 50). The sulfur-containing component, allicin, is considered to be the principal active ingredient of garlic, but several other bioactive ingredients have also been isolated. 

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