Oxidation in oil model systems

Chelation of metals by certain compounds decreases their prooxidant effect by reducing then-redox potential and stabilizing the oxidizing form of the metal. A few natural acids (citric, phosphoric, tartaric, oxalic, etc.) and ethylenediamintetraacetic acid (EDTA) can chelate metals and thereby increase oxidation stability in oil model systems. ... 

Chemical Antioxidant Systems. The antioxidant activity of tea extracts and tea polyphenols have been determined using in vitro model systems which are based on hydroxyl-, peroxyl-, superoxide-, hydrogen peroxide-, and oxygen-induced oxidation reactions (109—113). The effectiveness of purified tea polyphenols and cmde tea extracts as antioxidants against the autoxidation of fats has been studied using the standard Rancimat system, an assay based on air oxidation of fats or oils. A direct correlation between the antioxidant index of a tea extract and the concentration of epigallocatechin gallate in the extract was found (107). 

K. Taguchi, K. Iwami, M. Kawabata, and F. Ibuki, Antioxidant effects of wheat gliadin and hen s egg white in powder model systems protection against oxidative deterioration of safflower oil and sardine oil, Agric. Biol. Chem., 1988, 52, 539-545. 

Further work at EniTecnologies was conducted with Rhodococcus strains. Rhodococ-cus was selected for its metabolical versatility, easy availability in soils and water, and remarkable solvent tolerance. Its capabilities for catalyzing diverse transformation reactions of crude oils, such as sulfur removal, alkanes and aromatics oxidation and catabolism caught their attention. Hence, genetic tools for the engineering of Rhodococcus strains have been applied to improve its biotransformation performance and its tolerance to certain common contaminants of the crude oil, such as cadmium. The development of active biomolecules led to the isolation and characterization of plasmid vectors and promoters. Strains have been constructed in which the careful over-expression of selected components of the desulfurization pathway leads to the enhancement of the sulfur removal activity in model systems. Rhodococcus, Gordona, and Nocardia were transformed in this way trying to improve their catalytic performance in BDS. In a... 

Another SIMS study on model systems concerns molybdenum sulfide catalysts. The removal of sulfur from heavy oil fractions is carried out over molybdenum catalysts promoted with cobalt or nickel, in processes called hydrodesulfurization (HDS) [17]. Catalysts are prepared in the oxidic state but have to be sulfided in a mixture of H2S and H2 in order to be active. SIMS sensitively reveals the conversion of Mo03 into MoSi, in model systems of MoCf supported on a thin layer of Si02 [21]. 

The bulk of our knowledge regarding thermal oxidation has been derived from studies with model systems of fatty acids and their derivatives, or with individual natural oils (2,3,6,12,13,14,15,16). However, in biological systems as complex as food, lipids usually exist in a complicated environment markedly different from that of the single phase model system. In cell membranes, for example, the lipid molecules are highly ordered, relatively restricted in distance and mobility, and closely associated with different neighboring molecules, e.g., other lipids, protein, cholesterol, water, pro- and antioxidants. What influence does such an environment have on the oxidation of the lipids at elevated temperature Even in less organized systems, e.g., depot fat from animal or plant, the lipids... 

Volatile compounds generated by model systems of zeln, corn amylopectin and corn oil extruded at barrel temepratures of 120°C and 165°C were analyzed by GC and GC/MS. The largest quantities of lipid oxidation products were detected in systems containing all three components. In each system, the quantity of 2,4-deca-dienal was low relative to the quantities of hexanal, heptanal and benzaldehyde. Identification of the Maillard reaction products, 2-methyl-3(or 6)-pentyl-pyrazine, 2-methyl-3(or 6)-hexylpyrazine and 2,5-di-methyl-3-pentylpyrazine, suggested that lipid-derived aldehydes might be involved in the formation of substituted pyrazines. 4-Methylthiazole was identified as a major decomposition product of thiamin when corn meal containing 0.5% thiamin was extruded at a final temperature of 180°C. 

Farag, R.S., Osman, S.A., Hallabo, S.A.S., Nasr, A.A. 1978. Linoleic acid oxidation catalysed by various amino acids and cupric ions in freeze-dried model systems. J. Am. Oil Chem. Soc. 55, 703-710. 

Similarly, the reduction half-cell of the model has been constructed. In the latter system (Figure 6B) the electron acceptor dimethyl-4,4 -bipyridinium (methylvlologen, MV2+) and Ru(bipy)5 ( or the water soluble Zn-porphyrins (3) and (4) were dissolwd in the aqueous phase of the water-S-oil micro-emulsion with the electron donor, thlophenol, being concentrated at the water-oil interface. Illumination of this system results in the production of the viologen radical cation. This photosensitized electron transfer process results in the separation of the reduced photoproduct, M, from the oxidized product, diphenyldisul-flde, which is in the toluene phase. 

Recent studies on salmon flavors revealed that a single compound appears to be responsible for the characterizing cooked salmon flavor (39). The cooked salmon flavor compound was found to have an extremely low threshold, and was Initially detected only by odor assessment of a fraction eluting at Ig of 9.6-9.7 on a Carbowax 20M packed column when headspace volatiles were analyzed from canned salmon meat. Accelerated oxidation of salmon oil did not yield salmon-llke aromas before the development of fishy oxidized aromas. However, when salmon oil was coated onto Cellte supports, and allowed to oxidize at room temperature, a distinct salmon-loaf-llke aroma developed within 24 h after Initiation of oxidation. A variety of supports were evaluated In model systems with salmon oil for their ability to produce the salmon aroma compound. Odor assessments of the oxidizing systems Table II Indicated that a range of odors developed from salmon-loaf-llke to oxidized fishy aromas, and only the Cellte system provided the aroma. 

Drug delivery from LLC phases of oligo(ethylene oxide)-alkyl ether (i.e., (E0) -0-alkyl) surfactants have also been explored but to a much lesser extent than GMO. For example, the L, Qn, and Hu phases of commercial Brij-96 surfactant (i.e., (EO)io-O-oleyl) (Fig. 18) formed with water and other additives, have been explored for release of ephedrine hydrochloride, tenoxi-cam [145], and topical dermal delivery of benzocaine [146]. Work in this area has found that the amount of water swelling the hydrophilic domains of the LLC phase increases drug diffusion and release [145]. In addition to this work, the L phase of the (EO)2i-0-stearyl/oil/water system has been explored for dermal delivery of itraconazole [147] and the L and Hi phases of the (E0)7-0-Ci3 i5 (i.e., Symperonic A7)/water system have been explored for the release of the model drug chlorhexidine diacetate [148]. 

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