Lipid reaction rate

If one could conclusively show that there is an effect of plasticizers on reaction rate that is independent of moisture content or a , then this would demonstrate the significance of matrix properties for governing reaction rate. Labuza et al. (1977) studied the Maillard reaction and measured the effects of several parameters. These included temperature, reactant concentration, pH, buffers, and the addition of humectants. The formulation consisted of glucose and casein as reactants within a carrier matrix of microcrystalline cellulose and an inert lipid. Reaction rate was measured both as glucose loss, lysine loss, and pigment production (A42o). 

Several compounds can be oxidized by peroxidases by a free radical mechanism. Among various substrates of peroxidases, L-tyrosine attracts a great interest as an important phenolic compound containing at 100 200 pmol 1 1 in plasma and cells, which can be involved in lipid and protein oxidation. In 1980, Ralston and Dunford [187] have shown that HRP Compound II oxidizes L-tyrosine and 3,5-diiodo-L-tyrosine with pH-dependent reaction rates. Ohtaki et al. [188] measured the rate constants for the reactions of hog thyroid peroxidase Compounds I and II with L-tyrosine (Table 22.1) and showed that Compound I was reduced directly to ferric enzyme. Thus, in this case the reaction of Compound I with L-tyrosine proceeds by two-electron mechanism. In subsequent work these authors have shown [189] that at physiological pH TPO catalyzed the two-electron oxidation not only L-tyrosine but also D-tyrosine, A -acetyltyrosinamide, and monoiodotyrosine, whereas diiodotyrosine was oxidized by a one-electron mechanism. 

In case of lipases, one of the simplest methods to combine an enzyme with an organic solvent is to coat the lipase with a lipid or surfactant layer before lyophilisation. It is estimated that about 150 surfactant molecules are sufficient for encapsulating one lipase molecule. Following this route the surfactant coated lipase forms reverse micelles with a minimum of water concentration. The modified lipases are soluble in most organic solvents, and the reaction rates are increased compared to the suspended hpases due to the interfacial activation [59,60]. 

Compared to the base-catalyzed synthesis of biodiesel, fewer studies have dealt with the subject of acid-catalyzed transesterification of lipid feedstocks. Among acid catalysts, sulfuric acid has been the most widely studied. In the previously mentioned work of Freedman et al., the authors examined the transesterification kinetics of soybean oil with butanol using sulfuric acid. The three reaction regimes observed (in accordance with reaction rate) for base-catalyzed reactions were also observed here. A large molar ratio of alcohol-to-oil, 30 1, was required in this system in order to carry out the reaction in a reasonable time. As expected, transesterification followed pseudo-first-order kinetics for the forward reactions (Figure 2), while reverse reactions showed second-order kinetics. 

Thirdly, the economy of the whole process seems to be very favourable. The tremendous reaction rate makes the reactor very small. The concentration of the substrate in the solvent ( i.e., the loading) is crucial, as in any other solvent-based process. Single-phase conditions have been achieved at a loading of 15 - 20 wt.% for different lipids at a total pressure of 150 bar [29,35]. This would allow a moderate solvent recirculation. Based on these results, a company has decided to build a pilot plant, which will be put into operation in Goteborg, Sweden, during the spring of 2001. 

Han P, Bartels DM (1994) Encounters of H and D atoms with 02 in water relative diffusion and reaction rates. In Gauduel Y, Rossky P (eds) AIP conference proceedings 298. "Ultrafast reaction dynamics and solvent effects." AIP Press, New York, 72 pp Hasegawa K, Patterson LK (1978) Pulse radiolysis studies in model lipid systems formation and behavior of peroxy radicals in fatty acids. Photochem Photobiol 28 817-823 Herdener M, Heigold S, Saran M, Bauer G (2000) Target cell-derived superoxide anions cause efficiency and selectivity of intercellular induction of apoptosis. Free Rad Biol Med 29 1260-1271 Hildenbrand K, Schulte-Frohlinde D (1997) Time-resolved EPR studies on the reaction rates of peroxyl radicals of polyfacrylic acid) and of calf thymus DNA with glutathione. Re-examination of a rate constant for DNA. Int J Radiat Biol 71 377-385 Howard JA (1978) Self-reactions of alkylperoxy radicals in solution (1). In Pryor WA(ed) Organic free radicals. ACS Symp Ser 69 413-432... 

A plausible interpretation of the interaction between residual moisture and microorganism stability can be drawn from the works of Labuza et al. [18]. Figure 7 shows the progression of the lipid oxidation rate as a function of water activity (a ). This parameter reflects the availability of water for chemical reactions within the product. Its value varies from 0 for an anhydrous product to 1 for pure... 

Reaction preferences in lipid oxidation have mostly been deduced from product analyses the few rate constants available for lipid reactions have been determined... 

During 1-h lipidation reaction, equilibrate the Hu-column by passing through ten volumes of cold binding buffer. Dilute lipidation reaction mixture tenfold with cold binding buffer and load it on Hu-column at a slow rate, not exceeding... 

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