Enzyme-catalyzed lipid oxidation

It follows from the above that MPO may catalyze the formation of chlorinated products in media containing chloride ions. Recently, Hazen et al. [172] have shown that the same enzyme catalyzes lipid peroxidation and protein nitration in media containing physiologically relevant levels of nitrite ions. It was found that the interaction of activated monocytes with LDL in the presence of nitrite ions resulted in the nitration of apolipoprotein B-100 tyrosine residues and the generation of lipid peroxidation products 9-hydroxy-10,12-octadecadienoate and 9-hydroxy-10,12-octadecadienoic acid. In this case there might be two mechanisms of MPO catalytic activity. At low rates of nitric oxide flux, the process was inhibited by catalase and MPO inhibitors but not SOD, suggesting the MPO initiation. 

The ready oxidation of ascorbic acid will catalyze chemical changes in a number of other substances. Thus, unsaturated fatty acids in lecithins and tissues are catalytically oxidized in the presence of ascorbic acid to a substance producing color with thiobarbiturate (B21). The product of the ascorbic acid-catalyzed oxidation is malonaldehyde, which can also inhibit L-gulonolactone oxidase, the enzyme forming ascorbic acid (Cl). It has been suggested that this enzyme inhibition may occur in vivo in animals deficient in vitamin E, a compound believed to have antioxidant actions which would prevent the ascorbic acid-catalyzed lipid oxidation from giving rise to malonaldehyde. It is quite probable that the active intermediate in the formation of malonaldehyde is the monodehydroascorbate radical which initiates the lipid oxidation. 

Interestingly, early examples of carotenoid autoxidation in the literature described the influence of lipids and other antioxidants on the autoxidation of carotenoids." " In a stndy by Budowski et al.," the influence of fat was fonnd to be prooxidant. The oxidation of carotenoids was probably not only cansed by molecnlar oxygen bnt also by lipid oxidation products. This now well-known phenomenon called co-oxidation has been stndied in lipid solntions, in aqueons solntions catalyzed by enzymes," and even in food systems in relation to carotenoid oxida-tion." The inflnence of a-tocopherol on the antoxidation of carotenoids was also stndied by Takahashi et al. ° who showed that carotene oxidation was snppressed as... 

The mechanism of LOX-catalyzed LDL oxidation is still not clearly understood [31]. On one hand, it has been proposed that LDL oxidation may be initiated by oxygen radicals, which are released from the active site of the enzyme. On the other hand, the formation of lipid peroxide by direct oxygenation of unsaturated acids without the participation of free... 

The ALDs are a subset of the superfamily of medium-chain dehydrogenases/reductases (MDR). They are widely distributed, cytosolic, zinc-containing enzymes that utilize the pyridine nucleotide [NAD(P)+] as the catalytic cofactor to reversibly catalyze the oxidation of alcohols to aldehydes in a variety of substrates. Both endobiotic and xenobiotic alcohols can serve as substrates. Examples include (72) ethanol, retinol, other aliphatic alcohols, lipid peroxidation products, and hydroxysteroids (73). 

Food flavor is governed by many factors, including lipid oxidation and protein degradation. Enzyme-catalyzed oxidation ( ) and autoxidation (2) can substantially alter the flavor q ality of foods. In "addition, protein degradation, whether caused by enzymes, heat, or interactions with other compounds, can also affect flavor characteristics of certain foods (3, 4, ... 

Compounds such as superoxide anion and peroxides do not directly interact with lipids to initiate oxidation they interact with metals or oxygen to form reactive species. Superoxide anion is produced by the addition of an electron to the molecular oxygen. It participates in oxidative reactions because it can maintain transition metals in their active reduced state, can promote the release of metals that are bound to proteins, and can form the conjugated acid, perhydroxyl radical depending on pH, which is a catalyst of lipid oxidation (39). The enzyme superoxide dismu-tase that is found in tissues catalyzes the conversion of superoxide anion to hydrogen peroxide. 

Stmctured lipids possessing n-3 PUFAs, such as EPA and DHA, located at mid position, with MCFAs at the end positions, have gained considerable attention as nutritional and health supplements. These TAGs provide rapid delivery of energy via oxidation of the MCFAs and, at the same time, supply metabolically functional fatty acids in the same molecule. Senanayake and Shahidi (51) used an immobilized in-1,3-specific lipase from Mucor miehei to incorporate capric acid into seal blubber oil containing EPA and DHA. On enzyme-catalyzed acidolysis, a stmctured lipid containing 27.1% capric acid, 2.3% EPA, and 7.6% DHA was achieved. Lipase from Mucor miehei incorporated capric acid predominantly at the in-1,3 positions of the stmctured lipid. 

Lipid oxidation. Lipid oxidation is normally observed as a product discoloration and can be exacerbated with excess levels of bleach. It is catalyzed by metal ions, enzymes, and pigments. Acidic compounds can be used to complex the metal ions. Synthetic antioxidants, such as butylated hydroxtoluene (BHT) and butylated hydroxyanisole (BHA) can be added to the product, but are limited and coming under increased scrutiny due to toxicology concerns. It may be preferable to use natural antioxidants such as lecithin or vitamin E or to dry under vacuum or in an inert (nitrogen, steam) atmosphere. 

Several mechanisms of antioxidant action have been proposed. The presence of antioxidants may result in the decreased formation of the reactive oxygen and nitrogen species in the first place. Antioxidants may also scavenge the reactive species or their precursors. Vitamin E is an example of this latter behavior in its inhibition of lipid oxidation by reaction with radical intermediates generated from polyunsaturated fatty acids. Some antioxidants can bind the metal ions needed to catalyze the formation of the reactive oxidants. Other antioxidants can repair oxidative damage to biomolecules or can influence enzymes that catalyze repair mechanisms. 

Riisch gen. Klaas, M. Warwel, S. Lipase-catalyzed peroxy fatty acid generation and lipid oxidation. In Enzymes in Lipid Modification, Bornscheuer, U.T., Ed. Wiley-VCH Weinheim, Germany, 2000 116-127. 

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