Conjugated hydroperoxy fatty acid

The primary LOX metabolites, the hydroperoxy fatty acids, are further metabolized to an array of secondary products that may be classified into several groups according to their chemical structures (i) leukotrienes containing three conjugated double bonds, (ii) mono- and double-oxygenated polyenoic fatty acids that are not formed via a leukotriene intermediate and (iii) lipoxins and hepoxilins. 

LOXs catalyse the addition of dioxygen to methyl-interrupted cis double bond [(Z,Z)-pentadiene] in a polyunsaturated fatty acid to produce a hydroperoxy fatty acid containing a Z,E conjugated double bond system. Where multiple pentadienes occur in a single molecule such as arachidonic acid, position-specific oxygenation can take place, resulting in the production of 5-, 12- or 15-hydroperoxyeicosa-tetraenoic acids. These hydroperoxy acids may be subsequently converted into other oxylipins by enzymic or non-enzymic reactions [3]. Table 1 shows some examples of LOX products from fungi. 

Fig. 6. Three irnportam oxidative pathways for the metabolism of polyunsaturated fatty acids. A. The principal steps in the formation of prostaglandin endoperoxides from arachidonic acid. B. Likely mechanism for the formation of hydroperoxy cis.trans conjugated fatly acids by autooxidalion or by lipoxygena.sc.s. In the latter case, positional as well as stereospecificity arc normally found. The formed hydroperoxides may then be enzymatically transformed into leukotrienes (not shown) or to hydroxy acids. C. The enzymatic sequence in cytochrome P-450 mediated oxygenation. The first electron is donated from NADPH via the f lavoprotein (Fp) NADPH-cytochrome-P-450-reductase. while the second electron comes either from NADPH or NADH. In this way the monooxygenase enzymes inlrrxluce one oxygen from air into the substrate.

Peroxidation (lipoxygenase- catalyzed) Free fatty acid (C ) Hydroperoxy acid (C ) (conjugated) Oxygenated acids (C ) and various fragmentation products 0,... 

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