Hydroperoxides, linoleic acid

In contrast to numerous literature data, which indicate that protein oxidation, as a rule, precedes lipid peroxidation, Parinandi et al. [66] found that the modification of proteins in rat myocardial membranes exposed to prooxidants (ferrous ion/ascorbate, cupric ion/tert-butyl-hydroperoxide, linoleic acid hydroperoxide, and soybean lipoxygenase) accompanied lipid peroxidation initiated by these prooxidant systems. 

Effects of linoleic acid and linoleic acid hydroperoxides on the myofibrils and the solutions of myofibrillar proteins of cod muscle have been proved using the electron microscopy (80). Linoleic acid hydroperoxides were ten times more effective than linoleic acid in reducing the amount of the protein in KCl-extracts from the myofibrils incubated with the acid or its hydroperoxides. Linoleic acid seemed to prevent the dissolution of the myofibril frame work but appeared not to impair the extraction of myosin while hydroperoxides appeared to cause a retention of A-bands (myosin) in the myofibrils. 

Lipoxygenase-Catalyzed Oxidations. Lipoxygenase-1 catalyzes the incorporation of dioxygen into polyunsaturated fatty acids possessing a l(Z),4(Z)-pentadienyi moiety to yield ( ),(Z)-conjugated hydroperoxides. A highly active preparation of the enzyme from soybean is commercially available in purified form. From a practical standpoint it is important to mention that the substrate does not need to be in solution to undergo the oxidation. Indeed, the treatment of 28 g/L of linoleic acid [60-33-3] with 2 mg of the enzyme results in (135)-hydroperoxide of linoleic acid in 80% yield... 

Lipid hydroperoxides are either formed in an autocatalytic process initiated by hydroxyl radicals or they are formed photochemically. Lipid hydroperoxides, known as the primary lipid oxidation products, are tasteless and odourless, but may be cleaved into the so-called secondary lipid oxidation products by heat or by metal ion catalysis. This transformation of hydroperoxides to secondary lipid oxidation products can thus be seen during chill storage of pork (Nielsen et al, 1997). The secondary lipid oxidation products, like hexanal from linoleic acid, are volatile and provide precooked meats, dried milk products and used frying oil with characteristic off-flavours (Shahidi and Pegg, 1994). They may further react with proteins forming fluorescent protein derivatives derived from initially formed Schiff bases (Tappel, 1956). 

Garssen, G.J., Vliegenthart, J.F.G. and Boldingh, J. (1972). The origin and structures of dimeric fetty acids from the anaerobic reaction between soya-bean lipoxygenase, linoleic acid and its hydroperoxide. Biochem. J. 130, 435-442. 

Reaction yields depend on the nature of the substrate. Linseed oil contains two polyunsaturated fatty acids 50% linolenic acid and 18% linoleic acid. The corresponding hydroperoxides are obtained with low yields. 

Yeum, K. J., Y. C. Leekim et al. (1995). Similar metabolites formed from beta-carotene by human gastric-mucosal homogenates, lipoxygenase, or linoleic acid hydroperoxide. Arch. Biochem. Biophys. 321(1) 167-174. 

Figure 10.7 Autoxidation of a linoleic acid ester. In step 1 the reaction is initiated by the attack of a radical on one of the hydrogen atoms of the -CH2-group between the two double bonds this hydrogen abstraction produces a radical that is a resonance hybrid. In step 2 this radical reacts with oxygen in the first of two chain-propagating steps to produce an oxygen-containing radical, which in step 3 can abstract a hydrogen from another molecule of the linoleic ester (Lin-H). The result of this second chain-propagating step is the formation of a hydroperoxide and a radical (Lin ) that can bring about a repetition of step 2.

Potato LOX has the potential to be used as an alternative model to the mammalian enzyme because of its great availability(Lopez-Nicolas and others 2000). To date, three isoenzymes of potato LOX have been isolated. Several works have reported linoleic acid as the optimum substrate for potato LOX-1, 9-hydroperoxide being the main product of the reaction. Another LOX substrate, linolenic acid, has been reported as the preferred substrate for both potato LOX-2 and -3, which produce 13-hydroperoxide as the main product. 

Inhibition and stimulation of LOX activity occurs as a rule by a free radical mechanism. Riendeau et al. [8] showed that hydroperoxide activation of 5-LOX is product-specific and can be stimulated by 5-HPETE and hydrogen peroxide. NADPH, FAD, Fe2+ ions, and Fe3+(EDTA) complex markedly increased the formation of oxidized products while NADH and 5-HETE were inhibitory. Jones et al. [9] also demonstrated that another hydroperoxide 13(5)-hydroperoxy-9,ll( , Z)-octadecadienoic acid (13-HPOD) (formed by the oxidation of linoleic acid by soybean LOX) activated the inactive ferrous form of the enzyme. These authors suggested that 13-HPOD attached to LOX and affected its activation through the formation of a protein radical. Werz et al. [10] showed that reactive oxygen species produced by xanthine oxidase, granulocytes, or mitochondria activated 5-LOX in the Epstein Barr virus-transformed B-lymphocytes. 

Exposure of cardiolipin to oxygen gas resulted in a substantial loss of the lipid and most of the degradation products were hydroperoxide derivatives. Even though we have not done the comparative experiment, our experience tells us that cardiolipin is more sensitive to oxidative stress than free linoleic acid or trilinolein. Taking into account that mitochondria is the site where reactive oxygen species are often produced, we propose that peroxidation of cardiolipin may easily take place once the intracellular oxidative stress occurs. 

The most active diaryl telluride, bis(4-aminophenyl)telluride, demonstrated 348%, 530%, 995% and 900% of the catalytic activity of ebselen for the glutathione-dependent reduction of H2O2, f-butylhydroperoxide (TBH), cumene hydroperoxide and linoleic acid peroxide, respectively. ... 

The crosslinking process is different depending on whether the unsaturation is an unconjugated double bond as in oleic acid or a conjugated double bond as in linoleic acid. Unconjugated double bonds undergo crosslinking by the initial formation of an allylic hydroperoxide... 

RP-HPLC with nonaqueous solvents and UVD at 246 nm was developed for the determination of low level POVs of vegetable oils. These measurements are specific for conjugated diene peroxides derived from vegetable oils with relatively high linoleic acid content. These measurements may be supplemented by nonspecific UVD at 210 nm and ELSD for detection of all eluted species. The elution sequence of the triglycerides in a nonaqueous RP-HPLC is linearly dependent on the partition number of each species, Vp, which is defined as = Nq — 2Ni, where Nq is the carbon number and is the double bond number. In the case of hydroperoxides = Nq — 2Nd — Vhpo, where Vhpo is the number of hydroperoxyl groups in the molecule (usually 1 for incipient POV). For... 

CZE-ELD, with a An microelectrode at —0.6 V vs. SCSE and a Pt wire as auxiliary electrode, using sodium borate buffer and dodecyltrimethylammonium bromide for dynamic coating of the capillary internal surface, can be applied for separation and determination of hydroperoxides in ultra-trace amounts. Thus, various hydroperoxides derived from linoleic acid undergo total dissociation to carboxylates in borate buffer however, due to their similar molecular masses, in order to resolve the ELD signals, it is necessary to add /3 -cyclodextrin (83) to form complexes with the analytes and reduce their mobility, in accordance with the value of the complexation equilibrium constants . 

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