linoleic-acid and acetonitrile

We re-examined the antioxidative mechanism of allicin as a radical scavenger on the basis of the reactivity toward 2, 2-diphenyl-1-picrylhydrazyl (DPPH) and peroxyl radicals. Initially, it was found that allicin decomposed more rapidly in n-hexane and chlorobenzene than in acetonitrile, ethanol, and ethanol/water solutions and decomposed into ajoene and vinyldithiins in these solvents. Furthermore, the decomposition of allicin and the following formations of ajoene and vinyldithiins from allicin were accelerated by the reaction of allicin with DPPH and peroxyl radicals. These results show that 2-propenesulfenic acid, which arises by Cope elimination from allicin, is proposed to contribute to scavenge these radicals because ajoene and vinyldithiins were produced from allicin through the use of 2-propenesulfenic acid. Next, allicin was more effective at inhibiting the linoleic acid oxidation at 50 °C than at 30 °C and in cyclohexane than in acetonitrile. These results indicate that allicin decomposed rapidly at high temperatures in a hydrogen-bond-acceptor solution to 2-propenesulfenic acid. In addition, 2-propene-1-sulfinothionic acid S-methyl ester, which does not produce sulfenic acid through Cope elimination, has no activity against the radicals. On the other hand, methanesulfinothionic acid S-2-propenyl ester, which produces methanesulfenic acid through Cope elimination, has the same or increased activity as its allicin against the radicals. Based on these results, the Cope elimination product, sulfenic acid, from thiosulfinates with an α-sulfenyl proton was found to make a larger contribution to the radical scavenger than that of allicin itself.. We examined the antioxidant activity of allicin on the oxidation of cumene and linoleic acid in homogeneous solutions. It is obvious from these results that 2-propenesulfenic acid was found to make a larger contribution to the radical scavenger than that of allicin itself.

Topics: Acetonitriles; Antioxidants; Benzene Derivatives; Chlorobenzenes; Disulfides; Ethanol; Hexanes; Linoleic Acid; Oxidation-Reduction; Sulfenic Acids; Sulfinic Acids; Sulfoxides

Lipase-catalyzed esterification of conjugated linoleic acid (CLA) with L-carnitine in solvent-free system and acetonitrile was studied. Three lipases (Novzym 435, Amamo AY30 and Amano AYS) have been assayed as suitable biocatalysts in the reaction. It was found that Amano AY30 was the most effective biocatalyst in both solvent-free system and acetonitrile. The conversion rate varied from 8.05 to 60.9% in terms of reaction conditions such as the amount of lipase, the presence of water, the amount of molecular sieves and reaction time. The conversions of substrate in solvent-free system were higher than that in acetonitrile. When the substrates were 1 mmol CLA and 1 mmol L-carnitine, the maximum conversion (60.9%) was obtained in solvent-free system with 150 mg lipase AY30, 50% water content and 150 mg molecular sieves at the reaction time of 24 h. A novel CLA ester product was successfully isolated and characterized by ESI-MS and (1)H NMR.

Topics: Acetonitriles; Biotechnology; Carnitine; Catalysis; Chromatography, Gas; Esters; Fatty Acids; Linoleic Acid; Lipase; Magnetic Resonance Spectroscopy; Mass Spectrometry; Models, Chemical; Solvents; Spectrometry, Mass, Electrospray Ionization; Water

The oxidation of linoleic acid produces several products with biological activity including the hydroperoxy fatty acid 13-hydroperoxyoctadecadienoic acid (13-HPODE), the hydroxy fatty acid 13-hydroxyoctadecadienoic acid (13-HODE), and the 2,4-dienone 13-oxooctadecadienoic acid (13-OXO). In the present work, the peroxidase activity of glutathione transferases (GST) A1-1, M1-1, M2-2, and P1-1(Val 105) toward 13-HPODE has been examined. The alpha class enzyme is the most efficient peroxidase while the two enzymes from the mu class exhibit weak peroxidase activity toward 13-HPODE. It was also determined that the conjugated diene 13-HODE is not a substrate for GST from the alpha and mu classes but that 13-HODE does inhibit the GST-catalyzed conjugation of CDNB by enzymes from the alpha, mu, and pi classes. Finally, both 13-HODE and 13-OXO were shown to be inducers of GST activity in HT-29 and HCT-116 colon tumor cells. These data help to clarify the role of GST in the metabolic disposition of linoleic acid oxidation products.

Topics: Acetonitriles; Cell Line, Tumor; Dinitrochlorobenzene; Dose-Response Relationship, Drug; Glutathione; Humans; Kinetics; Linoleic Acid; Linoleic Acids; Linolenic Acids; Lipid Peroxides; Models, Chemical; Oxygen; Peroxidase

A major bioactive metabolite of linoleic acid formed by the action of 15-lipoxygenase-1 is 13(S)-hydroxy-cis-9, trans-11-octadecadienoic acid (13(S)-HODE). 13(S)-HODE is an important intracellular signal agent and is involved in cell proliferation and differentiation in various biological systems. Separation and quantification of 13(S)-HODE from biological materials has previously been achieved only by using radiolabeled linoleic acid as the substrate and two serially connected or two separate HPLC columns to achieve separation of 13(S)-HODE. In the current method, separation and quantification of 13(S)-HODE was achieved by use of a normal-phase HPLC and a solvent system containing hexane/isopropanol/acetonitrile/acetic acid (800/8/30/1, v/v) using isocratic elution with detection at 235 nm. With the currently described method, good separation from unreacted interfering compounds and quantification for 13(S)-HODE were achieved within 35 min with a minimum detection limit of 0.5 ng per injection.

Topics: 2-Propanol; Acetic Acid; Acetonitriles; Animals; Chromatography, High Pressure Liquid; Hexanes; Linoleic Acid; Linoleic Acids; Liver; Lung; Rats; Rats, Sprague-Dawley

A complex mixture of different lipid compounds, including phosphatidylcholine, phosphatidylserine, all trans-retinol, 15(S)-hydroperoxyeicosatetraenoic acid, D-alpha-tocopherol, saturated and unsaturated fatty acids can be separated by reversed phase HPLC by using a C-18, 120 mm x 4 mm, 3 microns particle size column and a step gradient from acetonitrile/water (1:1; v:v) to 100% acetonitrile at a flow rate of 0.8 ml/min. By applying this elution condition, separation of various groups of lipid hydroperoxides and lipid derivatives, each one originating from a different in vitro peroxidized polyunsaturated fatty acid, can be obtained. Simultaneous detection is carried out by a diode array detector at a wavelength accumulation range set up between 195 and 400 nm. The possibility of simultaneously having such a large number of measurements renders this chromatographic method particularly suitable in studies concerning lipid peroxidation where, in addition to the detection of free radical-induced lipid hydroperoxides, data on some key antioxidant molecules, i.e. vitamin A and E, as well as that of structural compounds of biological membranes, i.e. phosphatidylcholine and phosphatidylserine, can be achieved.

Topics: Acetonitriles; Arachidonic Acid; Chromatography, High Pressure Liquid; Fatty Acids, Unsaturated; gamma-Linolenic Acid; Leukotrienes; Linoleic Acid; Linoleic Acids; Lipid Peroxidation; Lipid Peroxides; Lipids; Membrane Lipids; Oleic Acid; Palmitic Acid; Phosphatidylcholines; Phosphatidylserines; Stearic Acids; Vitamin A; Vitamin E