Geometrical isomerism of monounsaturated fatty acids: thiyl radical catalysis and influence of antioxidant vitamins

• Published in: Free radical biology & medicine Vol. 33; no. 12; pp. 1681 - 1692
• Main Authors: Chatgilialoglu, Chryssostomos, Zambonin, Laura, Altieri, Alessio, Ferreri, Carla, Mulazzani, Quinto G, Landi, Laura
• Format: Journal Article
• Language: English
• Published: United States Elsevier Inc 15-12-2002
• Subjects: All-trans retinol; Antioxidants; Antioxidants - pharmacology; Ascorbic acid; Catalysis - radiation effects; Dose-Response Relationship, Radiation; Fatty acids; Fatty Acids, Monounsaturated - chemistry; Fatty Acids, Monounsaturated - metabolism; Fatty Acids, Monounsaturated - radiation effects; Free radicals; Free Radicals - chemistry; Gamma Rays; Isomerism; Lipids; Oleic Acids - chemistry; Oxidation-Reduction - radiation effects; Photolysis - radiation effects; tert-Butyl Alcohol; Thiols; Time Factors; Vitamins - pharmacology; α-Lipoic acid; α-Tocopherol; γ Radiolysis; Antioxidants; α-Lipoic acid; Free radicals; Thiols; Ascorbic acid; Lipids; α-Tocopherol; γ Radiolysis; Fatty acids; All-trans retinol
• ISSN: 0891-5849; 1873-4596
• DOI: 10.1016/S0891-5849(02)01143-7

Thiyl radicals generated either from thiols or disulfides act as the catalyst for the cis-trans isomerization of a variety of monounsaturated fatty acid methyl esters in homogeneous solution. Similar results have also been obtained using α-lipoic acid and its reduced form. The effectiveness of the isomerization processes in the presence of the most common antioxidants has been addressed. The ability of thiyl radical scavenging was found to increase along the series α-tocopherol < ascorbic acid < all-trans retinol. The cis-trans isomerization of fatty acid residues in multilamellar vesicles of dioleoyl phosphatidyl choline by thiyl radical, in the absence and presence of the various antioxidants, has also been studied in detail. The influence of the isomerization process on the phospholipid bilayer has been tested by permeability measurements of vesicles and it is clearly shown that trans fatty acid-containing membranes have intermediate properties between those formed by all-cis and saturated components. This study contributes to the understanding of radical processes that can alter or protect the naturally occurring cis geometry of unsaturated lipids in cell membranes and demonstrates a new role of essential antioxidants.