cis-trans isomerization of monounsaturated fatty acid residues in phospholipids by thiyl radicals

被引:110
作者
Chatgilialoglu, C
Ferreri, C
Ballestri, M
Mulazzani, QG
Landi, L
机构
[1] CNR, Icocea, I-40129 Bologna, Italy
[2] CNR, FRAE, I-40129 Bologna, Italy
[3] Univ Naples Federico II, Dipartimento Chim Organ & Biol, I-80134 Naples, Italy
[4] Univ Bologna, Dipartimento Biochim G Moruzzi, I-40126 Bologna, Italy
关键词
D O I
10.1021/ja994169s
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Thiyl radicals reversibly attack the double bonds of methyl oleate and dioleoyl phosphatidyl choline (DOPC), thus producing methyl elaidate and the corresponding phospholipids containing trans-fatty acid residues in high yield. These processes are radical chain reactions with relatively long chain lengths. The rate constant for the beta-elimination of a thiyl radical from the adduct radical has been estimated to be 6 x 10(6) s(-1) at ambient temperature. The cis-trans isomerization of fatty acid residues in DOPC vesicles (multilamellar vesicles and large unilamellar vesicles made by the extrusion technique) by a thiyl radical, generated from biologically relevant thiols, has also been studied in detail. The presence of 0.2 mM oxygen does not influence the effectiveness of cis-trans isomerization in both homogeneous solution and lipid vesicles. This process, which does not cause lipid degradation but permanent modification of the membrane constituents, ultimately influences the barrier properties and functions of biological membranes.
引用
收藏
页码:4593 / 4601
页数:9
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