Transformation of phospholipid membranes by thiyl radicals via cis-trans isomerization of fatty acid residues.
Transformation of phospholipid membranes by thiyl radicals via cis-trans isomerization of fatty acid residues.
复制标题
硫基自由基通过脂肪酸残基的顺反异构化来转化磷脂膜。
DOI：
10.1016/s0001-8686(00)00063-4
复制
发表时间：
2001
影响因子：
15.6
通讯作者：
O. Brede
中科院分区：
文献类型：
--
作者：
H. Sprinz;S. Adhikari;O. Brede
报道了巯基自由基介导的不饱和脂肪酸残基转化。除了引发脂质过氧化外，巯基自由基还能催化脂肪酸残基异构化。后一过程可以在均相溶液中观察到，也可以在有组织的组装中观察到，导致脂质双分子层脂肪酸残基的天然全顺式异构体变性。变性的程度与硫醇的双键数和疏水性的增加是平行的。对于花生四烯酸甲酯，观察到在胶束中1.8 kGy的伽马辐照剂量后，所有顺式异构体的衰变约为30%。在脂质体中，顺式/反式平衡与起始化合物的构型无关，证明了异构化反应的可逆性。
Thiyl radical-mediated transformation of unsaturated fatty acid residues are reported. Beside the initiation of lipid peroxidation, thiyl radicals can efficiently cause isomerization of fatty acid residues in a catalytic manner. The latter process is observed in homogeneous solutions as well as in organized assemblies, leading to a denaturation of the natural all-cis-isomers of fatty acid residues of lipid bilayers. The degree of denaturation goes parallel with an increase in the number of double bonds and in the hydrophobicity of thiols. For arachidonic acid methyl ester, a decay of the all-cis-isomer to approximately 30% after a gamma irradiation dose of 1.8 kGy in micelles is observed. The reversibility of the isomerization reaction is demonstrated in liposomes by the fact that the cis/trans-equilibrium is independent of configuration of the starting compound.