Easton C J, Robertson T A, Pitt M J, Rathjen D A, Ferrante A, Poulos A
Research School of Chemistry, Australian National University, Canberra, ACT, Australia.
Bioorg Med Chem. 2001 Feb;9(2):317-22. doi: 10.1016/s0968-0896(00)00246-7.
The modified fatty acids, (Z,Z,Z)-(octadeca-6,9,12-trienyloxy)acetic acid, (Z,Z,Z)-(octadeca-9,12,15-trienyloxy)acetic acid, (all-Z)-(eicosa-5,8,11,14-tetraenyloxy)acetic acid, (all-Z)-(eicosa-5,8,11,14-tetraenylthio)acetic acid, 3-[(all-Z)-(eicosa-5,8,11,14-tetraenylthio)]propionic acid, (all-Z)-(eicosa-5,8,11,14-tetraenylthio)succinic acid, N-[(all-Z)-(eicosa-5,8,11,14-tetraenoyl)]glycine and N-[(all-Z)-(eicosa-5,8,11,14-tetraenoyl)]aspartic acid, all react with soybean 15-lipoxygenase. The products were treated with triphenylphosphine to give alcohols, which were isolated using HPLC. Analysis of the alcohols using negative ion tandem electrospray mass spectrometry, and by comparison with compounds obtained by autoxidation of arachidonic acid, shows that each enzyme-catalysed oxidation occurs at the omega-6 position of the substrate. In a similar fashion, it has been found that (Z,Z,Z)-(octadeca-6,9,12-trienyloxy)acetic acid, (Z,Z,Z)-(octadeca-9,12,15-trienyloxy)acetic acid, (all-Z)-(eicosa-5,8,11,14-tetraenylthio)acetic acid and 3-[(all-Z)-(eicosa-5,8,11,14-tetraenylthio)]propionic acid each undergoes regioselective oxidation at the carboxyl end of the polyene moiety on treatment with potato 5-lipoxygenase. Neither (all-Z)-(eicosa-5,8,11,14-tetraenylthio)succinic acid nor N-[(all-Z)-(eicosa-5,8,11,14-tetraenoyl)]aspartic acid reacts in the presence of this enzyme, while N-[(all-Z)-(eicosa-5,8,11,14-tetraenoyl)]glycine affords the C11' oxidation product. The alcohol derived from (Z,Z,Z)-(octadeca-6,9,12-trienyloxy)acetic acid using the 15-lipoxygenase reacts at the C6' position with the 5-lipoxygenase.
修饰脂肪酸，即(Z,Z,Z)-(十八碳-6,9,12-三烯氧基)乙酸、(Z,Z,Z)-(十八碳-9,12,15-三烯氧基)乙酸、(全-Z)-(二十碳-5,8,11,14-四烯氧基)乙酸、(全-Z)-(二十碳-5,8,11,14-四烯硫基)乙酸、3-[(全-Z)-(二十碳-5,8,11,14-四烯硫基)]丙酸、(全-Z)-(二十碳-5,8,11,14-四烯硫基)琥珀酸、N-[(全-Z)-(二十碳-5,8,11,14-四烯酰基)]甘氨酸和N-[(全-Z)-(二十碳-5,8,11,14-四烯酰基)]天冬氨酸，均与大豆15-脂氧合酶发生反应。产物用三苯基膦处理得到醇类，通过高效液相色谱法进行分离。使用负离子串联电喷雾质谱法对醇类进行分析，并与花生四烯酸自氧化得到的化合物进行比较，结果表明每种酶催化氧化均发生在底物的ω-6位。以类似的方式发现，(Z,Z,Z)-(十八碳-6,9,12-三烯氧基)乙酸、(Z,Z,Z)-(十八碳-9,12,15-三烯氧基)乙酸、(全-Z)-(二十碳-5,8,11,14-四烯硫基)乙酸和3-[(全-Z)-(二十碳-5,8,11,14-四烯硫基)]丙酸在用马铃薯5-脂氧合酶处理时，均在多烯部分的羧基端发生区域选择性氧化。(全-Z)-(二十碳-5,8,11,14-四烯硫基)琥珀酸和N-[(全-Z)-(二十碳-5,8,11,14-四烯酰基)]天冬氨酸在该酶存在下均不发生反应，而N-[(全-Z)-(二十碳-5,8,11,14-四烯酰基)]甘氨酸生成C11'氧化产物。使用15-脂氧合酶从(Z,Z,Z)-(十八碳-6,9,12-三烯氧基)乙酸衍生得到的醇类与5-脂氧合酶在C6'位发生反应。
