Hamberg M
Biochim Biophys Acta. 1984 Mar 27;793(1):129-32. doi: 10.1016/0005-2760(84)90062-6.
Synthesis of intramolecularly labeled 6,9,12-[11,11-2H2,1-14C]octadecatrienoic acid is described. The doubly labeled acid was added to 6,9,12-[9,10-3H2]octadecatrienoic acid and the mixture was incubated with soybean and human platelet lipoxygenases and was subjected to autoxidation. Methyl 13-hydroxyoctadecanoate obtained in the three sets of experiments had a considerably reduced 14C/3H ratio compared to that of the starting material, i.e., 20-24% (autoxidation) and 12-15% (lipoxygenase oxygenations). This indicates that subtraction of a hydrogen atom from the methylene group of the cis,cis-pentadiene structure is the rate-limiting step in autoxidation as well as in the enzymatic oxygenations.
本文描述了分子内标记的6,9,12-[11,11-2H₂,1-¹⁴C]十八碳三烯酸的合成。将双标记的酸加入到6,9,12-[9,10-³H₂]十八碳三烯酸中，混合物与大豆和人血小板脂氧合酶一起孵育并进行自氧化。在三组实验中获得的13-羟基十八烷酸甲酯与起始原料相比，¹⁴C/³H比值显著降低，即自氧化时为20-24%，脂氧合酶氧化时为12-15%。这表明从顺,顺-戊二烯结构的亚甲基上减去一个氢原子是自氧化以及酶促氧化中的限速步骤。
