Jayakumar A, Chirala S S, Wakil S J
Verna and Marrs McLean Department of Biochemistry, Baylor College of Medicine, One Baylor Plaza, Houston, TX 77030, USA.
Proc Natl Acad Sci U S A. 1997 Nov 11;94(23):12326-30. doi: 10.1073/pnas.94.23.12326.
Our model of the native fatty acid synthase (FAS) depicts it as a dimer of two identical multifunctional proteins (Mr approximately 272,000) arranged in an antiparallel configuration so that the active Cys-SH of the beta-ketoacyl synthase of one subunit (where the acyl group is attached) is juxtaposed within 2 A of the pantetheinyl-SH of the second subunit (where the malonyl group is bound). This arrangement generates two active centers for fatty acid synthesis and predicts that if we have two appropriate halves of the monomer, we should be able to reconstitute an active fatty acid-synthesizing site. We cloned, expressed, and purified catalytically active thioredoxin (TRX) fusion proteins of the NH2-terminal half of the human FAS subunit protein (TRX-hFAS-dI; residues 1-1,297; Mr approximately 166) and of the C-terminal half (TRX-hFAS-dII-III; residues 1,296-2,504; Mr approximately 155). Adding equivalent amounts of TRX-hFAS-dI and TRX-hFAS-dII-III to a reaction mixture containing acetyl-CoA, malonyl-CoA, and NADPH resulted in the synthesis of long-chain fatty acids. The rate of synthesis was dependent upon the presence of both recombinant proteins and reached a constant level when they were present in equivalent amounts, indicating that the reconstitution of an active fatty acid-synthesizing site required the presence of every partial activity associated with the subunit protein. Analyses of the product acids revealed myristate to be the most abundant with small amounts of palmitate and stearate, possibly because of the way the fused recombinant proteins interacted with each other so that the thioesterase hydrolyzed the acyl group in its myristoyl state. The successful reconstitution of the human FAS activity from its domain I and domains II and III fully supports our model for the structure-function relationship of FAS in animal tissues.
我们构建的天然脂肪酸合酶(FAS)模型显示,它是由两个相同的多功能蛋白(分子量约为272,000)组成的二聚体,以反平行构型排列,使得一个亚基的β-酮酰基合酶的活性半胱氨酸巯基(酰基连接在此处)与第二个亚基的泛酰巯基乙胺巯基(丙二酰基结合在此处)在2埃的范围内并列。这种排列产生了两个脂肪酸合成的活性中心,并预测如果我们有单体的两个合适的半部分,应该能够重建一个活性脂肪酸合成位点。我们克隆、表达并纯化了人FAS亚基蛋白NH2末端半部分(TRX-hFAS-dI;第1至1297位氨基酸;分子量约为166)和C末端半部分(TRX-hFAS-dII-III;第1296至2504位氨基酸;分子量约为155)的具有催化活性的硫氧还蛋白(TRX)融合蛋白。将等量的TRX-hFAS-dI和TRX-hFAS-dII-III添加到含有乙酰辅酶A、丙二酰辅酶A和NADPH的反应混合物中,导致了长链脂肪酸的合成。合成速率取决于两种重组蛋白的存在,当它们以等量存在时达到恒定水平,这表明活性脂肪酸合成位点的重建需要与亚基蛋白相关的每一种部分活性的存在。对产物酸的分析表明,肉豆蔻酸是最丰富的,还有少量的棕榈酸和硬脂酸,这可能是由于融合的重组蛋白相互作用的方式,使得硫酯酶以其肉豆蔻酰状态水解酰基。从其结构域I以及结构域II和III成功重建人FAS活性,充分支持了我们关于动物组织中FAS结构-功能关系的模型。