LoGrasso P V, Soltis D A, Boettcher B R
Department of Atherosclerosis and Vascular Biology, Sandoz Research Institute, East Hanover, New Jersey 07936.
Arch Biochem Biophys. 1993 Nov 15;307(1):193-9. doi: 10.1006/abbi.1993.1578.
Yeast squalene synthetase which has been truncated by 24 amino acids at the C-terminus has been overexpressed in Escherichia coli and constitutes approximately 20% of the total soluble cell protein. For the first time, milligram quantities of this essential enzyme in the cholesterol biosynthetic pathway have been purified to near homogeneity by ammonium sulfate precipitation and Mono Q anion-exchange chromatography so that the steady-state rate constants could be measured. A combination of 10% methanol, 10% glycerol, 30 mM octyl-beta-D-glucopyranoside, 0.4% Brij-58, and 1 mM dithiothreitol in 25 mM sodium phosphate, pH 7.4, was essential for the stability and maximal enzyme activity of the near homogeneous enzyme. Kinetic analysis indicated a Km for farnesyl pyrophosphate of 2.5 microM, suggesting fairly tight binding of farnesyl pyrophosphate to truncated yeast squalene synthetase. The turnover number, kcat, for the conversion of farnesyl pyrophosphate to squalene was 0.53 s-1, and the apparent second order rate constant, kcat/Km, was 2.1 x 10(5) M-1 s-1, indicating a relatively slow conversion of farnesyl pyrophosphate to squalene and a low specificity constant for this enzyme. In addition, Km for NADPH and NADH was 0.5 and 3.6 mM, respectively. Moreover, truncated yeast squalene synthetase shows a preference for NADPH over NADH as reflected in the sevenfold higher kcat/Km value for NADPH similar to that for the native enzyme.
在C端截短了24个氨基酸的酵母鲨烯合酶已在大肠杆菌中过表达,约占细胞可溶性总蛋白的20%。首次通过硫酸铵沉淀和Mono Q阴离子交换色谱法将胆固醇生物合成途径中的这种必需酶纯化至接近均一,以便能够测量稳态速率常数。25 mM磷酸钠(pH 7.4)中10%甲醇、10%甘油、30 mM辛基-β-D-吡喃葡萄糖苷、0.4% Brij-58和1 mM二硫苏糖醇的组合对于接近均一的酶的稳定性和最大酶活性至关重要。动力学分析表明,法尼基焦磷酸的Km为2.5 μM,表明法尼基焦磷酸与截短的酵母鲨烯合酶结合相当紧密。法尼基焦磷酸转化为鲨烯的周转数kcat为0.53 s-1,表观二级速率常数kcat/Km为2.1×105 M-1 s-1,表明法尼基焦磷酸转化为鲨烯的速度相对较慢,且该酶的特异性常数较低。此外,NADPH和NADH的Km分别为0.5和3.6 mM。此外,截短的酵母鲨烯合酶对NADPH的偏好高于NADH,这反映在NADPH的kcat/Km值比天然酶高7倍。