Shen Weijun, McGath Molly K, Evande Ruby, Berkowitz David B
Department of Chemistry, University of Nebraska, Lincoln, NE 68588, USA.
Anal Biochem. 2005 Jul 1;342(1):103-10. doi: 10.1016/j.ab.2005.03.051.
We report a new continuous spectrophotometric assay for human cystathionine beta-synthase (hCBS). This assay relies upon the finding that hCBS will take cysteamine in place of L-homocysteine, thereby producing thialysine. Thialysine is, in turn, decarboxylated by lysine decarboxylase, releasing CO2 that is monitored by the sequential action of phosphoenolpyruvate carboxylase and L-malate dehydrogenase. The decrease in absorbance at 340 nm is monitored as reduced nicotinamide adenine dinucleotide is consumed. Using this four-enzyme couple, we find that Km(app) = 1.2+/-0.2 mM for L-serine and 5.6+/-2.2 mM for cysteamine, with kcat = 1.3+/-0.1s(-1) for the formation of thialysine by hCBS. For comparison purposes, the same hCBS reaction was monitored via a radioactive single time point assay using 14C-(C-1)-labeled L-serine and cysteamine as substrates, counting the thialysine product, following ion exchange chromatography. This assay yielded Km(app) = 2.2+/-0.5 mM for L-serine and 6.6+/-2.2 for cysteamine, with kcat = 2.5+/-0.4 s(-1). These numbers indicate that, although it possesses a shortened carbon chain and lacks a carboxyl group, cysteamine displays a catalytic efficiency (kcat/Km) with hCBS that is within an order of magnitude of that observed with its natural thiol cosubstrate, L-homocysteine.
我们报告了一种用于人胱硫醚β-合酶(hCBS)的新型连续分光光度测定法。该测定法基于以下发现:hCBS能够用半胱胺替代L-高半胱氨酸,从而生成硫代赖氨酸。硫代赖氨酸继而被赖氨酸脱羧酶脱羧,释放出二氧化碳,通过磷酸烯醇式丙酮酸羧化酶和L-苹果酸脱氢酶的顺序作用对其进行监测。随着烟酰胺腺嘌呤二核苷酸磷酸被消耗,监测340nm处吸光度的下降。使用这种四酶偶联体系,我们发现hCBS形成硫代赖氨酸时,L-丝氨酸的Km(app)=1.2±0.2mM,半胱胺的Km(app)=5.6±2.2mM,kcat=1.3±0.1s-1。为作比较,通过放射性单点测定法监测相同的hCBS反应,使用14C-(C-1)标记的L-丝氨酸和半胱胺作为底物,在离子交换色谱后对硫代赖氨酸产物进行计数。该测定法得出L-丝氨酸的Km(app)=2.2±0.5mM,半胱胺的Km(app)=6.6±2.2,kcat=2.5±0.4s-1。这些数据表明,尽管半胱胺具有缩短的碳链且缺乏羧基,但它与hCBS的催化效率(kcat/Km)与天然硫醇共底物L-高半胱氨酸所观察到的催化效率在一个数量级内。