腺苷 5'-O-(1-硫代三磷酸)非对映异构体的绝对构型：对大肠杆菌依赖 DNA 的 RNA 聚合酶聚合反应立体化学的影响。
Absolute configuration of the diastereomers of adenosine 5'-O-(1-thiotriphosphate): consequences for the stereochemistry of polymerization by DNA-dependent RNA polymerase from Escherichia coli.
作者信息
Burgers P M, Eckstein F
出版信息
Proc Natl Acad Sci U S A. 1978 Oct;75(10):4798-800. doi: 10.1073/pnas.75.10.4798.
Abstract
The diastereomers of uridyl-(3'-5')adenyl-O,O-phosphorothioate [Up(S)A] have been separated by high-performance liquid chromatography. Their identification as RP and SP follows from the RNase A digestion of these products. It was then shown, by the same method, that the R isomer is hydrolyzed by snake venom phosphodiesterase (PDEase) approximately 500 times faster than the S isomer. Similarly, the stereoisomer of adenosine 5'-O-(1-thiotriphosphate) (ATPalphaS), until now arbitrarily designated as isomer B, is hydrolyzed ca 400 times faster by PDEase than is isomer A. From these results it is concluded that the R isomers of Up(S)A and ATPalphaS, isomers B, have the same absolute configuration. It then follows that isomer A of ATPalphaS, the preferred of the two isomers as substrate for DNA-dependent RNA polymerase, has the S configuration. The implications for the stereochemistry of action of the latter enzyme are discussed.
摘要
尿苷酰 -（3'-5'）腺苷 - O，O - 硫代磷酸酯[Up(S)A]的非对映异构体已通过高效液相色谱法分离。通过对这些产物进行核糖核酸酶A消化确定它们为RP和SP。然后通过相同的方法表明，R异构体被蛇毒磷酸二酯酶（PDEase）水解的速度比S异构体快约500倍。同样，腺苷5'-O-（1-硫代三磷酸）（ATPαS）的立体异构体，直到现在被任意指定为异构体B，被PDEase水解的速度比异构体A快约400倍。从这些结果可以得出结论，Up(S)A和ATPαS的R异构体，即异构体B，具有相同的绝对构型。因此，ATPαS的异构体A，作为依赖DNA的RNA聚合酶的底物，两种异构体中更受青睐的一种，具有S构型。讨论了后者酶作用的立体化学意义。
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