Jaffe E K, Cohn M
J Biol Chem. 1978 Jul 25;253(14):4823-5.
31P NMR studies with Cd(II) and Zn(II) chelates of adenosine 5'-O-(3-thiotriphosphate) (ATPgammaS) and the Cd(II) chelate of adenosine 5'-O-(2-thiotriphosphate) (ATPbetaS) indicate that these metal ions chelate to the sulfur atom of the thiophosphate group. Since Mg(II) chelates to oxygen of the thiophosphate group of diastereoisomer is equivalent to the configuration of the Cd(II) chelate of the opposite diastereoisomer. As a consequence, an inversion of the stereospecificity is observed when Cd(II) is substituted for Mg(II) in the phosphoryl transfer reactions catalyzed by yeast hexokinase and rabbit muscle pyruvate kinase. When Co(II) is the activating ion for yeast hexokinase with ATPbetaS as substrate, no stereospecificity is observed. Since the absolute configuration for the diastereoisomer of Co(III)(NH3)4ATP which is the active substrate for yeast hexokinase has been established by Cornelius and Cleland (Cornelius, R. D., and Cleland, W. W. (1978) Biochemistry, in press), the absolute stereochemistry of the Mg(II) complex of the B isomer of ATPbetaS is now established by its stereospecificity in the hexokinase reaction.
用腺苷5'-O-(3-硫代三磷酸)(ATPγS)的镉(II)和锌(II)螯合物以及腺苷5'-O-(2-硫代三磷酸)(ATPβS)的镉(II)螯合物进行的31P NMR研究表明，这些金属离子与硫代磷酸基团的硫原子螯合。由于镁(II)与非对映异构体硫代磷酸基团的氧螯合等同于相反非对映异构体的镉(II)螯合物的构型。因此，在酵母己糖激酶和兔肌肉丙酮酸激酶催化的磷酰基转移反应中，当用镉(II)取代镁(II)时，会观察到立体特异性的反转。当以ATPβS为底物时，钴(II)作为酵母己糖激酶的激活离子，未观察到立体特异性。由于科尼利厄斯和克莱兰已经确定了作为酵母己糖激酶活性底物的Co(III)(NH3)4ATP非对映异构体的绝对构型（科尼利厄斯，R.D.，和克莱兰，W.W.（1978年），《生物化学》，即将出版），现在通过其在己糖激酶反应中的立体特异性确定了ATPβS的B异构体的镁(II)配合物的绝对立体化学。
