Conformational analysis of the adduct cis-[Pt(NH3)2 d(GpG)]+ in aqueous solution. A high field (500-300 MHz) nuclear magnetic resonance investigation.
Conformational analysis of the adduct cis-[Pt(NH3)2 d(GpG)]+ in aqueous solution. A high field (500-300 MHz) nuclear magnetic resonance investigation.
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水溶液中加合物 cis-[Pt(NH3)2 d(GpG)] 的构象分析。
DOI：
10.1093/nar/10.15.4715
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发表时间：
1982
影响因子：
14.9
通讯作者：
J. Reedijk
中科院分区：
文献类型：
--
作者：
J. H. J. D. Hartog;C. Altona;J. Chottard;Jean;Jean;Frank A. A. M. de Leeuw;A. Marcelis;J. Reedijk
用500、400和300 MHz质子核磁共振研究了顺-铂(NH3)2Cl2或顺-[铂(NH3)2(H2O)2](NO3)2与脱氧二核苷酸d(GPG)：cis-[铂(NH3)2d(GPG)]的反应产物。通过去耦合实验和计算机模拟完成了质子共振的指认，得到了高精度的高场产额质子-质子和质子-磷耦合常数。对这些偶联常数的分析表明，螯合d(GPG)部分5‘末端的脱氧核糖环为100%N(C3’-endo)构象。相反，分子的3‘-末端-PG部分表现出脱氧核糖的正常行为：糖环更喜欢采用S(C2’-endo)构象(约70%)。根据这一模型化合物推测，DNA的a-dGpdG-序列与铂的络合需要一个脱氧核糖基的S到N的构象变化作为主要的构象变化，并导致DNA的双螺旋结构中的一条链发生扭曲。
A 500, 400 and 300 MHz proton NMR study of the reaction product of cis-Pt(NH3)2Cl2 or cis-[Pt(NH3)2 (H2O)2] (NO3)2 with the deoxydinucleotide d(GpG): cis-[Pt(NH3)2 d(GpG)] was carried out. Complete assignment of the proton resonances by decoupling experiments and computer simulation of the high field part of the spectrum yield proton-proton and proton-phosphorus coupling constants of high precision. Analysis of these coupling constants reveal a 100% N (C3'-endo) conformation for the deoxyribose ring at the 5'-terminal part of the chelated d(GpG) moiety. In contrast, the 3'-terminal -pG part of the molecule displays the normal behaviour for deoxyriboses: the sugar ring prefers to adopt an S (C2'-endo) conformation (about 70%). Extrapolating from this model compound, it is suggested that Pt chelation by a -dGpdG- sequence of DNA would require a S to N conformational change of one deoxyribose moiety as the main conformational alteration and lead to a kink in one strand of the double-helical structure of DNA.