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首页> 外文期刊>Chemistry: A European journal >Internal versus terminal metalation of double-helical oligodeoxyribonucleotides
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Internal versus terminal metalation of double-helical oligodeoxyribonucleotides

机译：双螺旋寡脱氧核糖核苷酸的内部与末端金属化

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The formation of adducts between cis-[Pt(NH3)(2)Cl-2], Zn-II, and Mn-II and double-stranded oligodeoxynucleotides was studied by ID and 2D H-1, P-31, and N-15 NMR spectroscopy. For labile adducts involving Zn-II and Mn-II, both H-1 chemical shifts (Zn-II) and H-1 line-broadening effects (Mn-II) showed that in the hexamer [d(GGCGCC)](2) 1, the terminal G(1)-N7 is the exclusive binding site, while for the dodecamer [d(GGTACCGGTACC)](2) 11, which contains both a terminal and internal GG pair, the preference for metal binding is the internal guanine G(7). Zn-II binding to 11 was confirmed by natural-abundance 2D [H-1, N-15] HMBC NMR spectroscopy, which unambiguously showed that G(7)-N7 is the preferred binding site. The long duplex [d(GGTATATATACCGGTATA-TATACC)](2) III was expected to have a more pronounced accumulation of electrostatic potential towards the central part of the sequence (vs the terminal part) than does H. However, the Zn-II titration of III showed no increase in coordination with the internal Gs (vs the terminal Gs), compared with what was observed for H. The reaction between the nonlabile metal complex cis[PtCl2((NH3)-N-15)(2)] (cisplatin) and 11 showed a slight preference for the internal GG pair over the terminal GG pair. However, when the diaqua form of cisplatin cis-[Pt((NH3)-N-15)(2)(H2O)(2)] was reacted with 11 a more pronounced binding preference for the internal GG pair was observed.
机译：通过ID和2D H-1，P-31和N-研究了顺式[Pt（NH3）（2）Cl-2]，Zn-II和Mn-II与双链寡聚脱氧核苷酸之间加合物的形成15 NMR光谱。对于涉及Zn-II和Mn-II的不稳定加合物，H-1化学位移（Zn-II）和H-1线扩展作用（Mn-II）均显示六聚体[d（GGCGCC）]（2）如图1所示，末端G（1）-N7是排他性结合位点，而对于十二末端[d（GGTACCGGTACC）]（2）11，它同时包含末端和内部GG对，金属结合的偏好是内部鸟嘌呤。 G（7）。 Zn-II与11的结合是通过自然丰度的2D [H-1，N-15] HMBC NMR光谱证实的，它明确表明G（7）-N7是优选的结合位点。长双链体[d（GGTATATATACCGGTATA-TATACC）]（2）III预期比H具有更明显的朝向序列中心部分（相对于末端部分）的静电势积累。但是，Zn-II滴定与观察到的H相比，III的结果显示与内部Gs（相对于末端Gs）的配位没有增加。非不稳定金属络合物cis [PtCl2（（NH3）-N-15）（2）]之间的反应顺铂）和11表现出比末端GG对略微偏爱内部GG对。然而，当顺铂的顺铂形式与11反应时，观察到对内部GG对更明显的结合偏好。顺铂[-（Pt（（NH3）-N-15）（2）（H2O）（2））

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