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Ruthenation of duplex and single-stranded d(CGGCCG) by organometallic anticancer complexes

机译:有机金属抗癌复合物对双链和单链d(CGGCCG)的钌化

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摘要

We have studied the interaction of the organometallic anticancer ruthenium(II) complexes [(eta(6)-p-cymene)Ru(en)Cl][PF6] (1) and [(eta(6)-biphenyl)Ru(en)Cl][PF6] (2) (en=ethylenediamine) with the single-stranded (ss) DNA hexamer d(CGGCCG) (1) and the duplex d(CGGCCG)2 (H) by HPLC, ESI-MS, and one- and two-dimensional H-1 and N-15 NMR spectroscopy. For ss-DNA, all three G's are readily ruthenated with [(eta(6)-arene)-Ru(en)](2+), but for duplex DNA there is preferential ruthenation of G3 and G6, and no binding to G2 was detected. For monoruthenated duplexes, N7 ruthenation of G is accompanied by strong hydrogen bonding between GO6 and en-NH for the p-cymene adducts. Intercalation of the non-coordinated phenyl ring between G3 and C4 or G6 and C5 was detected in the biphenyl adducts of mono- and diruthenated duplexes, together with weakening of the G-O6(...)NH-en hydrogen bonding. The arene ligand plays a major role in distorting the duplex either through steric interactions (p-cymene) or through intercalation (biphenyl).
机译:我们已经研究了有机金属抗癌钌(II)配合物[(eta(6)-p-cymene)Ru(en)Cl] [PF6](1)和[(eta(6)-biphenyl)Ru(en)的相互作用)Cl] [PF6](2)(en =乙二胺),通过HPLC,ESI-MS和单链(ss)DNA六聚体d(CGGCCG)(1)和双链体d(CGGCCG)2(H)进行,一维和二维H-1和N-15 NMR光谱。对于ss-DNA,所有三个G都容易用[[eta(6)-arene)-Ru(en)](2+)钌化,但是对于双链DNA,G3和G6优先钌化,并且不与G2结合被检测到。对于单钌双链体,G的N7钌在GO6与en-NH之间形成强力氢键,从而形成对苯丙氨酸加合物。在单和双键双链体的联苯加合物中检测到G3和C4或G6和C5之间未配位的苯环的插入,同时削弱了G-O6(...)NH-en氢键。芳烃配体在通过空间相互作用(对苏木精)或通过嵌入(联苯)扭曲双链体中起主要作用。

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