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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >DNA binding selectivity of oligopyridine-ruthenium(ii)-lysine conjugate
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DNA binding selectivity of oligopyridine-ruthenium(ii)-lysine conjugate

机译：寡吡啶-钌（ii）-赖氨酸偶联物的DNA结合选择性

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摘要

The synthesis, characterization and DNA binding properties of the complex [Ru(terpy)(4,4′-(COLysCONH_2)_2bpy)Cl]~(3+) (1) have been studied. Complex (1) hydrolyzes to (2) with a calculated rate constant K_h = 2.35 ± 0.08 × 10~(-4) s ~(-1) and binds coordinatively to ct-DNA, with a saturation r-value at about 0.1. Stabilization of the ct-DNA helix at low electrolyte (NaClO _4) concentration (10 mM) and destabilization at higher electrolyte concentrations (50-200 mM) was observed. Circular dichroism studies indicate that the hydrolyzed complex binds to DNA, increasing the unwinding of the DNA helix with an unwinding angle calculated as Φ = 12 ± 2°. The positive LD signal observed at 350 nm indicates some kind of specificity in complex orientation towards the global DNA axis. Complex (2) binds specifically to G4 on the central part of the oligonucleotide duplexes d(CGCGCG)_2 and d(GTCGAC)_2, as evidenced by NMR spectroscopy. Both lysine moieties were found to interact most likely electrostatically with the DNA phosphates, assisting the coordinative binding and increasing the DNA affinity of the complex. Photoinduced DNA cleavage by (2), upon UVA irradiation was observed, but despite its relative high DNA affinity, it was incomplete (～12%).
机译：研究了复合物[Ru（terpy）（4,4'-（COLysCONH_2）_2bpy）Cl]〜（3+）（1）的合成，表征和DNA结合特性。配合物（1）以计算的速率常数K_h = 2.35±0.08×10〜（-4）s〜（-1）水解为（2），并与ct-DNA配位结合，饱和r值约为0.1。观察到ct-DNA螺旋在低电解质（NaClO_4）浓度（10 mM）下稳定，在高电解质浓度（50-200 mM）上不稳定。圆二色性研究表明，水解的复合物与DNA结合，以Φ= 12±2°的展开角增加了DNA螺旋的展开度。在350 nm处观察到的正LD信号表明在朝向全局DNA轴的复杂方向上有某种特异性。如NMR光谱所证实的，复合物（2）与寡核苷酸双链体d（CGCGCG）_2和d（GTCGAC）_2的中央部分上的G4特异性结合。发现两个赖氨酸部分都最有可能与DNA磷酸盐发生静电相互作用，从而有助于配位结合并增加复合物的DNA亲和力。 （2），在UVA照射下观察到光诱导的DNA裂解，但是尽管其具有较高的DNA亲和力，但仍不完全（〜12％）。

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