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首页> 外文期刊>Chemistry: A European journal >DNA Sequence and ancillary ligand modulate the biexponential emission decay of intercalated [Ru(L)_2dppz]~(2+) enantiomers
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DNA Sequence and ancillary ligand modulate the biexponential emission decay of intercalated [Ru(L)_2dppz]~(2+) enantiomers

机译：DNA序列和辅助配体调节嵌入的[Ru（L）_2dppz]〜（2+）对映异构体的双指数发射衰减

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摘要

The bi-exponential emission decay of [Ru(L)_2dppz]~(2+) (L=N,N'-diimine ligand) bound to DNA has been studied as a function of polynucleotide sequence, enantiomer, and nature of L (phenanthroline vs. bipyridine). The lifetimes (τ_i) and pre-exponential factors (α_i) depend on all three parameters. With [poly(dA-dT)] _2, the variation of α_i with [Nu]/[Ru] has little dependence on L for λ-[Ru(L)_2dppz]~(2+) but a substantial dependence for δ-[Ru(L)_2dppz]~(2+). With [poly(dG-dC)]_2, by contrast, the λ-enantiomer α_i values depend strongly on the nature of L, whereas those of the δ-enantiomer are relatively unaffected. DNA-bound linked dimers show similar photophysical behaviour. The lifetimes are identified with two geometries of minor-groove intercalated [Ru(L)_2dppz]~(2+), resulting in differential water access to the phenazine nitrogen atoms. Interplay of cooperative and anti-cooperative binding resulting from complex-complex and complex-DNA interactions is responsible for the observed variations of α_i with binding ratio. [Ru(phen) _2dppz]~(2+) emission is quenched by guanosine in DMF, which may further rationalise the shorter lifetimes observed with guanine-rich DNA.
机译：研究了与DNA结合的[Ru（L）_2dppz]〜（2+）（L = N，N'-diimine配体）的双指数发射衰减与多核苷酸序列，对映异构体和L（菲咯啉对联吡啶）。寿命（τ_i）和指数前因子（α_i）取决于所有三个参数。对于[poly（dA-dT）] _2，α_i随[Nu] / [Ru]的变化对λ-[Ru（L）_2dppz]〜（2+）的L依赖性很小，但对δ- [Ru（L）_2dppz]〜（2+）。相反，对于[poly（dG-dC）] _ 2，λ-对映体的α_i值很大程度上取决于L的性质，而δ-对映体的α-i值相对不受影响。与DNA结合的二聚体显示出相似的光物理行为。寿命是通过两种几何形状的小沟槽插入[Ru（L）_2dppz]〜（2+）来确定的，这导致水可分别进入吩嗪氮原子。由复合物-复合物和复合物-DNA相互作用产生的合作和反合作结合的相互作用是观察到的α_i随结合率的变化的原因。 [Ru（phen）_2dppz]〜（2+）的发射被DMF中的鸟苷淬灭，这可能进一步合理化了富含鸟嘌呤DNA的较短寿命。

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