Fast photoinduced electron transfer through DNA intercalation.
Fast photoinduced electron transfer through DNA intercalation.
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DOI：
10.1073/pnas.91.12.5315
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发表时间：
1994-06
影响因子：
11.1
通讯作者：
Catherine J. Murphy;M. Arkin;N. Ghatlia;Stefan H. Bossmann;N. Turro;Jacqueline K. Barton
中科院分区：
文献类型：
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作者：
Catherine J. Murphy;M. Arkin;N. Ghatlia;Stefan H. Bossmann;N. Turro;Jacqueline K. Barton
我们报告的证据快速光诱导的电子转移介导的DNA螺旋，需要金属络合物，是狂热的嵌入剂的DNA。在这里，供体双（菲咯啉）（二吡啶并吩嗪）钌（II）[Ru（phen）2dppz 2 +]和受体双（9，10-菲醌二亚胺）（菲咯啉）铑（III）[Rh（phi）2 phen 3 +]以Kb > 10（6）M-1嵌入DNA中。在两种不同长度的DNA存在下的发光猝灭实验产生向上弯曲的Stern-Volmer图，并且发光强度的损失远远超过发射寿命的变化。在非嵌入电子受体Ru（NH3）3+（6）的存在下，Ru（phen）2dppz 2+发光的猝灭效率远低于嵌入Rh（phi）2 phen 3+猝灭剂，并遵循线性Stern-Volmer动力学;稳态和时间分辨Stern-Volmer图在尺度上相当。这些实验与涉及嵌入剂之间通过DNA螺旋的快速长程电子转移的模型一致。
We report evidence for fast photoinduced electron transfer mediated by the DNA helix that requires metal complexes that are avid intercalators of DNA. Here the donor bis(phenanthroline)(dipyridophenazine)ruthenium(II) [Ru(phen)2dppz2+] and acceptor bis(9,10-phenanthrenequinone diimine)(phenanthroline)rhodium(III) [Rh(phi)2phen3+] intercalate into DNA with Kb > 10(6) M-1. Luminescence quenching experiments in the presence of two different lengths of DNA yield upward-curving Stern-Volmer plots and the loss of luminescence intensity far exceeds the change in emission lifetimes. In the presence of a nonintercalative electron acceptor, Ru(NH3)3+(6), Ru(phen)2dppz2+ luminescence is quenched much less efficiently compared to that found for the intercalative Rh(phi)2phen3+ quencher and follows linear Stern-Volmer kinetics; steady-state and time-resolved Stern-Volmer plots are comparable in scale. These experiments are consistent with a model involving fast long-range electron transfer between intercalators through the DNA helix.