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首页> 外文期刊>The journal of physical chemistry, C. Nanomaterials and interfaces >Perylenediimide-Linked DNA Dumbbells: Long-Distance Electronic Interactions and Hydrophobic Assistance of Base-Pair Melting
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Perylenediimide-Linked DNA Dumbbells: Long-Distance Electronic Interactions and Hydrophobic Assistance of Base-Pair Melting

机译:ylene二酰亚胺链接的DNA哑铃:远程电子相互作用和疏水辅助的基础对熔化。

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摘要

The synthesis and properties of synthetic DNA dumbbells having A-tract base pair domains consisting of 6-16 base pairs connected by perylenediimide (PDI) linkers are reported. The dumbbells were prepared in good yield by chemical ligation of nicked-dumbbell precursors having six or more A-T base pairs. The dumbbell structures have been investigated by a combination of electronic spectroscopy and molecular dynamics simulations. UV-visible spectra are indicative of the formation of monomeric dumbbells at room temperature in aqueous buffer in the absence of added salt. The long-wavelength region of the circular dichroism (CD) spectra is a composite of induced CD of the PDI monomers and intramolecular exciton-coupled CD between the two PDI chromophores. Weak exciton coupled CD can be observed between PDI chromophores separated by 13 base pairs, thus extending the reach of dumbbell molecular rulers. Upon heating, the dumbbells undergo base pair melting and intramolecular PDI-PDI association. Analysis of the temperature-dependent spectral data provides evidence for a three-state model in which base pair melting of the intact dumbbell results in the formation of an intermediate species which is in equilibrium with a collapsed dumbbell having intramolecular PDI-PDI stacking. The low melting temperatures of the shorter dumbbells are attributed to the partial compensation of PDI—PDI association for base pair dissociation.
机译:报道了合成的DNA哑铃的合成和性质,该哑铃具有由per二酰亚胺(PDI)接头连接的由6-16个碱基对组成的A段碱基对结构域。通过化学连接具有六个或更多A-T碱基对的切口哑铃前体,以高收率制备哑铃。通过结合电子光谱学和分子动力学模拟研究了哑铃结构。紫外可见光谱表明在室温下在没有添加盐的情况下,水性缓冲液中单体哑铃的形成。圆二色性(CD)光谱的长波区域是PDI单体的诱导CD和两个PDI生色团之间分子内的激子耦合CD的合成。在由13个碱基对分隔的PDI发色团之间可以观察到弱的激子耦合CD,从而扩展了哑铃分子标尺的作用范围。加热后,哑铃会经历碱基对熔化和分子内PDI-PDI缔合。对温度相关光谱数据的分析为三态模型提供了证据,其中完整哑铃的碱基对熔化导致形成中间物质,该中间物质与具有分子内PDI-PDI堆积的塌缩哑铃平衡。较短的哑铃的低熔化温度归因于PDI-PDI缔合对碱基对解离的部分补偿。

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