Self-assembly of cyclic metal-DNA nanostructures using ruthenium tris(bipyridine)-branched oligonucleotides.

Self-assembly of cyclic metal-DNA nanostructures using ruthenium tris(bipyridine)-branched oligonucleotides.
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使用钌三(联吡啶)支链寡核苷酸自组装环状金属-DNA 纳米结构。

DOI:
10.1002/anie.200460255
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发表时间:
2004
期刊:
影响因子:
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通讯作者:
H. Sleiman
H. Sleiman
中科院分区:
--
文献类型:
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作者:
Debbie Mitra;N. Di Césaré;H. Sleiman

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纳米科学的前景之一是创造包含可寻址分子成分的有序结构,这些分子成分旨在完成复杂的操作。[1]然而,尽管已经构建了许多功能性分子组件,但在纳米尺度上以故意设计的方式组装它们的方法还有待设计。[1,2]在这方面,DNA已经成为一个有前途的模板来完成这一任务,因为它独特的选择性自组装,易于编程,易于合成。[3-5]原则上,短的DNA链(10-30个碱基长)可以快速自组装成相对刚性,可编程的高阶DNA结构。[5]Seeman的开创性工作展示了在复杂的二维和三维纳米结构的组装中使用修饰的霍利迪结作为基于多核苷酸的顶点。[3a-c] DNA纳米结构也通过使用谷胱甘肽-金胶体颗粒、[3d-f]生物素-抗生物素蛋白相互作用、[3g]鸟嘌呤四联体、[3 h,i]和有机顶点来构建[3]。[3 j-l]我们感兴趣的是创建环状过渡金属-DNA纳米结构,其包含短DNA双链体作为臂和过渡金属中心作为顶点。在这些定义明确的超分子结构中,DNA作为一种纳米级的刚性分子,在空间上定位可寻址的过渡金属,这些过渡金属具有固有的性质,如发光和氧化还原活性,[6]进入有序阵列。尽管过渡金属已被用于生成3D DNA网络,[4a-c]线性DNA阵列,[4d]和金属化DNA,[4g-h]据我们所知,离散的环状金属-DNA结构以前尚未被访问。[4]在此,我们报道了一个分支的钌(ii)-DNA复合物的合成和性质,其中两个平行的DNA链连接到一个
One of the promises of nanoscience is the creation of ordered structures that contain addressable molecular components, which are designed to accomplish complex operations.[1] However, whereas many functional molecular components have already been constructed, methods to assemble them in a deliberately designed manner on the nanometer scale have yet to be devised.[1, 2] In this respect, DNA has emerged as a promising template to accomplish this task because of its uniquely selective self-assembly, ready programmability, and facile synthesis.[3–5] In principle, short (10–30-bases long) strands of DNA can rapidly self-assemble into relatively rigid, programmable, higher-order DNA structures.[5] Pioneering work by Seeman demonstrated the use of modified Holliday junctions as oligonucleotide-based vertices in the assembly of complex two-and three-dimensional nanostructures.[3a–c] DNA nanostructures have also been constructed [3] through the use of oligonucleotide–gold colloidal particles,[3d–f] biotin–avidin interactions,[3g] guanine quartets,[3h, i] and organic vertices.[3j–l]We are interested in the creation of cyclic transitionmetal–DNA nanostructures that contain short DNA duplexes as arms and transition-metal centers as vertices. In these welldefined supramolecular structures, DNA serves as a nanoscale rigid molecule to spatially position addressable transition metals, which have intrinsic properties such as luminescence and redox activity,[6] into an ordered array. Whereas transition metals have been used to generate 3D DNA networks,[4a–c] linear DNA arrays,[4d] and metalated DNA,[4g–h] to our knowledge, discrete cyclic metal–DNA structures have not been previously accessed.[4] Herein, we report the synthesis and properties of a branched ruthenium (ii)–DNA complex, in which two parallel DNA strands are linked to a