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Creation of structures and functions of artificial DNAs directed towards nano-assembly of metal complexes

创建针对金属复合物纳米组装的人工 DNA 的结构和功能

基本信息

批准号：
14340206
负责人：
SHIONOYA Mitsuhiko
金额：
$ 9.66万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2003
项目状态：
已结题

项目摘要

The strategy of replacing DNA natural bases by alternative ones has allowed the modification of DNA in a highly specific and site-selective manner, because DNA has a structural basis to array predesigned building blocks. We have recently envisioned the replacement of hydrogen-bonded base pairing present in natural DNA by metalmediated base pairing. Incorporation of such metal-induced base pairs into DNA would not only affect the assembly-disassembly processes and the structure of DNA double strands but also confer a variety of metal-based functions upon DNA. The chemistry thus interfaces with both life sciences and materials scienceAlong this line, we designed and synthesized metal-mediated base pairs with nucleosides bearing a phenylenediamine, a catechol, a 2-aminophenol, a pyridine, or a hydroxypyridone as the nucleobase. Some of them were successfully incorporated into DNA and were found to stabilize the duplex or triplex structures. Recently, we reported the synthesis of a series of artificial oligonucleotides, d(5 -GH_nC-3 ) (n = 1-5), using hydroxypyridone nucleobases (H) as flat bidentate ligands. Right-handed double helices of the oligonucleotides, nCu^<2+> d(5 -GH_nC-3 )_2 (n = 1-5), were quantitatively formed through Cu^<2+>-mediated alternative base pairing (H-Cu^<2+>-H), where the Cu^<2+> incorporated into each complex were aligned along the helix axes inside the duplexes with the Cu^<2+>-Cu^<2+> of 3.7 -0.1 angstrom. The Cu^<2+> ions were coupled ferromagnetically with one another through unpaired d electrons to form magnetic chains.

用替代碱基取代DNA天然碱基的策略使DNA能够以高度特异性和位点选择性的方式进行修饰，因为DNA具有排列预先设计的构建块的结构基础。我们最近设想用金属介导的碱基配对来取代天然DNA中存在的氢键碱基配对。将这种金属诱导的碱基对掺入DNA中，不仅会影响DNA的组装-拆解过程和DNA双链的结构，还会赋予DNA一系列基于金属的功能。在这条线上，我们设计和合成了以苯二胺、邻苯二酚、2-氨基苯酚、吡啶或羟基吡啶酮为碱基的核苷。其中一些化合物被成功地掺入到DNA中，并被发现稳定了双链或三链结构。最近，我们报道了一系列人工寡核苷酸d(5-GH_nC-3)(n=1-5)的合成。寡核苷酸的右旋双螺旋NCu^&lt；2+&gt；d(5-GH_NC-3)_2(n=1-5)是通过Cu^&lt；2+&gt；介导的替代碱基配对(H-Cu^&lt；2+&gt；-H)定量形成的，其中掺入每个络合物中的Cu^&lt；2+&gt；沿双链体内的螺旋轴与3.7-0.1埃的Cu^&lt；2+&gt；铜离子通过未成对的d电子相互铁磁耦合，形成磁链。