On the Chirality of Self-Assembled DNA Octahedra

On the Chirality of Self-Assembled DNA Octahedra
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DOI:
10.1002/anie.200904513
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发表时间:
2010-01-01
影响因子:
16.6
通讯作者:
Mao, Chengde
Mao, Chengde
中科院分区:
化学1区
文献类型:
--
作者:
He, Yu;Su, Min;Mao, Chengde

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手性是自然界的一个重要方面。[1]大多数生物分子,如氨基酸、糖、RNA、DNA和蛋白质,都是手性的,由这些分子组装而成的大实体也是手性的。酶和细胞受体容易区分手性底物的不同立体异构体(对映异构体)的能力导致高效和立体选择性的反应和结合。对手性的理解和控制能力对于有机合成,[2]分子分离,[3]客体封装,[4]药物设计[5]和其他努力至关重要。近年来,仿生超分子自组装的探索为研究手性物体的形成提供了一种手段。这种方法提出了一种在分子水平上理解和控制手性的方法。以前的研究主要集中在非生物有机分子通过非共价相互作用的不对称组装,[6-8]如氢键,金属配位或π-π相互作用。在此,我们报告了一个定义明确的手性纳米八面体结构,它是专门由DNA分子。DNA八面体的构建涉及一个相当简单的一锅法过程,只涉及三个独特的合成DNA单链。低温电子显微镜(Cryogenic electron microscopy,cryEM)显示了分辨率为12的三维结构图,清晰地显示了DNA八面体的手性特征。DNA具有良好的分子识别能力和明确的双螺旋结构,是一种极好的纳米级建筑材料。[9]多种DNA纳米结构[10-13]已由合成DNA分子改造而成。由于天然B型DNA采用立体异构纯右手双螺旋结构,大的DNA纳米结构可能也采用手性构象。然而,DNA组装体在纳米尺度上的手性
Chirality is an essential aspect in nature.[1] Most biomolecules, such as amino acids, sugars, RNA, DNA, and proteins, are chiral, as are the large entities assembled from these molecules. The ability of enzymes and cell receptors to readily distinguish different stereoisomers (enantiomers) of chiral substrates leads to highly efficient and stereoselective reactions and binding. An understanding of and ability to control chirality is of crucial importance for organic synthesis,[2] molecular separation,[3] guest encapsulation,[4] drug design,[5] and other endeavors. In recent years, the exploration of biomimetic supramolecular self-assembly has provided a means to study the formation of chiral objects. This approach suggests a way to understand and control chirality at the molecular level. Previous studies mostly focused on the asymmetric assembly of nonbiological organic molecules through noncovalent interactions,[6–8] such as hydrogen bonds, metal coordination, or π–π interactions. Herein, we report a well-defined chiral nanooctahedron structure which is exclusively composed of DNA molecules. The construction of the DNA octahedron involves a rather simple one-pot process involving only three unique synthetic DNA single strands. Cryogenic electron microscopy (cryoEM) revealed a three-dimensional (3D) structural map with a resolution of 12, from which the chiral features of the DNA octahedron could be identified clearly.DNA is a superb nanoscale building material owing to its excellent molecular-recognition capability and well-defined double-helical structure.[9] A variety of DNA nanostructures [10–13] have been engineered from synthetic DNA molecules. Since natural B-form DNA adopts a stereoisomerically pure right-handed double-helical structure, large DNA nanostructures can presumably also adopt chiral conformations. However, the chirality of DNA assemblies at the nanoscale