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手性组装钌(II)多吡啶配合物形成双螺旋。

Enantioselective assembly of a ruthenium(II) polypyridyl complex into a double helix.

机构信息

Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281-S3, 9000 Gent (Belgium).

出版信息

Angew Chem Int Ed Engl. 2014 Aug 18;53(34):8959-62. doi: 10.1002/anie.201404496. Epub 2014 Jul 7.

Abstract

Evolution can increase the complexity of matter by self-organization into helical architectures, the best example being the DNA double helix. One common aspect, apparently shared by most of these architectures, is the presence of covalent bonds within the helix backbone. Here, we report the unprecedented crystal structures of a metal complex that self-organizes into a continuous double helical structure, assembled by non-covalent building blocks. Built up solely by weak stacking interactions, this alternating tread stairs-like double helical assembly mimics the DNA double helix structure. Starting from a racemic mixture in aqueous solution, the ruthenium(II) polypyridyl complex forms two polymorphic structures of a left-handed double helical assembly of only the Λ-enantiomer. The stacking of the helices is different in both polymorphs: a crossed woodpile structure versus a parallel columnar stacking.

摘要

进化可以通过自组织成螺旋结构来增加物质的复杂性,最好的例子是 DNA 双螺旋。这些结构中一个共同的特点是螺旋骨架内存在共价键。在这里,我们报告了一个前所未有的金属配合物晶体结构,该金属配合物通过非共价键构建块自组装成连续的双螺旋结构。这种由弱堆积相互作用构建的交替梯级双螺旋组装模拟了 DNA 双螺旋结构。从水溶液中的外消旋混合物开始,钌(II)多吡啶配合物形成了只有 Λ-对映体的左手双螺旋组装的两种多晶型结构。两种多晶型结构中螺旋的堆积方式不同:交叉木垛结构与平行柱状堆积。

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