Bell T W, Jousselin H
Department of Chemistry, State University of New York, Stony Brook 11794-3400.
Nature. 1994 Feb 3;367(6462):441-4. doi: 10.1038/367441a0.
Spontaneous self-organization of helical and multiple-helical molecular structures occurs on several levels in living organisms. Key examples are alpha-helical polypeptides, double-helical nucleic acids and helical protein structures, including F-actin, microtubules and the protein sheath of the tobacco mosaic virus. Although the self-assembly of double-helical transition-metal complexes bears some resemblance to the molecular organization of double-stranded DNA, selection between monohelical, double-helical and triple-helical structures is determined largely by the size and geometrical preference of the tightly bound metal. Here we present an example of double-helical assembly induced by the weaker and non-directional interactions of an alkali-metal ion with an organic ligand that is pre-organized into a coil. We have characterized the resulting complex by two-dimensional NMR and fast-atom-bombardment mass spectrometry. These results provide a step toward the creation of molecular tubes or ion channels consisting of intertwined coils.
螺旋状和多螺旋状分子结构的自发自组装在生物体的多个层面上都会发生。关键例子包括α - 螺旋多肽、双螺旋核酸以及螺旋状蛋白质结构,其中有F - 肌动蛋白、微管和烟草花叶病毒的蛋白质外壳。尽管双螺旋过渡金属配合物的自组装与双链DNA的分子组织有一些相似之处,但单螺旋、双螺旋和三螺旋结构之间的选择很大程度上取决于紧密结合金属的大小和几何偏好。在此,我们展示了一个由碱金属离子与预先形成线圈状的有机配体之间较弱且无方向性的相互作用所诱导的双螺旋组装的例子。我们通过二维核磁共振和快原子轰击质谱对所得配合物进行了表征。这些结果为创建由相互缠绕的线圈组成的分子管或离子通道迈出了一步。