Walking a Supramolecular Tightrope: A Self-Assembled Dodecamer from an 8-Aryl-2′-deoxyguanosine Derivative

Walking a Supramolecular Tightrope: A Self-Assembled Dodecamer from an 8-Aryl-2′-deoxyguanosine Derivative
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DOI:
10.1021/ja9040384
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发表时间:
2009-08-05
影响因子:
15
通讯作者:
Rivera, Jose M.
Rivera, Jose M.
中科院分区:
化学1区
文献类型:
--
作者:
Rivera-Sanchez, Maria del C.;Andujar-de-Sanctis, Ivonne;Rivera, Jose M.

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通过内部参数(即亚基中的结构信息)控制自组装超分子的性质,使得能够可靠地构建具有世界定义的尺寸和组成的组件。在这里,我们证明了亲脂性8-(3-吡啶)-2‘-脱氧鸟苷衍生物的亚基之间排斥性(例如,立体)和吸引(例如,pi-pi,偶极-偶极)之间的非共价相互作用之间的最佳平衡,使得稳定和离散的自组装十二聚体的形成成为可能。相反,异构化的8-苯基-2‘-脱氧鸟苷衍生物组装成八聚体,因为它不能参与额外的偶极-偶极相互作用。将十二聚体添加到超分子构建工具箱中,其中已经包含由其他8-芳基-2‘-脱氧鸟苷衍生物制成的八聚体和十六聚体,应该能够制备各种自组装纳米结构,其中功能元件的大小和数量可以根据具体应用进行精确的微调。
Controlling the properties of self-assembled supramolecules via intrinsic parameters (i.e., structural information in the subunits) enables the reliable construction of assemblies of welt-defined size and composition. Here we show that an optimum balance between repulsive (e.g., steric) and attractive (e.g., pi-pi, dipole-dipole) noncovalent interactions between subunits of a lipophilic 8-(3-pyridyl)-2'-deoxyguanosine derivative enables the high fidelity formation of a stable and discrete self-assembled dodecamer. In contrast, the isosteric 8-phenyl-2'-deoxyguanosine derivative assembles into an octamer because it cannot engage in additional dipole-dipole interactions. Adding dodecamers to a supramolecular construction toolbox, already containing octamers and hexadecamers made from other 8-aryl-2'-deoxyguanosine derivatives, should enable the preparation of a wide variety of self-assembled nanostructures where the size and the number of functional elements can be precisely fine-tuned for specific applications.