Development of Toroidal Nanostructures by Self-Assembly: Rational Designs and Applications
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- 作者：Yongju Kim ; Wen Li ; Suyong Shin ; Myongsoo Lee
- 刊名：Accounts of Chemical Research
- 出版年：2013
- 出版时间：December 17, 2013
- 年：2013
- 卷：46
- 期：12
- 页码：2888-2897
- 全文大小：722K
- 年卷期：v.46,no.12(December 17, 2013)
- ISSN：1520-4898
文摘
Toroidal nanostructures are symmetrical ring-shaped structures with a central internal pore. Interestingly, in nature, many transmembrane proteins such as 尾-barrels and 伪-helical bundles have toroidal shapes. Because of this similarity, toroidal nanostructures can provide a template for the development of transmembrane channels. However, because of the lack of guiding principles for the construction of toroids, researchers have not widely studied the self-assembly of toroidal nanostructures as compared with the work on other supramolecular architectures.
In this Account, we describe our recent efforts to construct toroidal nanostructures through the self-assembly of rationally designed building blocks. In one strategy for building these structures, we induce interfacial curvatures within the building blocks. When we laterally graft a bulky hydrophilic segment onto a p-oligophenyl rod or 尾-sheet peptides, the backbones of the self-assembled structures can bend in response to the steric effect of these large side groups, driving the p-oligophenyl rod or 尾-sheet peptides to form nanosized toriods. In another strategy, we can build toroids from bent-shaped building blocks by stacking the macrocycles. Aromatic segments with an internal angle of 120掳 can associate with each other in aqueous solution to form a hexameric macrocycle. Then these macrocycles can stack on top of each other via hydrophobic and 蟺鈥撓€ interactions and form highly uniform toroidal nanostructures. We provide many examples that illustrate these guiding principles for constructing toroidal nanostructures in aqueous solution.
Efforts to create toroidal nanostructures through the self-assembly of elaborately designed molecular modules provide a fundamental approach toward the development of artificial transmembrane channels. Among the various toroids that we developed, a few nanostructures can insert into lipid membranes and allow limited transport in vesicles.
In this Account, we describe our recent efforts to construct toroidal nanostructures through the self-assembly of rationally designed building blocks. In one strategy for building these structures, we induce interfacial curvatures within the building blocks. When we laterally graft a bulky hydrophilic segment onto a p-oligophenyl rod or 尾-sheet peptides, the backbones of the self-assembled structures can bend in response to the steric effect of these large side groups, driving the p-oligophenyl rod or 尾-sheet peptides to form nanosized toriods. In another strategy, we can build toroids from bent-shaped building blocks by stacking the macrocycles. Aromatic segments with an internal angle of 120掳 can associate with each other in aqueous solution to form a hexameric macrocycle. Then these macrocycles can stack on top of each other via hydrophobic and 蟺鈥撓€ interactions and form highly uniform toroidal nanostructures. We provide many examples that illustrate these guiding principles for constructing toroidal nanostructures in aqueous solution.
Efforts to create toroidal nanostructures through the self-assembly of elaborately designed molecular modules provide a fundamental approach toward the development of artificial transmembrane channels. Among the various toroids that we developed, a few nanostructures can insert into lipid membranes and allow limited transport in vesicles.