LAUSR

ConspectusNanopore structures in nature play a crucial role in performing many sophisticated functions such as signal transduction, mass transport, ion channel, and enzyme reaction. Inspired by pore-forming proteins, considerable effort has been made to design self-assembling molecules that are able to form nanostructures with internal pores in aqueous media. These nanostructures offer ample opportunity for applications because their internal pores are able to perform a number of unique functions required for a confined nanospace. However, unlike nanopore assembly in nature, the synthetic nanopore structures are mostly based on a fixed pore that impedes performing adaptable regulation of properties to environmental change. This limitation can be overcome by integration of hydrophilic oligo(ethylene oxide) dendrons into aromatic building blocks for nanopore self-assembly, because the dendritic chains undergo large conformational changes triggered by environmental change. The transition of the oligoether chains triggers the aromatic nanopore assembly to undergo reversible pore deformation through closing, squeezing, and shape change without structural collapse. These switching properties allow the aromatic nanopore structures to perform adaptable, complex functions which are difficult to achieve using a fixed pore assembly.In this Account, we summarize our recent progress in the development of switchable nanopore structures by self-assembly of rigid aromatic amphiphiles grafted by hydrophilic oligo(ethylene oxide) dendrons in aqueous media. We show that combining oligoether chains into aromatic segments generates switchable aromatic nanopore structures in aqueous media such as hollow tubules, toroidal structures, and 2D porous sheets depending on the shape of the aromatic building block. Next, we discuss the chemical principle behind the switching motion of the aromatic nanopore structures triggered by external stimuli. We show that the internal pores of the aromatic nanostructures are able to undergo reversible switching between open-closed or expanded-contracted states triggered by external stimuli such as temperature, pH, and salts. In the case of toroidal structures, closed ring-like aromatic frameworks can be spirally open triggered by heat treatment, which spontaneously initiate helical polymerization. Additionally, we discuss switchable functions carried out by the aromatic nanopores such as driving helicity inversion of DNA, consecutive enzymatic action, reversible actuation of lipid vesicles, and pumping of captured guests out of internal pores. By understanding the underlying chemical principle required for dynamic mechanical motion, aromatic assembly can be exploited more broadly to create emergent nanopore structures with functions as complex as those of biological systems.