Morphological Transitions of a Photoswitchable Aramid Amphiphile Nanostructure.

Kim, Dae-Yoon; Christoff-Tempesta, Ty; Lamour, Guillaume; Zuo, Xiaobing; Ryu, Ki-Hyun; Ortony, Julia H · Nano Lett · 2021

basic_science · Level V

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Abstract

Self-assembly of small amphiphilic molecules in water can lead to nanostructures of varying geometries with pristine internal molecular organization. Here we introduce a photoswitchable aramid amphiphile (AA), designed to exhibit extensive hydrogen bonding and robust mechanical properties upon self-assembly, while containing a vinylnitrile group for photoinduced <i>cis-trans</i> isomerization. We demonstrate spontaneous self-assembly of the vinylnitrile-containing AA in water to form nanoribbons. Upon UV irradiation, <i>trans</i>-to-<i>cis</i> isomerizations occur concomitantly with a morphological transition from nanoribbons to nanotubes. The nanotube structure persists in water for over six months, stabilized by strong and collective intermolecular interactions. We demonstrate that the nanoribbon-to-nanotube transition is reversible upon heating and that switching between states can be achieved repeatedly. Finally, we use electron microscopy to capture the transition and propose mechanisms for nanoribbon-to-nanotube rearrangement and vice versa. The stability and switchability of photoresponsive AA nanostructures make them viable for a range of future applications.