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Kameta, N; Shimizu, T
Nanoscale, 2020-Feb-06, Volume: 12, Issue: 5Journal Article
Self-assembly of a polythiophene-conjugated glycolipid exclusively produced square sheets a few micrometers on each side. Seventeen hours after the sheets were dispersed in ethanol at 25 °C, they suddenly started to roll up, and eventually they were completely transformed into nanotubes. The onset timing of the roll-up was temperature-dependent. The roll-up involved rearrangement of the molecular packing within the bilayer membranes, which was accompanied by strengthening of the intermolecular hydrogen bonds, alteration of the polythiophene aggregation mode and enhancement of supramolecular chirality due to chiral packing. The nanotubes exhibited not only strong fluorescence derived from J-type aggregation of the polythiophene aromatic moiety but also circularly polarized luminescence (CPL) originating from the left-handed helicity of the polythiophene main chain backbone. Because the CPL onset was concurrent with the sheet roll-up, the CPL onset was also able to be controlled by varying the temperature. Such delayed CPL onset has never been reported in chiral supramolecular structures, in which CPL onset and helicity inversion usually begin immediately upon application of a stimulus and then progress either quickly or gradually. Our findings can be expected to facilitate the development of new stimulus-responsive supramolecular structures that can be used for delayed-action capsules or optical switching devices.
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