Co-solvent polarity tuned thermochromic nanotubes of cyclic dipeptide–polydiacetylene supramolecular system

Abstract

The cooperative non-covalent interactions arising from structurally integrated multiple molecules have emerged as a powerful tool for the creation of functional supramolecular structures. Herein, we constructed cyclic dipeptide (CDP)–polydiacetylene (PDA) conjugate (CDP–DA) by introducing cyclo(L-Phe-L-Lys) to the linear 10,12-pentacosadiynoic acid. Owing to extensive hydrogen bonding characteristics, together with structural chirality of cyclo(L-Phe-L-Lys) and strong π–π stacking diacetylenic template, CDP–DA generated supramolecular nanotubes. The structural visualization using scanning and transmission electron microscopy revealed chloroform/methanol co-solvent polarity tuned morphological transformation of intrinsic lamellar assemblies into nanotubes comprising single-wall and multi-wall structure. The mechanistic understanding by X-ray diffraction patterns confirms bilayer organization in lamellar structure, which forms nanotubes via a gradual lamellar curling-to-scrolling process. The supramolecular CDP–DA nanotubes are transformed into the rigid covalently cross-linked blue-phase polydiacetylene (CDP–PDA) by UV irradiation. Very interestingly, the blue-phase nanotubes display reversible thermochromic changing temperature up to 150 °C with excellent repeatability over a dozen thermal cycles. This work provides an efficient strategy for precise morphological control and aiding the perspective for development in nanostructures for functional devices.