Owing to a unique colorimetric (typically blue-to-red) feature upon environmental stimulation, polydiacetylenes (PDAs) have been actively employed in chemosensor systems. We developed a highly accurate and simple volatile organic compound (VOC) sensor system that can be operated using a conventional smartphone. The procedure begins with forming an array of four different PDAs on conventional paper using inkjet printing of four corresponding diacetylenes followed by photopolymerization. A database of color changes (i.e., red and hue values) is then constructed on the basis of different solvatochromic responses of the 4 PDAs to 11 organic solvents. Exposure of the PDA array to an unknown solvent promotes color changes, which are imaged using a smartphone camera and analyzed using the app. A comparison of the color changes to the database promoted by the 11 solvents enables the smartphone app to identify the unknown solvent with 100% accuracy. Additionally, it was demonstrated that the PDA array sensor was sufficiently sensitive to accurately detect the 11 VOC gases.

Tubular materials formed by self-assembly of small organic molecules find great utility in chemical and material science. Conventional tubular structures often lack stability because noncovalent molecular interactions are responsible for their conformational integrities. Herein we report the development of covalently linked chromogenic organic nanotubes which are prepared by using topochemical polymerization of self-assembled macrocyclic diacetylenes (MCDAs). Crystal structures of five MCDAs having different diameters were elucidated, and four of these substances were transformed to tubular polydiacetylenes (PDA) by UV-induced polymerization. Surprisingly, MCDA-1 was found to self-assemble in stacks with a tilt angle of 62.1°, which significantly deviates from the optimal value for polymerization of 45°. This observation suggests that geometric parameters derived using linear diacetylene (DA) models might not be strictly applicable to polymerization of MCDA systems. Blue-phase PDAs obtained by polymerization of MCDA-1 and MCDA-3 have different thermochromic and solvatochromic properties, which enable them to be utilized for colorimetric differentiation of aromatic solvents including isomeric xylenes. The observations made and information obtained in this study should enhance the understanding and design of stimulus-responsive rigid organic nanotubes.

Creation of tubular structures through the self-assembly of macrocyclic molecules has gained great attention in the chemical, biochemical, and material sciences. Through a designed introduction of two octaethylene oxide and two diacetylene moieties, we prepared a macrocycle MCDA–BisOEG, which is water-soluble and photopolymerizable and displays a lower critical solution temperature (LCST) behavior. The hydrodynamic diameter of MCDA–BisOEG, measured by dynamic light scattering method, was ca. 6.5 nm at 25 °C and increased sharply to ca. 2 μm at temperatures above 34 °C (LCST). Below the LCST, the macrocycle in aqueous solution formed tubular structures, which upon UV irradiation generated blue conjugated polydiacetylene (PDA) nanotubes. The PDA nanotubes undergo a blue-to-red color change when heated above the LCST. No polymerization occurs above the LCST owing to the disordered aggregation of the diacetylene monomer. This is the first example of the preparation of a macrocycle-based, thermoresponsive, conjugated polymer nanotube in aqueous solution.

Sodium batteries have been recognized as a promising alternative to lithium‐ion batteries. However, the liquid electrolyte used in these batteries has inherent safety problems. Polymer electrolytes have been considered as safer and more reliable electrolyte systems for rechargeable batteries. Herein, a thermoplastic polyurethane elastomer‐based gel polymer electrolyte with high ionic conductivity and high elasticity was reported. It had an ambient‐temperature ionic conductivity of 1.5 mS cm−1 and high stretchability, capable of withstanding 610 % strain. Coordination between Na+ ions and polymer chains increased the degree of salt dissociation in the gel polymer electrolyte compared with the liquid electrolyte. An Na/Na3V2(PO4)3 cell assembled with gel polymer electrolyte exhibited good cycling performance in terms of discharge capacity, cycling stability, and rate capability, which was owing to the effective trapping ability of organic solvents in the polymer matrix and uniform flux of sodium ions through the gel polymer electrolyte.

Owing to their capability of forming extensive hydrogen bondings and the facile introduction of chirality, cyclic dipeptides (CDPs) have gained great attention as scaffolds for functional supramolecules. Surprisingly, introduction of a photopolymerizable diacetylene (DA) moiety to the CDP afforded nanotubular structures with enhanced stability and reversible thermochromism. A series of CDP-containing DAs (CDP-DAs) are prepared by coupling 10,12-pentacosadiynoic acid with CDPs, cyclo(-Gly-Ser) and cis/trans cyclo(-Ser-Ser). Fabrication of CDP-DA self-assemblies in a polar chloroform and methanol solvent mixture affords nanotubes comprising single-wall and multiwall structures. The self-assembly behavior and morphology characteristic are examined by scanning electron microscopy and transmission electron microscopy. Next, X-ray diffraction analysis confirms well-ordered lamellar structures with a perfect agreement with the bilayer formation leading to the tubular structure via lamellar scrolling behavior. Upon UV irradiation, monomeric CDP-DA tubular assemblies result in the blue-colored CDP/polydiacetylene (PDA) nanotubes. Interestingly, CDP/PDA nanotubes exhibit a reversible blue-to-red color change for over 10 consecutive thermal cycles. The CDP-DA/PDA supramolecular system demonstrates potential applications in developing stimulus-responsive functional materials.