Supramolecular Polymer Network-Mediated Structural Phase Transitions within Polymeric Micelles in Aliphatic Alcohols.

Self-complementary supramolecular polymers (SCSPs), an efficient combination of sextuple hydrogen-bonded dimer moieties and a temperature-responsive polymer, can promote the construction of stable supramolecular polymer networks (SPNs) that enable the formation of well-defined nanospherical micelles in aliphatic alcohols. These micelles undergo tailorable, thermoresponsive phase transitions at the upper critical solution temperature (UCST) and have a desirable spherical morphology and size ranges, thus, are potential candidates for applications in interfacial engineering and biomedical fields. Moreover, concentration-dependent UCST measurements and variable-temperature experiments indicated that the hydrogen-bonded complexes are strong enough to form stable intermolecularly entangled SPNs within the micelles, even above the UCST or at low concentrations in solution, which enables the micelles to undergo reversible temperature-dependent conformational changes between insoluble and soluble globules without significant changes in particle size or size distribution. Thus, this newly discovered system offers a new approach toward the development of next-generation temperature-responsive SCSPs with the desired structural stability that undergoes UCST transitions.