In the past two decades, we have witnessed significant progress in developing high performance stimuli-responsive polymeric materials. This review focuses on recent developments in the preparation and application of patterned stimuli-responsive polymers, including thermoresponsive layers, pH/ionic-responsive hydrogels, photo-responsive film, magnetically-responsive composites, electroactive composites, and solvent-responsive composites. Many important new applications for stimuli-responsive polymers lie in the field of nano- and micro-fabrication, where stimuli-responsive polymers are being established as important manipulation tools. Some techniques have been developed to selectively position organic molecules and then to obtain well-defined patterned substrates at the micrometer or submicrometer scale. Methods for patterning of stimuli-responsive hydrogels, including photolithography, electron beam lithography, scanning probe writing, and printing techniques (microcontact printing, ink-jet printing) were surveyed. We also surveyed the applications of nanostructured stimuli-responsive hydrogels, such as biotechnology (biological interfaces and purification of biomacromoles), switchable wettability, sensors (optical sensors, biosensors, chemical sensors), and actuators.
Environmental stimuli-responsive nucleobase-functionalized supramolecular polymers, a combination of oligomeric polypropylene glycol segments as a thermosensitive element and hydrogen-bonded uracil as a photosensitive moiety, were successfully developed and undergo spontaneous self-assembly to form uniform nanosized micelles via self-complementary double hydrogen bonding interactions between the uracil moieties in an aqueous environment. These micelles exhibit unique properties such as dual thermo-and photoresponsiveness, controllable lower critical concentration solution temperature (LCST), photoreactivity, and morphological transformation, making them highly attractive for various applications. More importantly, phase transitions and morphological studies confirmed the LCST behavior, size, and shape of the micelles can be easily tuned by adjusting the concentration and duration of ultraviolet irradiation of samples in aqueous solution, indicating introduction of uracil molecules into a water-soluble polymer matrix may represent a promising approach toward development of multiple stimuliresponsive polymeric micelles whose self-assembly behavior can be manipulated. In view of the ease of fabrication, high biocompatibility, multifunctionality, and tailorable micellar properties, this newly developed supramolecular micelle may be a promising candidate nanocarrier for controlled drug delivery and bioimaging systems.
Polyimide-silica (PI-SiO 2 ) hybrids with a nanostructure was obtained using the nonaqueous sol-gel process by polycondensation of phenyltriethoxysilane in a polyamic acid solution. Self-catalyzed hydrolysis of phenyl-substituted akoxysilane and modification on the polyimide structure are applied and result in highly compatible PI-SiO 2 hybrids. Transparent PI-SiO 2 with a high silica content of about 45% was thus obtained. The prepared PI-SiO 2 films were characterized by infrared spectrometry, 29 Si-NMR, thermogravimetric analysis, differential scanning calorimetry, and scanning electron microscopy. These characterizations showed the silica influence on the properties of the hybrid. The thermal expansion coefficient of the PI-SiO 2 and the temperature correlation were also established for probing the potential for application.
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