The structure and stability of water-in-water emulsions was investigated in the presence of spherical, pH-sensitive microgels. The emulsions were formed by mixing aqueous solutions of dextran and PEO. The microgels consisted of cross-linked, synthetic polymers with a radius that steeply increased from 60 to 220 nm with increasing pH within a narrow range around 7.0. At all pH values between 5.0 and 7.5, the microgels were preferentially situated at the interface, but only in a narrow range between pH 7.0 and 7.5, the emulsions were stable for at least 1 week. The droplet size was visualized with confocal laser scanning microscopy and was found to be smallest in the stable pH range. Emulsions could be stabilized or destabilized by small changes of the pH. Addition of small amounts of salt led to a shift of the pH range where the emulsions were stable. The effects of varying the microgel concentration and the polymer composition were investigated.

General strategies leading to scale-span molecular self-assembly are of crucial importance in creating bulk supramolecular materials. Here, we report that under mechanical pressure, caking of the precipitated molecular self-assemblies led to bulk supramolecular films. Massive fabrication of supramolecular films became possible by employing a simple household noodle machine. The film could be endowed to acquire diversified functions by depositing various functional ingredients via coprecipitation. We expect that our current work opens up a new paradigm leading to large-scale functional solid molecular self-assembled materials.

Fabrication strategies for programmed hydrogels that provide precise spatial control with predetermined responses to external stimuli are highly desirable. In this study, a partially reversible light‐driven assembly (PRLDA) method is introduced to construct multiresponsive hydrogels utilizing microgel (MG) particle building blocks (swollen diameter of 107 nm). No other material is required to prepare the gels beyond the MGs themselves. Facile preparation of multiresponsive hydrogels that are reversibly responsive to light, pH, and temperature using phototriggered covalent interlinking of coumarin‐based MGs is demonstrated. The gels have phototuneable moduli and swelling ratios and show light‐assisted healing and reshaping. Remarkably, the intrinsic fluorescence of the gels undergoes a reversible light‐triggered wavelength‐shift. The emission peak blueshifted from 420 to 390 nm upon irradiation with 365 nm light. The PRLDA gels can be constructed using either positive or negative photopatterning. It is shown that the gels can be exploited for multiresponsive cytocompatible actuators, grippers, and ON/OFF circuit components as well as anticounterfeit gels. The PRLDA method provides new insight into programmed gel property control and has excellent potential for biomaterial and optoelectronic applications.

A new family of pH-responsive microgel-colloidosomes was prepared using microgel particles as the building blocks and macro-crosslinker. Our simple and versatile method used covalent inter-linking of vinyl-functionalised microgel particles adsorbed to oil droplets to form shells of doubly crosslinked microgels (DX MGs) and was demonstrated using two different microgel types.