Temperature-induced changes in the internal structures of poly(N-isopropylacrylamide) (pNIPAm) microgels were evaluated by small-angle X-ray scattering (SAXS), and the results were used to explain organic dye uptake by the microgels. The dye uptake experiments were conducted using two organic dyes: cationic rhodamine 6G (R6G) and anionic erythrosine. In the SAXS investigation, the internal structures of the microgels were characterized in terms of the correlation length, ξ, and the distance, d*, which originated from the local packing of the isopropyl groups of two neighboring chains. With increasing temperature up to the volume phase transition temperature (VPTT) of the microgels, the correlation length, ξ, was increased and the distance, d*, was decreased. At the same time, the amounts of the dyes taken up by the pNIPAm microgels were increased, despite a decrease in the volume of the microgels. The results indicated that the pNIPAm chains were closer to each other due to the hydrophobic association of isopropyl groups, which resulted in the growth of the hydrophobic domains. Thus, the hydrophobic interactions between the dyes and pNIPAm were probably accompanied by the domain formation. With a further increase of temperature above the VPTT, the correlation length, ξ, was decreased and then not defined because the Ornstein-Zernike type contribution disappeared, and the distance, d*, was not largely changed. At the same time, the uptake amounts of the dyes per unit volume of the microgels were also not largely changed, which behaved similar to the distance, d*. It was probably due to the fact that the internal structures of the microgels were not largely changed because the isopropyl groups were in contact with each other. The view was supported by the result of the uptake study of the nonthermoresponsive microgels which did not have the hydrophobic isopropyl groups.

The unique drying behavior of aqueous droplets that contain soft hydrogel microspheres (microgels) upon evaporation was systematically investigated. Compared to the ring-shaped deposits that are obtained from drying solid microsphere dispersions, we have previously reported that uniformly ordered thin films are obtained from drying ∼1.2 μm-sized poly( N-isopropyl acrylamide) microgel dispersions. In the present study, we thoroughly investigated several hitherto unexplored aspects of this self-organization, such as the effect of the size, chemical structure, and "softness" of the microgels (or rigid microspheres). For the macro- and microscopic observation of the drying behavior of various microsphere dispersions, an optical microscope and a digital camera were employed. The results suggested that the convection in the aqueous droplets plays an important role for the transportation of the microgels to the air/water interface, where the softness and surface activity of the microgels strongly affects the adsorption of the microgels. On the basis of these discoveries, a design concept for the rapid formation of uniform thin films of soft microgels was proposed.

Despite the tremendous efforts devoted to the structural analysis of hydrogel microspheres (microgels), many details of their structures remain unclear. Reported in this study is that thermoresponsive poly(N‐isopropyl acrylamide) (pNIPAm)‐based microgels exhibit not only the widely accepted core–shell structures, but also inhomogeneous decanano‐sized non‐thermoresponsive spherical domains within their dense cores, which was revealed by temperature‐controlled high‐speed atomic force microscopy (TC‐HS‐AFM). Based on a series of experiments, it is concluded that the non‐thermoresponsive domains are characteristic for pNIPAm microgels synthesized by precipitation polymerization, and plausible structures for microgels prepared by other polymerization techniques are proposed.

The deformation of soft hydrogel microspheres (microgels) adsorbed at the air/water interface was investigated for the first time using large poly(N-isopropyl acrylamide)-based microgels synthesized by a modified aqueous precipitation polymerization method. The deformation of the micron-sized soft microspheres could be visualized clearly and analyzed quantitatively at the air/water interface.