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We report on the swelling of a polymeric network in doubly thermoresponsive microgels. Silica-core double-shell and hollow double-shell microgels made of an inner poly(N-isopropylmethacrylamide) and an outer poly(N-isopropylacrylamide) shell are studied by exploiting the distinct temperature sensitivities of the polymers. The swelling states of the two shells can be tuned by temperature changes enabling three different swelling states: above, below, and between the distinct volume phase transition temperatures of the two polymers. This enables to investigate the effect of different constraints on the swelling of the inner network. Small-angle neutron scattering with contrast variation in combination with computer simulation discloses how the expansion of the inner shell depends on the material and swelling state of its constraints. In the presence of the stiff core, the microgels show a considerable interpenetration of the polymeric shells: the inner network expands into the outer deswollen shell. This in...

Characterization of switchable microgels is a major task in drug delivery science. The study of soft polymeric devices requires a combined use of spectroscopy, microscopy, and scattering approaches enabling the characterization of nanostructured features across a volume phase transition. In this work the structural changes of poly(vinyl alcohol) based thermoreversible microgel particles which incorporate p(NiPAAm-co-methacrylate) chains across the transition temperature occurring at 33 °C have been addressed by utilizing reciprocal and direct space approaches such as small angle neutron scattering, SANS, dynamic light scattering, DLS, soft transmittance X-ray microscopy, STXM, and confocal laser scanning microscopy, CLSM, respectively. The comparison between the results obtained from those approaches allows an evaluation of the driving forces acting in the transition and reveals the changes in the microgel structure at nanoscale level. The structure of the poly(vinyl alcohol) based microgel particles, inc...