Thermoresponsive microgels are one of the most investigated types of soft colloids, thanks to their ability to undergo a Volume Phase Transition (VPT) close to ambient temperature. However, this fundamental phenomenon still lacks a detailed microscopic understanding, particularly regarding the presence and the role of charges in the deswelling process. This is particularly important for the widely used poly(N-isopropylacrylamide)–based microgels, where the constituent monomers are neutral but charged groups arise due to the initiator molecules used in the synthesis. Here, we address this point combining experiments with state-of-the-art simulations to show that the microgel collapse does not happen in a homogeneous fashion, but through a two-step mechanism, entirely attributable to electrostatic effects. The signature of this phenomenon is the emergence of a minimum in the ratio between gyration and hydrodynamic radii at the VPT. Thanks to simulations of microgels with different cross-linker concentrations, charge contents, and charge distributions, we provide evidence that peripheral charges arising from the synthesis are responsible for this behavior and we further build a universal master curve able to predict the two-step deswelling. Our results have direct relevance on fundamental soft condensed matter science and on applications where microgels are involved, ranging from materials to biomedical technologies. Significance Microgels, colloidal-scale polymer networks, are the prototype soft colloids. When the constituent polymers are thermoresponsive, they undergo a volume phase transition (VPT) from a swollen to a collapsed state at a characteristic temperature, close to ambient one, of great appeal for several applications. To describe this phenomenon, microgels are usually treated as neutral, but here we show that electrostatics needs to be taken into account. In particular, deswelling occurs via a two-step, rather than a homogeneous, particle collapse, mainly driven by peripheral charges located on the microgel corona, for which we also establish a unifying framework encompassing all studied microgels. Our work thus provides a change of perspective to describe these fascinating systems.

The low-frequency limit of the electrical conductivity (dc conductivity) of differently flexible polyions in aqueous solutions has been measured over an extended polyion concentration range, covering both the dilute and semidilute (entangled and unentangled) regime, up to the concentrated regime. The data have been analyzed taking into account the different flexibility of the polymer chains according to the scaling theory of polyion solutions, in the case of flexible polyions, and according to the Manning model, in the case of rigid polyions. In both cases, the fraction $f$ of free counterions, released into the aqueous phase from the ionizable polyion groups, has been evaluated and its dependence on the polyion concentration determined. Our results show that the counterion condensation follows at least three different regimes in dependence on the polyion concentration. The fraction $f$ of free counterions remains constant only in the semidilute regime (a region that we have named the Manning regime), while there is a marked dependence on the polyion concentration both in the dilute and in the concentrated regime. These results are briefly discussed in the light of the scaling theory of polyelectrolyte aqueous solutions.

We study the fingering instability of the interface between two miscible fluids, a colloidal suspension and its own solvent. The temporal evolution of the interface in a Hele-Shaw cell is found to be governed by the competition between the nonlinear viscosity of the suspension and an off-equilibrium, effective surface tension ${\mathrm{$\Gamma${}}}_{e}$. By studying suspensions in a wide range of volume fractions, ${\mathrm{$\Phi${}}}_{C}$, we show that ${\mathrm{$\Gamma${}}}_{e}$\sim${}{\mathrm{$\Phi${}}}_{C}^{2}$, in agreement with Korteweg's theory for miscible fluids. The surface tension exhibits an anomalous increase with particle size, which we account for using entropy arguments.

The formation and properties of smart (stimuli-responsive) membranes are reviewed, with a special focus on temperature and pH triggering of gating to water, ions, polymers, nanoparticles, or other molecules of interest. The review is organized in two parts, starting with all-smart membranes based on intrinsically smart materials, in particular of the poly(N-isopropylacrylamide) family and similar polymers. The key steps of membrane fabrication are discussed, namely the deposition into thin films, functionalization of pores, and the secondary crosslinking of pre-existing microgel particles into membranes. The latter may be free-standing and do not necessitate the presence of a porous support layer. The temperature-dependent swelling properties of polymers provide a means of controlling the size of pores, and thus size-sensitive gating. Throughout the review, we highlight “positive” (gates open) or “negative” (closed) gating effects with respect to increasing temperature. In the second part, the functionalization of porous organic or inorganic membranes of various origins by either microgel particles or linear polymer brushes is discussed. In this case, the key steps are the adsorption or grafting mechanisms. Finally, whenever provided by the authors, the suitability of smart gating membranes for specific applications is highlighted.

The interfacial tension between immiscible fluids is responsible for a wealth of every-day phenomena, from the spherical shape of small drops and bubbles to the ability to walk on water of many insects. More than a century ago, physicist and mathematician D. Korteweg postulated the existence of an effective interface tension for miscible fluids, whenever a composition gradient exists, as encountered, e.g., in many flow geometries. In this mini-review, we discuss experimental work performed in the last decades that demonstrates the existence of a positive effective interface tension in a variety of systems, from molecular, near-critical liquids to complex fluids such as polymer solutions and colloidal suspensions. The various experimental strategies that have been deployed are discussed, together with their advantages and limitations. Finally, some of the key theoretical questions still open are outlined.