The complete understanding of the mechanism driving colloid-polyelectrolyte complexation still represents a fundamental problem of great interest in soft matter. Polyelectrolyte adsorption onto oppositely charged surfaces represents the core of this problem and a number of theoretical studies, using different approaches, have been published on this subject.During the past few decades, colloid-multivalent ion complexation has been investigated by using either model systems, such as solid hard colloids, soft colloids of biological interests, or hydrophilic globular proteins6. In all cases two distinct but intimately related phenomena accompany and drive the self-assembly, i.e. charge-inversion and reentrant condensation.Although these phenomena have been observed in a variety of polyelectrolyte-colloid mixtures in different conditions, in all previously reported works the charge density on the colloid surface was fixed, or, at least, it could not be changed without changing the ionic strength or the pH of the suspending medium. Thermoresponsive microgels, whose synthesis is initiated by charged groups and is equivalent to an end-group functionalization, are characterized by a thermodynamic volume phase transition (VPT) that gives the opportunity to tune finely the adsorption of polyelectrolytes simply by changing temperature. Indeed, by controlling the particle volume, the VPT affects dramatically the microgel charge density and hence the polyelectrolyte adsorption.We investigated the complexation of thermoresponsive anionic poly(Nisopropylacrylamide) (PNiPAM) microgels and cationic -polylysine (epsilon-PLL) chains. By combining electrophoresis, light scattering, transmission electron microscopy (TEM) and dielectric spectroscopy (DS) we studied the adsorption of epsilon-PLL onto the microgel networks and its effect on the stability of the suspensions. We show that the volume phase transition (VPT) of the microgels triggers a large polyion adsorption. Two interesting phenomena with unique features occur: a temperature-dependent microgel overcharging and a complex reentrant condensation. The latter may occur at fixed polyion concentration, when temperature is raised above the VPT of microgels, or by increasing the number density of polycations at fixed temperature. TEM and DS measurements unambiguously show that short PLL chains adsorb onto microgels and act as electrostatic glue above the VPT. By performing thermal cycles, we further show that polyion-induced clustering is a quasi-reversible process: within the time of our experiments large clusters form above the VPT and partially re-dissolve as the mixtures are cooled down.Finally we give a proof that the observed phenomenology is purely electrostatic in nature: an increase of the ionic strength gives rise to the polyion desorption from the microgel outer shell. By showing that the VPT of thermoresponsive ionic microgels can be employed to trigger polyion adsorption and tune reentrant microgel condensation, our work lays the foundation for a groundbreaking strategy to tune electroadsorption ruled by temperature and that can be employed in a variety of fields spanning wastewater and soil remediation, nanoencapsulation of small charged nanoparticles, and selective drug delivery.

By combining rheology, light scattering, small angle X-ray scattering and simulations we explore the glassy dynamics of soft colloids using microgels and charged particles interacting by steric and screened Coulomb interactions, respectively. In the supercooled regime, the structural relaxation time (SRT) of both systems grows steeply with volume fraction, reminiscent of the behavior of colloidal hard sphere systems [1]. This suggests that softness has no impact on the growth of the SRT on approaching the glass transition, as confirmed by computer simulations. We show that the onset of a finite yield-stress, occurring within the supercooled regime, systematically corresponds to a minimum of the stretching exponent characterizing the decay of the two-time intensity autocorrelation function.Softness becomes relevant only at very large packing fractions, when the system falls out of equilibrium. In this non-equilibrium regime, the SRT depends surprisingly weakly on packing fraction and time correlation functions exhibit compressed exponential decays consistent with internal stress-driven relaxation. The transition to this novel regime coincides with the onset of an anomalous decrease of local order with increasing density, reminiscent of the reentrant glass transition predicted theoretically in ultrasoft systems [2,3], and corresponds to a weakening of the volume fraction dependence of the plateau modulus of the suspensions. We propose that these peculiar dynamics result from a competition between the non-equilibrium aging dynamics of the glassy state and the tendency of soft systems to refluidize at high packing fractions.

In our work we report the measurement of non-equilibrium interfacial tension of polymer and hard sphere suspensions in contact with their own solvent. By visualizing fingering instability (VF) in radial Hele-Shaw geometry, appearing when the solvent displaces suspensions of colloids or polymers, we measure interfacial tensions in function of the volume fraction of the suspended objects, showing that the internal degrees of freedom of the particles drive the low volume fraction behavior (Figure 1). Our results support the existence of a positive tension between miscible fluids, confirm the quadratic scaling predicted by Korteweg [4] for long linear and crosslinked polymers and show a positive rapidly growing tension for hard sphere suspensions up to maximum packing, whose description necessitates a theoretical framework going beyond the classic square gradient model. We rationalize our findings assuming the suspension/solvent interface in local thermodynamic equilibrium, computing explicitly the square gradient contribution to the interfacial tension for polymer/solvent and simple molecular liquid mixtures and proposing a phenomenological model capturing the compositional dependence of the interfacial tension for large concentration gradients. Finally we include and analyze data reported in literature and obtained via spinning drop tensiometry that validate the model and we propose the analysis of fluid dynamic instability as a new tool to probe interfacial stresses.

We explore the glassy dynamics of soft colloids using microgels and charged particles interacting by steric and screened Coulomb interactions, respectively. In the supercooled regime, the structural relaxation time τα of both systems grows steeply with volume fraction, reminiscent of the behavior of colloidal hard spheres. Computer simulations confirm that the growth of τα on approaching the glass transition is independent of particle softness. By contrast, softness becomes relevant at very large packing fractions when the system falls out of equilibrium. In this nonequilibrium regime, τα depends surprisingly weakly on packing fraction, and time correlation functions exhibit a compressed exponential decay consistent with stress-driven relaxation. The transition to this novel regime coincides with the onset of an anomalous decrease in local order with increasing density typical of ultrasoft systems. We propose that these peculiar dynamics results from the combination of the nonequilibrium aging dynamics expected in the glassy state and the tendency of colloids interacting through soft potentials to refluidize at high packing fractions.