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.
Recent progress has been made in the numerical modelling of neutral microgel particles with a realistic, disordered structure. In this work we extend this approach to the case of co-polymerised microgels where a thermoresponsive polymer is mixed with acidic groups. We compare the cases where counterions directly interact with microgel charges or are modelled implicitly through a Debye-Hückel description. We do so by performing extensive numerical simulations of single microgels across the volume phase transition varying the temperature and the fraction of charged monomers. We find that the presence of charges considerably alters the microgel structure, quantified by the monomer density profiles and by the form factors of the microgels, particularly close to the volume phase transition (VPT). We observe significant deviations between the implicit and explicit models, with the latter comparing more favourably to available experiments. In particular, we observe a shift of the VPT temperature to larger values as the amount of charged monomers increases. We also find that below the VPT the microgel-counterion complex is almost neutral, while it develops a net charge above the VPT. Interestingly, under these conditions the collapsed microgel still retains a large amount of counterions inside its structure. Since these interesting features cannot be captured by the implicit model, our results show that it is crucial to explicitly include the counterions in order to realistically model ionic thermoresponsive microgels.
Ionic microgel particles are intriguing systems in which the properties of thermo-responsive polymeric colloids are enriched by the presence of charged groups. In order to rationalize their properties and predict the behaviour of microgel suspensions, it is necessary to develop a coarse-graining strategy that starts from the accurate modelling of single particles. Here, we provide a numerical advancement of a recently-introduced model for charged co-polymerized microgels by improving the treatment of ionic groups in the polymer network. We investigate the thermoresponsive properties of the particles, in particular their swelling behaviour and structure, finding that, when charged groups are considered to be hydrophilic at all temperatures, highly charged microgels do not achieve a fully collapsed state, in favorable comparison to experiments. In addition, we explicitly include the solvent in the description and put forward a mapping between the solvophobic potential in the absence of the solvent and the monomer–solvent interactions in its presence, which is found to work very accurately for any charge fraction of the microgel. Our work paves the way for comparing single-particle properties and swelling behaviour of ionic microgels to experiments and to tackle the study of these charged soft particles at a liquid–liquid interface.
Poly(N-isopropylacrylamide)-based microgels are soft colloids undergoing a volume phase transition (VPT) close to ambient temperature. Although widely employed for fundamental research and application purposes, the modifications of the microgel internal structure occurring at the VPT are not yet completely understood, especially concerning the role of electrostatics. Here we study in detail, both experimentally and numerically, the effect of the addition of acrylic acid (AAc) comonomer on the microgel deswelling process. By combining viscosimetry, light scattering, and electrophoresis, we show that the progressive addition of AAc increases the microgel size, modifying their mass-to-permeability ratio, and suppresses the occurrence of the VPT, progressively shifting the microgel collapse to higher temperatures. Most interestingly, however, we find that AAc addition highly enhances the two-step deswelling of these submicronsized networks, so that the inner core collapses at temperatures always lower than those marking the transition of the outer corona. These results indicate that a net increase of the charge-density mismatch between the bulk and the surface of the microgels takes place. Numerical simulations fully confirm this scenario and clarify the impact of the charge distribution on the two-step deswelling, with mobile counterions efficiently screening the charges within the inner core while leaving more monomers ionized on the surface. Our work unambiguously shows how electrostatic interactions influence the behavior of thermosensitive microgels in an aqueous environment close to the VPT.
Hollow microgels are fascinating model systems at the crossover between polymer vesicles, emulsions, and colloids as they deform, interpenetrate, and eventually shrink at higher volume fraction or when subjected to an external stress. Here, we introduce a system consisting of microgels with a micrometer-sized cavity enabling a straightforward characterization in situ using fluorescence microscopy techniques. Similarly to elastic capsules, these systems are found to reversibly buckle above a critical osmotic pressure, conversely to smaller hollow microgels, which were previously reported to deswell at high volume fraction. Simulations performed on monomer-resolved in silico hollow microgels confirm the buckling transition and show that the presented microgels can be described with a thin shell model theory. When brought to an interface, these microgels, that we define as microgel capsules, strongly deform and we thus propose to utilize them to locally probe interfacial properties within a theoretical framework adapted from the Johnson–Kendall–Roberts (JKR) theory. Besides their capability to sense their environment and to address fundamental questions on the elasticity and permeability of microgel systems, microgel capsules can be further envisioned as model systems mimicking anisotropic responsive biological systems such as red blood and epithelial cells thanks to the possibility offered by microgels to be synthesized with custom-designed properties.
This paper was selected as Featured ARTICLES YOU MAY BE INTERESTED INTuning the permeability of regular polymeric networks by the cross-link ratio
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