Peculiarities of Emulsions Stabilized by Stimuli-Responsive Interpenetrating Polymeric Network Microgels.

Emulsions have become a crucial product form in various industries in modern times. Expanding the class of substances used to stabilize emulsions can improve their stability or introduce new properties. Particularly, the use of stimuli-responsive microgels makes it possible to create "smart" emulsions whose stability can be controlled by changing any of the specified stimuli. Thus, finding new ways to stabilize emulsions may broaden their application. In this work, for the first time, we applied microgels based on interpenetrating polymeric networks (IPNs) of poly(N-isopropylacrylamide) (PNIPAM) and poly(acrylic acid) (PAA) as stabilizing agents for "oil-in-water" emulsions. We have demonstrated that emulsions stabilized by such soft particles can remain colloidally stable for an extended period, even after being heated up to 40 °C, which is above the lower critical solution temperature (LCST) of PNIPAM. On the contrary, the emulsions stabilized by PNIPAM homopolymer microgels were broken upon heating. To understand the stabilization mechanism of the emulsions, mesoscopic computer simulations were performed to study the IPN microgels at the liquid-liquid interface. The simulations demonstrated that when the first subnetwork (PNIPAM) collapses, the particle adopts a flattened core-shell morphology with a highly swollen PAA-rich shell and a collapsed PNIPAM-rich core. Unlike its PNIPAM homopolymer counterpart, the IPN microgel maintains its three-dimensional shape, which provides stability to the microgel-based emulsions over a wide range of temperatures. Our combined findings could be useful in developing new approaches to emulsions' storage, biphasic catalysis, and lubrication of mechanisms in various operating and climatic conditions.

Compression and Ordering of Hollow Microgels in Monolayers Formed at Liquid-Liquid Interfaces.

Monolayers of polymer microgels with a spherical cavity adsorbed at the liquid-liquid interface were studied using mesoscopic computer simulations. One liquid, named water, was always considered as a good solvent, while the microgel solubility in the second liquid, named oil, was varied. The symmetric and asymmetric cases of vanishing and the strong differences in solubility between the network particles and the liquids were considered. The simulations provided us with an insight into the shape and volume changes of the microgels upon compression, making it possible to relate the response of the individual network with the collective order and structure of the monolayer. Similar to regular microgels, the compression of the monolayer of hollow particles led to a decrease in lateral sizes accompanied by shape transformation from a flattened to a nearly spherical shape. However, the presence of a cavity filled with solvent caused some unique differences in the behavior of the system. The adsorption pathway of hollow microgels at the liquid interface predefines: (a) the position of the particles with respect to the interface and (b) the structure of the monolayer. A striking discovery is that in the symmetric case of similar solubility of the microgel in both liquids, it is possible to produce a monolayer in which one part of the network faces the aqueous phase and the other part faces the oil phase. The polymer concentration profiles plotted along the normal to the interface reveal a redistribution of polymeric mass of the microgels relative to the interface, distinguishing between the microgels whose cavities are filled with water and oil, respectively. Moreover, the ratio between the microgels faced in water and oil does not change upon compression and predetermines the response and order of the monolayer.

Swelling, collapse and ordering of rod-like microgels in solution: Computer simulation studies.

Polymer microgels have proven to be highly promising macromolecular objects for a wide variety of applications. In particular, the soft particles of an anisotropic (rod-like) shape are of special interest because of their potential use in tissue engineering or materials design. However, a little is known about the physical behavior of such microgels in solution, which inspired us to study them using mesoscopic computer simulations. For single networks, depending on the solvent quality, the dimensional characteristics were obtained for microgels of different molecular weight, crosslinking density and aspect ratio. In particular, the conditions for the rod-to-rod (preserving the nonspherical shape) and rod-to-sphere collapse were found. In addition, the effect of the liquid-crystalline (LC) ordering was demonstrated for the ensemble of rod-like microgels at different swelling ratios, and the influence of microgel aspect ratio on the volume fraction of the LC transition was shown.

Swift Janitor: Efficient Absorption of a Minor Component from the Mixtures of Immiscible Liquids by Thermoresponsive Macroscopic and Microscopic Hydrogels.

Polymer hydrogels are known to be efficient absorbents of various aqueous solutions. Along with the hydrophilicity of the polymer network, the presence of specific functional groups is required for the absorption of respective solutes. Alternatively, a selective uptake can be realized without any specific attraction of solutes to the network, which is shown in this paper. By combining experimental and simulation approaches, we demonstrated that thermoresponsive poly(N-isopropylacrylamide) gels and microgels in compositionally strongly asymmetric water/1-octanol mixtures selectively uptake the minor (1-octanol) component. Initially swollen in water, the gels substitute water by the organic solvent upon the addition of its small fraction into aqueous solution. In turn, for microgels, it was shown that the single particles could absorb the amount of the organic liquid more than two times higher than their mass while preserving the colloidal stability. At the same time, the accumulation of 1-octanol in the networks "switches off" the temperature response. The mesoscopic computer simulations revealed a physical reason and molecular picture of the phenomenon. Absorption of the minor component by the gels is caused by the decrease in water/1-octanol interfacial tension due to the formation of the dense polymer layer at the interface. The simulations allowed tracking the evolution of the size and the internal structure of the single microgels with changing 1-octanol concentration.

Morphological Transitions in Micelles of Amphiphilic Bottlebrushes upon the Adsorption and Compression at the Liquid Interface.

Densely grafted comb-like macromolecules (bottlebrushes) with alternating solvophobic and solvophilic side chains were studied in a selective solvent and at the liquid interface using mesoscopic computer simulations. The effects of backbone length and copolymer composition were considered. While self-assembly in solution revealed only spherical aggregates for all ar-chitectures studied, adsorption onto the liquid interface in particular cases resulted in morpho-logical changes, with worm-like aggregates or a continuous monolayer observed. In turn, the compression of macromolecules at the interface also leads to morphological transitions, includ-ing the formation of a mesh-like percolated structure. The obtained results may be useful for the preparation of solid nanoparticles of anisotropic shape or nanostructured ultra-thin copolymer films.

Swelling and Collapse of Cylindrical Polyelectrolyte Microgels.

In this study, we propose computer simulations of charged cylindrical microgels. The effects of cross-linking density, aspect ratio, and fraction of charged groups on the microgel swelling and collapse with a variation in the solvent quality were studied. The results were compared with those obtained for equivalent neutral cylindrical microgels. The study demonstrated that microgels' degree of swelling strongly depends on the fraction of charged groups. Polyelectrolyte microgels under adequate solvent conditions are characterized by a larger length and thickness than their neutral analogues: the higher the fraction of charged groups, the longer their length and greater their thickness. Microgels' collapse upon solvent quality decline is characterized by a decrease in length and non-monotonous behavior of its thickness. First, the thickness decreases due to the attraction of monomer units (beads) upon collapse. The further thickness increase is related to the surface tension, which tends to reduce the anisotropy of collapsed objects (the minimum surface energy is known to be achieved for the spherical objects). This reduction is opposed by the network elasticity. The microgels with a low cross-linking density and/or a low enough aspect ratio reveal a cylinder-to-sphere collapse. Otherwise, the cylindrical shape is preserved in the course of the collapse. Aspect ratio as a function of the solvent quality (interaction parameter) demonstrates the maximum, which is solely due to the electrostatics. Finally, we plotted radial concentration profiles for network segments, their charged groups, and counterions.

Correction: Effect of network topology and crosslinker reactivity on microgel structure and ordering at liquid-liquid interface.

Correction for 'Effect of network topology and crosslinker reactivity on microgel structure and ordering at liquid-liquid interface' by Rustam A. Gumerov et al., Soft Matter, 2022, 18, 3738-3747, https://doi.org/10.1039/D2SM00269H.

Effect of network topology and crosslinker reactivity on microgel structure and ordering at liquid-liquid interface.

Polymer microgels synthesized in silico were studied at a liquid-liquid interface via mesoscopic computer simulations and compared to microgels with ideal (diamond-like) structure. The effect of crosslinkers reactivity ratio on the single particle morphology at the interface and monolayer behavior was examined. It was demonstrated that single particles deform into an explicit core-corona morphology when adsorbed at the interface. An increase in the crosslinker reactivity ratio decreased both the deformation ratio and the ratio between the core and corona sizes. Meanwhile, the compression of microgel monolayers revealed the existence of five distinct interparticle contact regimes, which have been observed experimentally in the literature. The crosslinker reactivity ratio appeared to define the compression range in these regimes and the sharpness of the transition between them. In particular, the higher the crosslinker reactivity ratio, the smaller the corona, and in turn, the narrower the range of the intermediate regime comprising both core-core and corona-corona contacts. The obtained results demonstrate that the more realistic model of microgels synthesized via precipitation polymerization allows for a more accurate prediction of the properties of the microgels at a liquid-liquid interface in comparison to the conventional diamond-like lattice model.

Tuning the Elasticity of Nanogels Improves Their Circulation Time by Evading Immune Cells.

Peptide receptor radionuclide therapy is used to treat solid tumors by locally delivering radiation. However, due to nephro- and hepato-toxicity, it is limited by its dosage. To amplify radiation damage to tumor cells, radiolabeled nanogels can be used. We show that by tuning the mechanical properties of nanogels significant enhancement in circulation half-life of the gel could be achieved. We demonstrate why and how small changes in the mechanical properties of the nanogels influence its cellular fate. Nanogels with a storage modulus of 37 kPa were minimally phagocytosed by monocytes and macrophages compared to nanogels with 93 kPa modulus. Using PET/CT a significant difference in the blood circulation time of the nanogels was shown. Computer simulations affirmed the results and predicted the mechanism of cellular uptake of the nanogels. Altogether, this work emphasizes the important role of elasticity even for particles that are inherently soft such as nano- or microgels.

Rigid-to-Flexible Transition in a Molecular Brush in a Good Solvent at a Semidilute Concentration.

The structures of a molecular brush in a good solvent are investigated using synchrotron small-angle X-ray scattering in a wide range of concentrations. The brush under study, PiPOx239-g-PnPrOx14, features a relatively long poly(2-isopropenyl-2-oxazoline) (PiPOx) backbone and short poly(2-n-propyl-2-oxazoline) (PnPrOx) side chains. As a solvent, ethanol is used. By model fitting, the overall size and the persistence length as well as the interaction length and interaction strength are determined. At this, the interplay between form and structure factor is taken into account. The conformation of the molecular brush is traced upon increasing the solution concentration, and a rigid-to-flexible transition is found near the overlap concentration. Finally, the results of computer simulations of the molecular brush solutions confirm the experimental results.

Self-assembly of miktoarm palm tree-like star copolymers in a selective solvent.

Amphiphilic miktoarm star copolymers with one long solvophobic arm (a "stem") and several short solvophilic arms (the "leaves") were studied in a selective solvent using mesoscopic computer simulations. The conventional morphologies (spherical, cylindrical and vesicular) as well as the mixed ones were obtained. However, the resulting diagram of states appeared to be different from the diagram of the linear diblock copolymer with the analogous composition. Namely, the increase of the number of leaves at fixed solvophobic-solvophilic ratio leads to the transition from the vesicles to the cylinders, while the latter ones eventually transform into spherical micelles in the case of highly branched copolymers. The observed effect appears due to the increase of the interfacial area between the collapsed and swollen blocks per single macromolecule. In turn, the increase of the solvent selectivity shifts the stability region of the cylindrical micelles to the region of more symmetric copolymer composition. Meanwhile, the compatibility between the blocks has a weak effect on the resulting morphology. Finally, it was found that the increase in the number of leaves and the simultaneous decrease in their length results in the localization of higher amount of solvophilic segments near the core-solvent interface, which in the case of cylindrical micelles significantly affects the shape of the aggregates making them thinner and longer.

Controlling microgel deformation via deposition method and surface functionalization of solid supports.

Soft matter at solid-liquid interfaces plays an important role in multiple scientific disciplines as well as in various technological fields. For microgels, representing highly interesting soft matter systems, we demonstrate that the preparation method, i.e. the way how the microgel is applied to the specific surface, plays a key role. Focusing on the three most common sample preparation methods (spin-coating, drop-casting and adsorption from solution), we performed a comparative study of the deformation behavior of microgels at the solid-liquid interface on three different surfaces with varying hydrophilicities. For in situ visualization of the deformation of pNIPMAM microgels, we conducted highly sensitive 3D super resolution fluorescence microscopy methods. We furthermore performed complementary molecular dynamics simulations to determine the driving force responsible for the deformation depending on the surface and the deposition method. The combination of experiments and simulations revealed that the simulated equilibrium structure obtained after simulation of the completely dry microgel after deposition is retained after rehydration and subsequent fluorescent imaging.

Compression and Ordering of Microgels in Monolayers Formed at Liquid-Liquid Interfaces: Computer Simulation Studies.

Monolayers of polymer microgels adsorbed at the liquid interfaces were studied by dissipative particle dynamics simulations. The results demonstrated that the compressibility of the monolayers can be widely tuned by varying the cross-linking density of the microgels and their (in)compatibility with the immiscible liquids. In particular, the compression of the monolayers (increase of 2D concentration of the microgels) leads to the decrease of their lateral size. Herewith, the shape of the individual soft particles gradually changes from oblate (diluted 2D system) to nearly spherical (compressed monolayer). The polymer concentration profiles plotted along the normal to the interface reveal a nonmonotonous shape with a sharp maximum at the interface. This is a consequence of the shielding effect: saturation of the interface by monomer units of the subchains is driven by minimization of unfavorable contacts between the immiscible liquids and is opposed by elasticity of the network. The decrease of the interfacial tension upon concentration (compression) of the monolayer is quantified. It has been demonstrated that the interfacial tension significantly differs if the solubility of the polymer chains of the microgel network in the liquids changes. These results correlate well with experimental data. The examination of the microgels' crystalline ordering in monolayers demonstrated a nonmonotonous dependency on the compression degree (microgel concentration). Finally, the worsening of the solvent quality leads to the collapse of the microgels in monolayer and nonmonotonous behavior of the interfacial tension.

Amphiphilic PVCL/TBCHA microgels: From synthesis to characterization in a highly selective solvent.

Thermoresponsive copolymer microgels based on the biocompatible monomer N-vinylcaprolactam (VCL) and the hydrophobic comonomer 4-tert-butylcyclohexylacrylate (TBCHA) with highly tunable comonomers ratio were for the first time synthesized by miniemulsion polymerization. Their physical properties in aqueous solution and at the solid interface were characterized using dynamic light scattering (DLS), atomic force microscopy (AFM) and dissipative particle dynamics (DPD) simulations. The results show a significant decrease of the swelling rate of the obtained microgels with an increase of the amount of the hydrophobic comonomer. In the case when the fraction of TBCHA is equal or higher than the fraction of VCL, the microgels become almost insensitive to the temperature changes, and the amount of water inside the microgels appeared to be diminishingly small. In the opposite case, if the VCL fraction is major, the copolymer microgels preserve their softness and deformability while being adsorbed onto a solid surface. At the same time, all samples have shown a good colloidal stability and a low polydispersity in size. Thus, the presented polymerization technique is applicable for the fabrication of microgels using hydrophobic monomers, which are not accessible by conventional precipitation polymerization. We demonstrate that the mechanical properties and the temperature-responsiveness of the copolymer microgels can be precisely adjusted by the content of the hydrophobic comonomer.

Metal Coordination Induces Phase Segregation in Amphipolar Arborescent Copolymers with a Core-Shell-Corona Architecture.

Arborescent copolymers with a core-shell-corona (CSC) architecture were synthesized and the topology of the molecules was challenged (constrained) through intramolecular interactions, resulting in phase separation breaking the symmetry of radial density. The inner poly(2-vinylpyridine) shell of these arborescent polystyrene-g-[poly(2-vinylpyridine)-b-polystyrene] molecules can self-assemble by binding metallic salts and acids in apolar and intermediate-polarity solvents. Upon loading with HAuCl4, the characteristics of the polymer templates govern the "loading sites" of the metal within the molecules. Unique morphologies were observed for the metal-loaded G0-G4 arborescent copolymers investigated, namely, spherical, toroidal, raspberry-like, spherical nanocage, and a new worm-in-sphere morphology. The reason for the emergence of such morphologies is the interplay among intramolecular interactions of unlike polymer segments, solvent selectivity, the entropic elasticity of the arborescent substrate, and phase segregation induced by coordination with the charged metallic species. Meanwhile, the stability of the arborescent molecules against aggregation provides intramolecular phase segregation with imposed "confined" geometry and thus leads to nonconventional morphologies. Furthermore, the size of the arborescent molecules is much smaller than that of other known particles (droplets) serving as confined geometries. Computer simulations were used to model the mesostructure of the arborescent copolymers, to demonstrate the influence of solvent selectivity, together with HAuCl4 loading, on the evolution of the morphology of the macromolecules.

Scavenging One of the Liquids versus Emulsion Stabilization by Microgels in a Mixture of Two Immiscible Liquids.

It is known that microgels can serve as soft, permeable and stimuli-responsive alternative of solid colloidal particles to stabilize oil-water emulsions. The driving force for the adsorption of the microgels on interface of two immiscible liquids is a shielding of unfavorable oil-water contacts by adsorbed subchains, that is, the decrease of the surface tension between the liquids. Such phenomenon usually proceeds if volume fractions of the two liquids are comparable with each other and the microgel concentration is not high enough. The natural question arises: what is going on with the system in the opposite case of strongly asymmetric mixture (one of the liquids (oil) has a very small fraction) or high microgel concentration (the overall volume of the microgels exceeds the volume of the minor oil component)? Here we demonstrate that the microgels uptake the oil whose concentration within the microgels can be orders of magnitude higher than outside, leading to the additional microgel swelling (in comparison with the swelling in water). Thus, the microgels can serve as scavengers and concentrators of liquids dissolved in water. At first glance, this effect seems counterintuitive. However, it has a clear physical reason related to the incompatibility of oil and water. Absorption of the oil by microgels reduces unfavorable oil-water contacts by microgel segments: the microgels have a higher concentration of the segments at the periphery, forming a shell. The microgels with uptaken oil are stable toward aggregation at very small oil concentration in the mixture. However, an increase in the oil concentration can lead to aggregation of the microgels into dimers, trimers, and so on. The increasing concentration of oil mediates the attraction between the microgels: the oil in the aggregates appears to be localized in-between the microgels instead of their interior, which is accompanied by the release of the elastic stress of the microgels. A further increase in the oil concentration results in a growth of the size of the oil droplets between the microgels and the number of the microgels at the droplet's periphery, that is, the emulsion is formed.

Enhanced catalyst performance through compartmentalization exemplified by colloidal l-proline modified microgel catalysts.

Exploring and controlling chemical reactions in compartments opens new platforms for designing bioinspired catalysts and energy-autonomous systems. Aqueous polymer networks or hydrogels serve as a perfect model for biological tissues, allowing systematic investigations of chemical transformations in compartments. Herein, we report the synthesis of a versatile, colloidal microgel catalyst containing covalently bound l-proline as an organocatalyst. The key finding of our work is that the catalytic activity can be tuned by adjusting the distribution of the organocatalyst in the microgel network as well as the properties of the solvent. We demonstrate that l-proline groups integrated into microgels enable the reaction of 4-nitrobenzaldehyde and cyclohexanone in a heterogeneous reaction mixture in which free l-proline is not active. By controlling the localization of the l-proline groups within the microgel network (core or corona), the rate of the aldol reaction in homogenous and heterogeneous reaction mixtures can be modulated. Furthermore, microgels with covalently attached catalysts can be recycled and reused in sequential catalytic runs without deterioration of the catalyst performance in terms of activity and selectivity. The internal structure of the microgel in heterogeneous reaction mixtures was studied by computer simulations.

Effect of the 3D Swelling of Microgels on Their 2D Phase Behavior at the Liquid-Liquid Interface.

We investigate soft, temperature-sensitive microgels at fluid interfaces. Though having an isotropic, spherical shape in bulk solution, the microgels become anisotropic upon adsorption. The structure of microgels at interfaces is described by a core-corona morphology. Here, we investigate how changing temperature across the microgel volume phase transition temperature, which leads to swelling/deswelling of the microgels in the aqueous phase, affects the phase behavior within the monolayer. We combine compression isotherms, atomic force microscopy imaging, multiwavelength ellipsometry, and computer simulations. At low compression, the interaction between adsorbed microgels is dominated by their highly stretched corona and the phase behavior of the microgel monolayers is the same. The polymer segments within the interface lose their temperature-sensitivity because of the strong adsorption to the interface. At high compression, however, the portions of the microgels that are located in the aqueous side of the interface become relevant and prevail in the microgel interactions. These portions are able to collapse and, consequently, the isostructural phase transition is altered. Thus, the temperature-dependent swelling perpendicular to the interface ("3D") affects the compressibility parallel to the interface ("2D"). Our results highlight the distinctly different behavior of soft, stimuli-sensitive microgels as compared to rigid nanoparticles.

Deformation of Microgels at Solid-Liquid Interfaces Visualized in Three-Dimension.

Solid-liquid interfaces play an important role for functional devices. Hence, a detailed understanding of the interaction of soft matter objects with solid supports and of the often concomitant structural deformations is of great importance. We address this topic in a combined experimental and simulation approach. We investigated thermoresponsive poly(N-isopropylmethacrylamide) microgels (µGs) at different surfaces in an aqueous environment. As super-resolution fluorescence imaging method, three-dimensional direct stochastical optical reconstruction microscopy (dSTORM) allowed for visualizing µGs in their three-dimensional (3D) shape, for example, in a "fried-egg" conformation depending on the hydrophilicity of the surface (strength of adsorption). The 3D shape, as defined by point clouds obtained from single-molecule localizations, was analyzed. A new fitting algorithm yielded an isosurface of constant density which defines the deformation of µGs at the different surfaces. The presented methodology quantifies deformation of objects with fuzzy surfaces and allows for comparison of their structures, whereby it is completely independent from the data acquisition method. Finally, the experimental data are complemented with mesoscopic computer simulations in order to (i) rationalize the experimental results and (ii) to track the evolution of the shape with changing surface hydrophilicity; a good correlation of the shapes obtained experimentally and with computer simulations was found.

Amphiphilic microgels adsorbed at oil-water interfaces as mixers of two immiscible liquids.

Amphiphilic microgels adsorbed at an oil-water interface were studied by means of dissipative particle dynamics (DPD) simulations. The hydrophobic (A) and hydrophilic (B) monomer units in the polymer network are considered to be randomly distributed. Effects of the crosslinking density, interfacial tension between the liquids, their selectivity as solvents towards species A and B, and the degree of incompatibility between the A and B units on the internal microgel structure and distribution of the liquids are considered. The most important predictions are that (i) two immiscible liquids can homogeneously be mixed within the microgels and (ii) the adsorbed microgels contain a high fraction of the liquids (they are swollen at the interface). Simultaneous fulfillment of these two conditions can have a high impact on the design of new and efficient catalytic systems. In particular, such microgels can mix immiscible reactants dissolved in water and oil and trigger chemical reactions in the presence of a catalyst embedded into the microgel.