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The adsorption of ellipsoidal colloidal particles on liquid interfaces induces interfacial deformation, resulting in anisotropic interface-mediated interactions and the formation of superstructures. Soft prolate-shaped microgels at the air-water interface offer an ideal model for studying spontaneous capillary-driven self-assembly due to their tunable aspect ratio, controlled functionality, and softness. These microgels consist of a polystyrene core surrounded by a cross-linked, fluorescently labeled poly([Formula: see text]-isopropylmethylacrylamide) shell. By uniaxially stretching the particles embedded in polyvinyl alcohol films, the aspect ratio [Formula: see text] can be finely adjusted. [Formula: see text] was found to vary from 1 to 8.8 as estimated in their swollen conformation at 20 ° C from confocal laser scanning microscopy. The spontaneous interfacial self-assembly at the air-water interface is investigated through fluorescence microscopy, theoretical calculations, and computer simulations. A structural transition occurs from a seemingly random assembly for small aspect ratios to compact clusters, which transform into a side-to-side assembly forming long chains for high aspect ratios. The influence of the poly([Formula: see text]-isopropylmethacrylamide) shell on the assembly indicates a significant [Formula: see text]-dependent microgel deformation. This deformation, in turn, determines the average distance between the particles. Consequently, capillary-driven self-assembly of soft anisotropic colloids becomes a powerful mechanism for structuring interfaces and designing microstructured materials., Competing Interests: Competing interests statement:The authors declare no competing interest.

Thin films made of deformable micro- and nano-units, such as biological membranes, polymer interfaces, and particle-laden liquid surfaces, exhibit a complex behavior during drying, with consequences for various applications like wound healing, coating technologies, and additive manufacturing. Studying the drying dynamics and structural changes of soft colloidal films thus holds the potential to yield valuable insights to achieve improvements for applications. In this study, interfacial monolayers of core-shell (CS) microgels with varying degrees of softness are employed as model systems and to investigate their drying behavior on differently modified solid substrates (hydrophobic vs hydrophilic). By leveraging video microscopy, particle tracking, and thin film interference, this study shed light on the interplay between microgel adhesion to solid surfaces and the immersion capillary forces that arise in the thin liquid film. It is discovered that a dried replica of the interfacial microstructure can be more accurately achieved on a hydrophobic substrate relative to a hydrophilic one, particularly when employing softer colloids as opposed to harder counterparts. These observations are qualitatively supported by experiments with a thin film pressure balance which allows mimicking and controlling the drying process and by computer simulations with coarse-grained models., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Surface-active polymers have important applications as effective and responsive emulsifiers, foaming agents, and coatings. In this contribution, we explore the impact of the polymer architecture on the behavior at oil-water interfaces by comparing different poly( N -isopropylacrylamide) (pNIPAM)-based systems, namely, monolayers of linear and star-shaped macromolecules, ultralow cross-linked, regular cross-linked, and hollow microgels. Compression isotherms were determined experimentally as well as by computer simulations. The latter provides information about the conformational changes of the individual macromolecules as well as the interfacial properties of the monolayer, including the surface structure and the density distribution of an ensemble of interacting macromolecules near an interface. Surprisingly, the isotherms of the linear polymer, of the star polymer, and of the ultralow cross-linked microgel have an identical shape that differs from the isotherms of regular and hollow microgels. We introduced the mass fraction of adsorbed polymer, which gives a measure of the polymer segments contributing to the isotherm in relation to the most flexible architecture, i.e., the linear polymer, and allows a comparison of polymers with different architectures. The data demonstrate that increasing the number of cross-links leads to a significantly lower amount of polymer in the proximity of the interface as the increase in cross-linker reduces the deformability or softness of the polymers at the interface. The volume fraction profiles along the normal to the interface are essentially different in the microgel monolayers as compared to those in the linear and star polymer. The profiles through the microgel contact line and their growth upon initial compression are similar to those of the linear chains. Herewith, the profiles through the center of mass practically do not change upon compression. Therefore, the initial growth in the microgel surface pressure reveals the polymer-like behavior and is related to the deformation of the peripheral part of the microgel. Further compression of the microgel monolayer leads to 3D interactions of the microgels within the aqueous side of the interface and soft colloid-like behavior.

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.

Hypothesis: Recently, it has become possible to synthesize hollow polyelectrolyte nano- and microgels. The shell permeability can be controlled by external stimuli, while the cavity can serve as a storage place for guest molecules. However, there is a lack of a detailed understanding at the molecular level regarding the role of the network topology, inhomogeneities of the distribution of cross-links, and the impact of the electrostatics on the structural response of hollow microgel to external stimuli. To bridge these gaps, molecular dynamics (MD) of computer simulations are used., Experiments: Here, we propose a fresh methodology to create realistic hollow microgel particles in silico. The technique involves a gradual change in the average local length of subchains depending on the distance to the center of mass of the microgel particles resulting in the microgels with a non-uniform distribution of cross-linking species. In particular, a series of microgels with (i) a highly cross-linked inner part of the shell and gradually decreased cross-linker concentration towards the periphery, (ii) microgels with loosely cross-linked inner and outer parts, as well as (iii) microgels with a more-or-less homogeneous structure, have been created and validated. Counterions and salt ions are taken into account explicitly, and electrostatic interactions are described by the Coulomb potential., Findings: Our studies reveal a strong dependence of the microgel swelling response on the network topology. Simple redistribution of cross-links plays a significant role in the structure of the microgels, including cavity size, microgel size, fuzziness, and extension of the inner and outer parts of the microgels. Our results indicate the possibilities of qualitative justification of the structure of the hollow microgels in the experiments by measuring the relative change in the size of the sacrificial core to the size of the cavity and by estimation of a power law function, [Formula: see text] , of the hydrodynamic radius of the hollow microgels as a function of added salt concentration., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Anisotropic, submicrometer-sized particles are versatile systems providing interesting features in creating ordering in two-dimensional systems. Combining hard ellipsoids with a soft shell further enhances the opportunities to trigger and control order and alignment. In this work, we report rich 2D phase behavior and show how softness affects the ordering of anisotropic particles at fluid oil-water interfaces. Three different core-shell systems were synthesized such that they have the same elliptical hematite-silica core but differ with respect to thickness and stiffness of the soft microgel shell. Compression isotherms, the shape of individual core-shell microgels, and their 2D order at a decane-water interface are investigated by means of the Langmuir-Blodgett technique combined with ex-situ atomic force microscopy (AFM) imaging as well as dissipative particle dynamics (DPD) simulations. We show how the softness, size, and anisotropy of the microgel shell affect the side-to-side vs tip-to-tip ordering of anisotropic hybrid microgels as well as the alignment with respect to the direction of compression in the Langmuir trough. A large, soft microgel shell leads to an ordered structure with tip-to-tip alignment directed perpendicular to the direction of compression. In contrast, a thin and harder microgel shell leads to side-to-side ordering orientated parallel to the compression direction. In addition, the thin and harder microgel shell induces clustering of the microgels in the dilute state, indicating the presence of strong capillary interactions. Our findings highlight the relevance of softness for the complex ordering of anisotropic hybrid microgels at interfaces.

Microgels, cross-linked polymers with submicrometer size, are ideal soft model systems. While spherical microgels have been studied extensively, anisotropic microgels have hardly been investigated. In this study, we compare the interfacial deformation and assembly of anisotropic core-shell and hollow microgels. The core-shell microgel consists of an elliptical core of hematite covered with a thin silica layer and a thin shell made of poly( N -isopropylacrylamide). The hollow microgels were obtained after a two-step etching procedure of the inorganic core. The behavior of these microgels at the oil-water interface was investigated in a Langmuir-Blodgett trough combined with ex situ atomic force microscopy. First, the influence of the architecture of anisotropic microgels on their spreading at the interface was investigated experimentally and by dissipative particle dynamic simulations. Hereby, the importance of the local shell thickness on the lateral and longitudinal interfacial deformation was highlighted as well as the differences between the core-shell and hollow architectures. The shape of the compression isotherms as well as the dimensions, ordering, and orientation of the microgels at the different compressions were analyzed. Due to their anisotropic shape and stiffness, both anisotropic microgels were found to exhibit significant capillary interactions with a preferential side-to-side assembly leading to stable microgel clusters at low interfacial coverage. Such capillary interactions were found to decrease in the case of the more deformable hollow anisotropic microgels. Consequently, anisotropic hollow microgels were found to distribute more evenly at high surface pressure compared to stiffer core-shell microgels. Our findings emphasize the complex interplay between the colloid design, anisotropy, and softness on the interfacial assembly and the opportunities it therefore offers to create more complex ordered interfaces.