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Microgels are soft colloidal particles constituted by cross-linked polymer networks with a high potential for applications. In particular, after adsorption at a fluid interface, interfacial tension provides two-dimensional (2D) confinement for microgel monolayers and drives the reconfiguration of the particles, enabling their deployment in foam and emulsion stabilization and in surface patterning for lithography, sensing and optical materials. However, most studies focus on systems of fluids with a high interfacial tension, e.g. alkanes/ or air/water interfaces, which imparts similar properties to the assembled monolayers. Here, instead, we compare two organic fluid phases, hexane and methyl tert-butyl ether, which have markedly different interfacial tension () values with water and thus tune the deformation of adsorbed microgels. We rationalize how controls the single-particle morphology, which consequently modulates the structural and mechanical response of the monolayers at varying interfacial compression. Specifically, when is low, the microgels are less deformed within the interface plane and their polymer networks can rearrange more easily upon lateral compression, leading to softer monolayers. Selecting interfaces with different surface energy offers an additional control to customize the 2D assembly of soft particles, from the fine-tuning of particle size and interparticle spacing to the tailoring of mechanical properties., Journal of Colloid and Interface Science, 608 (3), ISSN:0021-9797, ISSN:1095-7103

Anisotropic colloidal particles exhibit complex dynamics which play a crucial role in their functionality, transport and phase behaviour. In this work, we investigate the two-dimensional diffusion of smoothly curved colloidal rods -- also known as colloidal bananas -- as a function of their opening angle, {\alpha}. We measure the translational and rotational diffusion coefficients of the particles with opening angles ranging from 0{\deg} (straight rods) to nearly 360{\deg}(closed rings). In particular, we find that the anisotropic diffusion of the particles varies non-monotonically with their opening angle and that the axis of fastest diffusion switches from the long to the short axis of the particles when {\alpha}>180{\deg}. We also find that the rotational diffusion coefficient of nearly closed rings is approximately an order of magnitude higher than that of straight rods of the same length. Finally, we show that the experimental results are consistent with Slender Body Theory, indicating that the dynamical behavior of the particles arises primarily from their local drag anisotropy. These results highlight the impact of curvature on the Brownian Motion of elongated colloidal particles, which must be taken into account when seeking to understand the behaviour of curved colloidal particles., Comment: 5 pages (including references) and 4 figures

The reconfiguration of individual soft and deformable particles upon adsorption at a fluid interface underpins many aspects of their dynamics and interactions, ultimately regulating the properties of monolayers of relevance for applications. In this work, we demonstrate that atomic force microscopy can be used for the in situ reconstruction of the three-dimensional conformation of model poly(N-isopropylacrylamide) microgels adsorbed at an oil-water interface. We image the particle topography from both sides of the interface to characterize its in-plane deformation and to visualize the occurrence of asymmetric swelling in the two fluids. In addition, the technique enables investigating different fluid phases and particle architectures, as well as studying the effect of temperature variations on particle conformation in situ. We envisage that these results open up an exciting range of possibilities to provide microscopic insights into the single-particle behavior of soft objects at fluid interfaces and into the resulting macroscopic material properties., Science Advances, 8 (45), ISSN:2375-2548

The self-assembly of colloids at fluid interfaces is a well-studied research field both for gaining fundamental insights and for material fabrication. The fluid interface allows the confinement of particles in two dimensions and may act as a template for guiding their organization into soft and reconfigurable structures. Additives (e.g., surfactants, salts, and polymers) in the colloidal suspension are routinely used as a practical and effective tool to drive particle adsorption and tune their interfacial organization. However, some phenomena lying at the heart of the accumulation and self-assembly of particles at fluid interfaces remain poorly understood. This Feature Article aims to critically analyze the mechanisms involved in the adsorption and self-organization of micro- and nanoparticles at various fluid interfaces. In particular, we address the role of additives in both promoting the adsorption of particles from the bulk suspension to the fluid interface and in mediating the interactions between interfacial particles. We emphasize how different types of additives play a crucial role in controlling the interactions between suspended particles and the fluid interface as well as the interactions between adsorbed particles, thus dictating the final self-assembled structure. We also critically summarize the main experimental protocols developed for the complete adsorption of particles initially suspended in the bulk. Furthermore, we highlight some special properties (e.g., reconfigurability upon external stimulation and dissipative self-assembly) and the application potential of structures formed by colloid self-organization at fluid interfaces mediated/promoted by additives. We believe our contribution serves both as a practical roadmap to scientists coming from other fields and as a valuable information resource for all researchers interested in this exciting research field., Langmuir, 37 (31), ISSN:0743-7463, ISSN:1520-5827

Understanding globular protein adsorption to fluid interfaces, their interfacial assembly, and structural reorganization is not only important in the food industry, but also in medicine and biology. However, due to their intrinsic structural complexity, a unifying description of these phenomena remains elusive. Herein, we propose N-isopropylacrylamide microgels as a promising model system to isolate different aspects of adsorption, dilatational rheology, and interfacial structure at fluid interfaces with a wide range of interfacial tensions, and compare the results with the ones of globular proteins. In particular, the steady-state spontaneously-adsorbed interfacial pressure of microgels correlates closely to that of globular proteins, following the same power-law behavior as a function of the initial surface tension. However, the dilatational rheology of spontaneously-adsorbed microgel layers is dominated by the presence of a loosely packed polymer corona spread at the interface, and it thus exhibits a similar mechanical response as flexible, unstructured proteins, which are significantly weaker than globular ones. Finally, structurally, microgels reveal a similar spreading and flattening upon adsorption as globular proteins do. In conclusion, microgels offer interesting opportunities to act as powerful model systems to unravel the complex behavior of proteins at fluid interfaces., Colloids and Surfaces B: Biointerfaces, 217, ISSN:0927-7765, ISSN:1873-4367

International audience; Optically addressable colloidal assembly at fluid interfaces is a highly desired component to generate reconfigurable 2D materials, but has rarely been achieved and only with specific interface engineering. Here we describe a generic method to get optically reconfigurable colloidal crystals at the air/water interface and emphasize a new mechanism to convert light into tunable lattice properties. We use light-absorbing anionic particles adsorbed at the air/water interface in the presence of minute amounts of cationic surfactant, which self-assembled into closely-packed polycrystalline structures by collectively deforming the surrounding interface. Low-intensity irradiation of these colloidal crystals results in unprecedented control of the interparticle spacing (IPS) in a preserved crystalline state while, at a higher intensity, cycles of melting/recrystallization with a controllable transition kinetics can be achieved upon successive on/off stimulations. We show that this photoreversible melting originates from an initial thermocapillary stress, expanding the colloidal assembly against the local confinement, and an increase in particles diffusivity imposing the transition kinetics. With this mechanism, local irradiation leads to highly dynamic patterns, including self-healing or self-fed "living" crystals, while multi-responsive assembly is also achieved by controlling particle organization with both light and magnetic stimuli.

Monolayers of soft colloidal particles confined at fluid interfaces are at the core of a broad range of technological processes, from the stabilization of responsive foams and emulsions to advanced lithographic techniques. However, establishing a fundamental relation between their internal architecture, which is controlled during synthesis, and their structural and mechanical properties upon interfacial confinement remains an elusive task. To address this open issue, which defines the monolayer's properties, we synthesize core-shell microgels, whose soft core can be chemically degraded in a controlled fashion. This strategy allows us to obtain a series of particles ranging from analogues of standard batch-synthesized microgels to completely hollow ones after total core removal. Combined experimental and numerical results show that our hollow particles have a thin and deformable shell, leading to a temperature-responsive collapse of the internal cavity and a complete flattening after adsorption at a fluid interface. Mechanical characterization shows that a critical degree of core removal is required to obtain soft disk-like particles at an oil-water interface, which present a distinct response to compression. At low packing fractions, the mechanical response of the monolayer is dominated by the outer polymer chains forming a corona surrounding the particles within the interfacial plane, regardless of the presence of a core. By contrast, at high compression, the absence of a core enables the particles to deform in the direction orthogonal to the interface and to be continuously compressed without altering the monolayer structure. These findings show how fine, single-particle architectural control during synthesis can be engineered to determine the interfacial behavior of microgels, enabling one to link particle conformation with the resulting material properties., ACS Nano, 15 (8), ISSN:1936-0851, ISSN:1936-086X

The “flipping method” is a new straightforward way to both adsorb and organize microparticles at a liquid interface, with ultralow amounts of a surfactant and no other external forces than gravity. Here we demonstrate that it allows the adsorption of a variety of inorganic nanoparticles at an air/water interface, in an organized way, which is directly controlled by the surfactant concentration, ranging from amorphous to highly crystalline two-dimensional assemblies. With micromolar amounts of a conventional cationic surfactant (dodecyltrimethylammonium bromide, DTAB), nanoparticles of different compositions (silica, silver, and gold), sizes (down to 100 nm) and shapes (spheres and cubes) adsorb from the bulk and directly organize at the air/water interface, resulting in marked optical properties such as reflectivity or intense structural coloration.

International audience; Control over particle interactions and organization at liquid interfaces is of great importance both for fundamental studies and practical applications. Rendering these systems stimulus-responsive is thus a desired challenge both for investigating dynamic phenomena and realizing reconfigura-ble materials. Here, we describe the first reversible photo-control of two-dimensional colloidal crystallization at the air/ water interface, where millimeter-sized assemblies of micro-particles can be actuated through the dynamic adsorption/ desorption behavior of a photosensitive surfactant added to the suspension. This allows us to dynamically switch the particle organization between a highly crystalline (under light) and a disordered (in the dark) phase with a fast response time (crystallization in % 10 s, disassembly in % 1 min). These results evidence a new kind of dissipative system where the crystalline state can be maintained only upon energy supply.

International audience; We precisely measure the effect of moderate magnetic field intensity on the surface tension of liquids, by placing pendant drops inside uniform fields where bulk forces due to gradients are eliminated. The surface tension of water is unaffected while that of paramagnetic salt solutions slightly decreases with increasing field strength.

Shape-persistent azobenzene tetramers functionalized at the periphery with alkyloxy substituents of different lengths have been synthesized and their photochemical behaviour has been investigated. Efficient E -> Z photoisomerization of the azobenzene units takes place both in solution and in the solid state, a highly desirable yet uncommon property for azobenzene-type photochromic compounds. The solid state E -> Z photoisomerization is accompanied by an isothermal crystal-amorphous phase transformation; successively, anisotropic crystals can be grown upon promoting the Z -> E isomerization by thermal annealing of the irradiated samples. These results validate the strategy of engineering multiphotochromic architectures with a rigid star-shaped geometry to preserve the solution-based photoreactivity also in the solid state. The observed unexpected photoinduced alignment makes these materials potentially attractive for the development of photo-patternable and photo-responsive surfaces.

Controlling the organization of particles at liquid–gas interfaces usually relies on multiphasic preparations and external applied forces. Here, we show that micromolar amounts of a conventional cationic surfactant induce, in a single step, both adsorption and crystallization of various types of nanometer- to micrometer-sized anionic particles at the air–water interface, without any additional phase involved or external forces other than gravity. Contrary to conventional surfactant-induced particle adsorption through neutralization and hydrophobization at a surfactant concentration close to the critical micellar concentration (CMC), we show that in our explored concentration regime (CMC/1000-CMC/100), particles adsorb with a low contact angle and maintain most of their charge, leading to the formation of two-dimensional assemblies with different structures, depending on surfactant (Cs) and particle (Cp) concentrations. At low Cs and Cp, particles are repulsive and form disordered assemblies. Increasing Cp...

International audience; The magnetic actuation of deposited drops has mainly relied on volume forces exerted on the liquid to be transported, which is poorly efficient with conventional diamagnetic liquids such as water and oil, unless magneto-sensitive particles are added. Herein, we describe a new and additive-free way to magnetically control the motion of discrete liquid entities. Our strategy consists of using a paramagnetic liquid as a deformable substrate to direct, using a magnet, the motion of various floating liquid entities, ranging from naked drops to liquid marbles. A broad variety of liquids, including diamagnetic (water, oil) and nonmagnetic ones, can be efficiently transported using the moderate magnetic field (ca. 50 mT) produced by a small permanent magnet. Complex trajectories can be achieved in a reliable manner and multi-plexing potential is demonstrated through on-demand drop fusion. Our paramagnetofluidic method advantageously works without any complex equipment or electric power, in phase with the necessary development of robust and low-cost analytical and diagnostic fluidic devices.