Active particles induce large shape deformations in giant lipid vesicles.

Biological cells generate intricate structures by sculpting their membrane from within to actively sense and respond to external stimuli or to explore their environment1-4. Several pathogenic bacteria also provide examples of how localized forces strongly deform cell membranes from inside, leading to the invasion of neighbouring healthy mammalian cells5. Giant unilamellar vesicles have been successfully used as a minimal model system with which to mimic biological cells6-11, but the realization of a minimal system with localized active internal forces that can strongly deform lipid membranes from within and lead to dramatic shape changes remains challenging. Here we present a combined experimental and simulation study that demonstrates how self-propelled particles enclosed in giant unilamellar vesicles can induce a plethora of non-equilibrium shapes and active membrane fluctuations. Using confocal microscopy, in the experiments we explore the membrane response to local forces exerted by self-phoretic Janus microswimmers. To quantify dynamic membrane changes, we perform Langevin dynamics simulations of active Brownian particles enclosed in thin membrane shells modelled by dynamically triangulated surfaces. The most pronounced shape changes are observed at low and moderate particle loadings, with the formation of tether-like protrusions and highly branched, dendritic structures, whereas at high volume fractions globally deformed vesicle shapes are observed. The resulting state diagram predicts the conditions under which local internal forces generate various membrane shapes. A controlled realization of such distorted vesicle morphologies could improve the design of artificial systems such as small-scale soft robots and synthetic cells.

Unifying Atoms and Colloids near the Glass Transition through Bond-Order Topology.

In this combined experimental and simulation study, we utilize bond-order topology to quantitatively match particle volume fraction in mechanically uniformly compressed colloidal suspensions with temperature in atomistic simulations. The obtained mapping temperature is above the dynamical glass transition temperature, indicating that the colloidal systems examined are structurally most like simulated undercooled liquids. Furthermore, the structural mapping procedure offers a unifying framework for quantifying relaxation in arrested colloidal systems.

A microrheological examination of insulin-secreting ß-cells in healthy and diabetic-like conditions.

Pancreatic ß-cells regulate glucose homeostasis through glucose-stimulated insulin secretion, which is hindered in type-2 diabetes. Transport of the insulin vesicles is expected to be affected by changes in the viscoelastic and transport properties of the cytoplasm. These are evaluated in situ through particle-tracking measurements using a rat insulinoma ß-cell line. The use of inert probes assists in decoupling the material properties of the cytoplasm from the active transport through cellular processes. The effect of glucose-stimulated insulin secretion is examined, and the subsequent remodeling of the cytoskeleton, at constant effects of cell activity, is shown to result in reduced mobility of the tracer particles. Induction of diabetic-like conditions is identified to alter the mean-squared displacement of the passive particles in the cytoplasm and diminish its reaction to glucose stimulation.

Ductile-to-brittle transition and yielding in soft amorphous materials: perspectives and open questions.

Soft amorphous materials are viscoelastic solids ubiquitously found around us, from clays and cementitious pastes to emulsions and physical gels encountered in food or biomedical engineering. Under an external deformation, these materials undergo a noteworthy transition from a solid to a liquid state that reshapes the material microstructure. This yielding transition was the main theme of a workshop held from January 9 to 13, 2023 at the Lorentz Center in Leiden. The manuscript presented here offers a critical perspective on the subject, synthesizing insights from the various brainstorming sessions and informal discussions that unfolded during this week of vibrant exchange of ideas. The result of these exchanges takes the form of a series of open questions that represent outstanding experimental, numerical, and theoretical challenges to be tackled in the near future.

Comparative analysis of fluctuations in viscoelastic stress: A comparison of the temporary network and dumbbell models.

Traditionally, stress fluctuations in flowing and deformed materials are overlooked, with an obvious focus on average stresses in a continuum mechanical approximation. However, these fluctuations, often dismissed as "noise," hold the potential to provide direct insights into the material structure and its structure-stress coupling, uncovering detailed aspects of fluid transport and relaxation behaviors. Despite advancements in experimental techniques allowing for the visualization of these fluctuations, their significance remains largely untapped as modeling efforts continue to target Newtonian fluids within the confines of Gaussian noise assumptions. In the present work, a comparative analysis of stress fluctuations in two distinct microstructural models is carried out: the temporary network model and the hydrodynamic dumbbell model. Despite both models conforming to the upper convected Maxwell model at a macroscopic level, the temporary network model predicts non-Gaussian fluctuations. We find that stress fluctuations within the temporary network model exhibit more pronounced abruptness at the local scale, with only an enlargement of the control volume leading to a gradual Gaussian-like noise, diminishing the differences between the two models. These findings underscore the heightened sensitivity of fluctuating rheology to microstructural details and the microstructure-flow coupling, beyond what is captured by macroscopically averaged stresses.

Antibodies Adsorbed to the Air-Water Interface Form Soft Glasses.

When monoclonal antibodies are exposed to an air-water interface, they form aggregates, which negatively impacts their performance. Until now, the detection and characterization of interfacial aggregation have been difficult. Here, we exploit the mechanical response imparted by interfacial adsorption by measuring the interfacial shear rheology of a model antibody, anti-streptavidin immunoglobulin-1 (AS-IgG1), at the air-water interface. Strong viscoelastic layers of AS-IgG1 form when the protein is adsorbed from the bulk solution. Creep experiments correlate the compliance of the interfacial protein layer with the subphase solution pH and bulk concentration. These, along with oscillatory strain amplitude and frequency sweeps, show that the viscoelastic behavior of the adsorbed layers is that of a soft glass with interfacial shear moduli on the order of 10-3 Pa m. Shifting the creep compliance curves under different applied stresses forms master curves consistent with stress-time superposition of soft interfacial glasses. The interfacial rheology results are discussed in the context of the interface-mediated aggregation of AS-IgG1.

Divide, Conquer, and Stabilize: Engineering Strong Fluid-Fluid Interfaces.

In multiphase materials, structured fluid-fluid interfaces can provide mechanical resistance against destabilization. Coarsening, coalescence, and significant deformation can be stalled with appropriate interfacial rheology and thus preserve interface integrity. Often, interfacial "strength" is generated by dense, packed surface populations, which are challenging to achieve through gradual, equilibrium-limited adsorption. Recent efforts have focused on developing new methods to produce kinetically trapped interfacial structures that possess desirable viscoelasticity or viscoplasticity, sometimes even with sparse populations. In creating these interfaces, we should recognize that the processing history is deterministic and offers alternative handles to engineer useful rheology. In this Perspective, we consider what can be achieved by designing not only the intrinsic qualities of surface-active species but also the process that brings them to the interface. We contrast different classes of processing history through a somewhat historical lens: after creating an interface ("divide"), what ("conquering") strategies exist for populating it with agents that ensure stabilization? Navigating the delicate interplay among property, structure, and processing history is required to improve material and energy use and to realize unique multiphase materials.

From Individual Liquid Films to Macroscopic Foam Dynamics: A Comparison between Polymers and a Nonionic Surfactant.

Foams can resist destabilizaton in ways that appear similar on a macroscopic scale, but the microscopic origins of the stability and the loss thereof can be quite diverse. Here, we compare both the macroscopic drainage and ultimate collapse of aqueous foams stabilized by either a partially hydrolyzed poly(vinyl alcohol) (PVA) or a nonionic low-molecular-weight surfactant (BrijO10) with the dynamics of individual thin films at the microscale. From this comparison, we gain significant insight regarding the effect of both surface stresses and intermolecular forces on macroscopic foam stability. Distinct regimes in the lifetime of the foams were observed. Drainage at early stages is controlled by the different stress-boundary conditions at the surfaces of the bubbles between the polymer and the surfactant. The stress-carrying capacity of PVA-stabilized interfaces is a result of the mutual contribution of Marangoni stresses and surface shear viscosity. In contrast, surface shear inviscidity and much weaker Marangoni stresses were observed for the nonionic surfactant surfaces, resulting in faster drainage times, both at the level of the single film and the macroscopic foam. At longer times, the PVA foams present a regime of homogeneous coalescence where isolated coalescence events are observed. This regime, which is observed only for PVA foams, occurs when the capillary pressure reaches the maximum disjoining pressure. A final regime is then observed for both systems where a fast coalescence front propagates from the top to the bottom of the foams. The critical liquid fractions and capillary pressures at which this regime is obtained are similar for both PVA and BrijO10 foams, which most likely indicates that collapse is related to a universal mechanism that seems unrelated to the stabilizer interfacial dynamics.

Variations in human saliva viscoelasticity affect aerosolization propensity.

Some contagious diseases, such as COVID-19, spread through the transmission of aerosols and droplets. Aerosol and droplet formation occurs inside and outside of the respiratory tract, the latter being observed during speaking and sneezing. Upon sneezing, saliva is expelled as a flat sheet, which destabilizes into filaments that subsequently break up into droplets. The presence of macromolecules (such as mucins) in saliva influences the dynamics of aerosol generation, since elasticity is expected to stabilize both fluid sheets and filaments, hence deterring droplet formation. In this study, the process of aerosol formation outside the respiratory tract is systematically replicated using an impinging jet setup, where two liquid jets collide and form a thin fluid sheet that can fragment into ligaments and droplets. The experimental setup enables us to investigate a range of dynamic conditions, quantified by the relevant non-dimensional numbers, which encompass those experienced during sneezing. Experiments are conducted with human saliva provided by different donors, revealing significant variations in their stability and breakup. We quantify the effect of viscoelasticity via shear and extensional rheology experiments, concluding that the extensional relaxation time is the most adequate measure of a saliva's elasticity. We summarize our results in terms of the dimensionless Weber, Reynolds, and Deborah numbers and construct universal state diagrams that directly compare our data to human sneezing, concluding that the aerosolization propensity is correlated with diminished saliva elasticities, higher emission velocities, and larger ejecta volumes. This could entail variations in disease transmission between individuals which hitherto have not been recognized.

Dynamic stabilisation during the drainage of thin film polymer solutions.

The drainage and rupture of polymer solutions was investigated using a dynamic thin film balance. The polymeric nature of the dissolved molecules leads to significant resistance to the deformation of the thin liquid films. The influence of concentration, molecular weight, and molecular weight distribution of the dissolved polymer on the lifetime of the films was systematically examined for varying hydrodynamic conditions. Depending on the value of the capillary number and the degree of confinement, different stabilisation mechanisms were observed. For low capillary numbers, the lifetime of the films was the highest for the highly concentrated, narrowly-distributed, low molecular weight polymers. In contrast, at high capillary numbers, the flow-induced concentration differences in the film resulted in lateral osmotic stresses, which caused a dynamic stabilisation of the films and the dependency on molecular weight distribution in particular becomes important. Phenomena such as cyclic dimple formation, vortices, and dimple recoil were observed, the occurrence of which depended on the relative magnitude of the lateral osmotic and the hydrodynamic stresses. The factors which lead to enhanced lifetime of the films as a consequence of these flow instabilities can be used to either stabilise foams or, conversely, prevent foam formation.

Breakup of Thin Liquid Films: From Stochastic to Deterministic.

The thinning and rupture of thin liquid films is a ubiquitous process, controlling the lifetime of bubbles, antibubbles, and droplets. A better understanding of rupture is important for controlling and modeling the stability of multiphase products. Yet literature reports that film breakup can be either stochastic or deterministic. Here, we employ a modified thin film balance to vary the ratio of hydrodynamic to capillary stresses and its role on the dynamics of thin liquid films of polymer solutions with adequate viscosities. Varying the pressure drop across planar films allows us to control the ratio of the two competing timescales, i.e., a controlled hydrodynamic drainage time and a timescale related to fluctuations. The thickness fluctuations are visualized and quantified, and their characteristics are for the first time directly measured experimentally for varying strengths of the flow inside the film. We show how the criteria for rupture depend on the hydrodynamic conditions, changing from stochastic to deterministic as the hydrodynamic forces inside the film damp the fluctuations.

Assessing the Interfacial Activity of Insoluble Asphaltene Layers: Interfacial Rheology versus Interfacial Tension.

Asphaltenes have been suggested to play an important role in the remarkable stability of some water-in-crude oil emulsions, although the precise mechanisms by which they act are not yet fully understood. Being one of the more polar fractions in crude oils, asphaltenes are surface active and strongly adsorb at the oil/water interface, and as the interface becomes densely packed, solid-like mechanical properties emerge, which influence many typical interfacial experiments. The present work focuses on purposefully measuring the rheology in the limit of an insoluble, spread Langmuir monolayer in the absence of adsorption/desorption phenomena. Moreover, the changes in surface tension are deconvoluted from the purely mechanical contribution to the surface stress by experiments with precise interfacial kinematics. Compression "isotherms" are combined with the measurement of both shear and dilatational rheological properties to evaluate the relative contributions of mechanical versus thermodynamic aspects, i.e., to evaluate the "interfacial rheological" versus the standard interfacial activity. The experimental results suggest that asphaltene nanoaggregates are not very efficient in lowering interfacial tension but rather impart significant mechanical stresses. Interestingly, physical aging effects are not observed in the spread layers, contrary to results for adsorbed layers. By further studying asphaltene fractions of different polarity, we investigate whether mere packing effects or strong interactions determine the mechanical response of the dense asphaltene systems as either soft glassy or gel-like responses have been reported. The compressional and rheological data reflect the dense packing, and the behavior is captured well by the soft glassy rheology model, but a more complicated multilayer structure may develop as coverage is increased. Potential implications of the experimental observations on these model and insoluble interfaces for water-in-crude oil emulsion stability are briefly discussed.

Mimicking coalescence using a pressure-controlled dynamic thin film balance.

The dynamics of thin films containing polymer solutions are studied with a pressure-controlled thin film balance. The setup allows the control of both the magnitude and the sign as well as the duration of the pressure drop across the film. The process of coalescence can be thus studied by mimicking the evolution of pressure during the approach and separation of two bubbles. The drainage dynamics, shape evolution and stability of the films were found to depend non-trivially on the magnitude and the duration of the applied pressure. Film dynamics during the application of the negative pressure step are controlled by an interplay between capillarity and hydrodynamics. A negative hydrodynamic pressure gradient promoted the thickening of the film, while the time-dependent deformation of the Plateau border surrounding it caused its local thinning. Distinct regimes in film break-up were thus observed depending on which of these two effects prevailed. Our study provides new insight into the behaviour of films during bubble separation, allows the determination of the optimum conditions for the occurrence of coalescence, and facilitates the improvement of population balance models.

Viscoelastic cluster densification in sheared colloidal gels.

Many biological materials, consumer products and industrial formulations are colloidal suspensions where the suspending medium is itself a complex fluid, and such suspensions are effectively soft matter composites. At rest, the distortion of the microstructure in the suspending fluid by the particles leads to attractive interactions between them. During flow, the presence of a microstructure in the viscoelastic suspending medium changes the hydrodynamic forces due to the non-Newtonian and viscoelastic effects. However, little is known about the structural development, the rheology and the final properties of such materials. In the present study, a model flocculated suspension in both a Newtonian and a viscoelastic medium was studied by combined rheological and rheo-confocal methods. To this extent, micrometer-sized fluorescent PMMA particles were dispersed in polymeric matrices (PDMS). The effect of fluid viscoelasticity is studied by comparing the results for a linear and a branched polymer. Stress jump experiments on the suspensions were used to de-convolute the rate dependence of the viscous and elastic stress contributions in both systems. These results were compared to a qualitative and quantitative analysis of the microstructure during flow as studied by fast structured illumination confocal microscopy, using a counter-rotating rheometer. At comparable interaction strength, as quantified by equal Bingham numbers, the presence of medium viscoelasticity leads to an enhanced densification of the aggregates during steady-state flow, which is reflected in lower limiting high shear viscosities. Following a strong preshear, the structural and mechanical recovery is also altered between the Newtonian and viscoelastic matrix with an increase in the percolation threshold, but with the potential to build stronger materials exploiting the combination of processing history and medium rheology at higher volume fractions.

Arresting dissolution by interfacial rheology design.

A strategy to halt dissolution of particle-coated air bubbles in water based on interfacial rheology design is presented. Whereas previously a dense monolayer was believed to be required for such an "armored bubble" to resist dissolution, in fact engineering a 2D yield stress interface suffices to achieve such performance at submonolayer particle coverages. We use a suite of interfacial rheology techniques to characterize spherical and ellipsoidal particles at an air-water interface as a function of surface coverage. Bubbles with varying particle coverages are made and their resistance to dissolution evaluated using a microfluidic technique. Whereas a bare bubble only has a single pressure at which a given radius is stable, we find a range of pressures over which bubble dissolution is arrested for armored bubbles. The link between interfacial rheology and macroscopic dissolution of [Formula: see text] 100 [Formula: see text]m bubbles coated with [Formula: see text] 1 [Formula: see text]m particles is presented and discussed. The generic design rationale is confirmed by using nonspherical particles, which develop significant yield stress at even lower surface coverages. Hence, it can be applied to successfully inhibit Ostwald ripening in a multitude of foam and emulsion applications.

Stress Contributions in Colloidal Suspensions: The Smooth, the Rough, and the Hairy.

The collective properties of colloidal suspensions, including their rheology, reflect an interplay between colloidal and hydrodynamic forces. The surface characteristics of the particles play a crucial role, in particular, for applications in which interparticle distances become small, i.e., at high concentrations or in aggregates. In this Letter, we directly investigate this interplay via the linear viscoelastic response of the suspensions in the high-frequency regime, using particles with controlled surface topographies, ranging from smooth to hairy and rough particles. We focus directly on the stresses at the particle level and reveal a strong impact of the surface topography on the short-range interactions, both dissipative and elastic. As the particle topography becomes more complex, the local stresses depend on how the topography is generated. The findings in this Letter, in particular, show how changes in topography can both screen or enhance the dissipation, which can be used to engineer the properties of dense or aggregated suspensions.

Effects of particle stiffness on the extensional rheology of model rod-like nanoparticle suspensions.

The linear and nonlinear rheological behavior of two rod-like particle suspensions as a function of concentration is studied using small amplitude oscillatory shear, steady shear and capillary breakup extensional rheometry. The rod-like suspensions are composed of fd virus and its mutant fdY21M, which are perfectly monodisperse, with a length on the order of 900 nm. The particles are semiflexible yet differ in their persistence length. The effect of stiffness on the rheological behavior in both, shear and extensional flow, is investigated experimentally. The linear viscoelastic shear data is compared in detail with theoretical predictions for worm-like chains. The extensional properties are compared to Batchelor's theory, generalized for the shear thinning nature of the suspensions. Theoretical predictions agree well with the measured complex moduli at low concentrations as well as the nonlinear shear and elongational viscosities at high flow rates. The results in this work provide guidelines for enhancing the elongational viscosity based on purely frictional effects in the absence of strong normal forces which are characteristic for high molecular weight polymers.

Toward Realistic Large-Area Cell Membrane Mimics: Excluding Oil, Controlling Composition, and Including Ion Channels.

Capacitance measurements provide unique insights into the thickness, compressibility, and composition of large-area membrane bilayers and are used here in addition to demonstrate the successful incorporation of model ion channels. The simultaneous ability to control the bilayer size, manipulate tension, and optically monitor and electrically stimulate freestanding membranes enables precise determination of their specific capacitance and thickness across a wide range of areas. We confirm that membranes formed by this recently developed technique have capacitive properties similar to those formed by existing protocols, including solvent-free approaches, and discuss the effect using either hexadecane or squalene as the oil solvent. The results obtained here are relevant for other methods where lipid membranes are reconstituted from a bulk oil solvent. Because biological membranes have a diverse phospholipid profile, we show that the technique can successfully reconstitute membranes with binary composition mixtures. As an outlook, we show the capability of model membrane proteins, specifically α-hemolysin and alamethicin, to be incorporated into the formed bilayers and measure ion transport.

Rheo-optical Analysis of Functionalized Graphene Suspensions.

Wet processing of graphene sheets is a potentially interesting route for the economically viable creation of graphene-based composites. In the present work, flow dichroism and small-angle light scattering are used to investigate the dispersion of functionalized graphene sheets in a suspension and their response to shear flow. In line with expectations from scaling theory at rest, the functionalized graphene sheets are present as Brownian flat sheets, and there is no evidence of significant crumpling. More surprisingly, we find that the rate-dependent orientation of these molecularly thin sheets can be described by numerical predictions for hard spheroidal sheets, making quantitative predictions of the flow-induced orientation possible. Further comparison of the flow-induced orientation of thick gold decahedra with the thin graphene sheets shows that, except for effects of polydispersity, the flow-induced orientation is predicted well quantitatively. Adequate prediction of the effects of flow on the orientation of graphene sheets makes it possible to design wet processed graphene-based composite materials.

Emulsions Stabilized by Chitosan-Modified Silica Nanoparticles: pH Control of Structure-Property Relations.

In food-grade emulsions, particles with an appropriate surface modification can be used to replace surfactants and potentially enhance the stability of emulsions. During the life cycle of products based on such emulsions, they can be exposed to a broad range of pH conditions and hence it is crucial to understand how pH changes affect stability of emulsions stabilized by particles. Here, we report on a comprehensive study of the stability, microstructure, and macroscopic behavior of pH-controlled oil-in-water emulsions containing silica nanoparticles modified with chitosan, a food-grade polycation. We found that the modified colloidal particles used as stabilizers behave differently depending on the pH, resulting in unique emulsion structures at multiple length scales. Our findings are rationalized in terms of the different emulsion stabilization mechanisms involved, which are determined by the pH-dependent charges and interactions between the colloidal building blocks of the system. At pH 4, the silica particles are partially hydrophobized through chitosan modification, favoring their adsorption at the oil-water interface and the formation of Pickering emulsions. At pH 5.5, the particles become attractive and the emulsion is stabilized by a network of agglomerated particles formed between the droplets. Finally, chitosan aggregates form at pH 9 and these act as the emulsion stabilizers under alkaline conditions. These insights have important implications for the processing and use of particle-stabilized emulsions. On one hand, changes in pH can lead to undesired macroscopic phase separation or coalescence of oil droplets. On the other hand, the pH effect on emulsion behavior can be harnessed in industrial processing, either to tune their flow response by altering the pH between processing stages or to produce pH-responsive emulsions that enhance the functionality of the emulsified end products.