Autonomous engulfment of active colloids by giant lipid vesicles.

Our ability to design artificial micro/nanomachines able to perform sophisticated tasks crucially depends on our understanding of their interaction with biosystems and their compatibility with the biological environment. Here, we design Janus colloids fuelled only by glucose and light, which can autonomously interact with cell-like compartments and trigger endocytosis. We evidence the crucial role played by the far-field hydrodynamic interaction arising from the puller/pusher swimming mode and adhesion. We show that a large contact time between the active particle and the lipid membrane is required to observe the engulfment of a particle inside a floppy giant lipid vesicle. Active Janus colloids showing relatively small velocities and a puller type swimming mode are able to target giant vesicles, deform their membranes and subsequently get stably engulfed. An instability arising from the unbound membrane segment is responsible for the transition between partial and complete stable engulfment. These experiments shed light on the physical criteria required for autonomous active particle engulfment in giant vesicles, which can serve as general principles in disciplines ranging from drug delivery and microbial infection to nanomedicine.

Dynamics of prolate spheroids in the vicinity of an air-water interface.

In this article, we present the mobilities of prolate ellipsoidal micrometric particles close to an air-water interface measured by dual wave reflection interference microscopy. Particle's position and orientation with respect to the interface are simultaneously measured as a function of time. From the measured mean square displacement, five particle mobilities (3 translational and 2 rotational) and two translational-rotational cross-correlations are extracted. The fluid dynamics governing equations are solved by the finite element method to numerically evaluate the same mobilities, imposing either slip and no-slip boundary conditions to the flow at the air-water interface. The comparison between experiments and simulations reveals an agreement with no-slip boundary conditions prediction for the translation normal to the interface and the out-of-plane rotation, and with slip ones for parallel translations and in-plane rotation. We rationalize these evidences in the framework of surface incompressibility at the interface.

Sunflower Proteins at Air-Water and Oil-Water Interfaces.

The adsorption of a sunflower protein extract at two air-water and oil-water interfaces is investigated using tensiometry, dilational viscoelasticity, and ellipsometry. For both interfaces, a three step mechanism was evidenced thanks to master curve representations of the data taken at different aging times and protein concentrations. At short times, a diffusion limited adsorption of proteins at interfaces is demonstrated. First, a two-dimensional protein film is formed with a partition of the polypeptide chains in the two phases that depends strongly on the nature of the hydrophobic phase: most of the film is in the aqueous phase at the air-water interface, while it is mostly in the organic phase at the oil-water interface. Then a three-dimensional saturated monolayer of proteins is formed. At short times, adsorption mechanisms are analogous to those found with typical globular proteins, while strong divergences are observed at longer adsorption times. Following the saturation step, a thick layer expands in the aqueous phase and appears associated with the release of large objects in the bulk. The kinetic evolution of this second layer is compatible with a diffusion limited adsorption of the minor population of polymeric complexes with hydrodynamic radius RH ∼ 80 nm, evidenced in equilibrium with hexameric globulins (RH ∼ 6 nm) in solution. These complexes could result from the presence of residual polyphenols in the extract and raise the question of the role of these compounds in the interfacial properties of plant protein extracts.

Active colloids orbiting giant vesicles.

Living or artificial self-propelled colloidal particles show original dynamics when they interact with other objects like passive particles, interfaces or membranes. These active colloids can transport small cargos or can be guided by passive objects, performing simple tasks that could be implemented in more complex systems. Here, we present an experimental investigation at the single particle level of the interaction between isolated active colloids and giant unilamellar lipid vesicles. We observed a persistent orbital motion of the active particle around the vesicle, which is independent of both the particle and the vesicle sizes. Force and torque transfers between the active particle and the vesicle is also described. These results differ in many aspects from recent theoretical and experimental reports on active particles interacting with solid spheres or liquid drops, and may be relevant for the study of swimming particles interacting with cells in biology or with microplastics in environmental science.

Multistable interaction between a spherical Brownian particle and an air-water interface.

We report the measurement of the interaction energy between a charged Brownian polystyrene particle and an air-water interface. The interaction potential is obtained from the Boltzmann equation by tracking particle interface distance with a specifically designed Dual-Wave Reflection Interference Microscopy (DW-RIM) setup. The particle has two equilibrium positions located at few hundreds of nanometers from the interface. The farthest position is well accounted by a DLVO model complemented by gravity. The closest one, not predicted by current models, more frequently appears in water solutions at relatively high ions concentrations, when electrostatic interaction is screened out. It is accompanied by a frozen rotational diffusion dynamics that suggests an interacting potential dependent on particle orientation and stresses the decisive role played by particle surface heterogeneities. Building up on both such experimental results, the important role of air nanobubbles pinned on the particle interface is discussed.

Van der Waals Emulsions: Emulsions Stabilized by Surface-Inactive, Hydrophilic Particles via van der Waals Attraction.

Surface-inactive, highly hydrophilic particles are utilized to effectively and reversibly stabilize oil-in-water emulsions. This is a result of attractive van der Waals forces between particles and oil droplets in water, which are sufficient to trap the particles in close proximity to oil-water interfaces when repulsive forces between particles and oil droplets are suppressed. The emulsifying efficiency of the highly hydrophilic particles is determined by van der Waals attraction between particle monolayer shells and oil droplets enclosed therein and is inversely proportional to the particle size, while their stabilizing efficiency is determined by van der Waals attraction between single particles and oil droplets, which is proportional to the particle size. This differentiation in mechanism between emulsification and stabilization will significantly advance our knowledge of emulsions, thus enabling better control and design of emulsion-based technologies in practice.

Janus Colloids Actively Rotating on the Surface of Water.

Biological or artificial microswimmers move performing trajectories of different kinds such as rectilinear, circular, or spiral ones. Here, we report on circular trajectories observed for active Janus colloids trapped at the air-water interface. Circular motion is due to asymmetric and nonuniform surface properties of the particles caused by fabrication. Motion persistence is enhanced by the partial wetted state of the Janus particles actively moving in two dimensions at the air-water interface. The slowing down of in-plane and out-of-plane rotational diffusions is described and discussed.

Brownian diffusion of a partially wetted colloid.

The dynamics of colloidal particles at interfaces between two fluids plays a central role in microrheology, encapsulation, emulsification, biofilm formation, water remediation and the interface-driven assembly of materials. Common intuition corroborated by hydrodynamic theories suggests that such dynamics is governed by a viscous force lower than that observed in the more viscous fluid. Here, we show experimentally that a particle straddling an air/water interface feels a large viscous drag that is unexpectedly larger than that measured in the bulk. We suggest that such a result arises from thermally activated fluctuations of the interface at the solid/air/liquid triple line and their coupling to the particle drag through the fluctuation-dissipation theorem. Our findings should inform approaches for improved control of the kinetically driven assembly of anisotropic particles with a large triple-line-length/particle-size ratio, and help to understand the formation and structure of such arrested materials.

Multiwalled Carbon Nanotube/Cellulose Composite: From Aqueous Dispersions to Pickering Emulsions.

A mild and simple way to prepare stable aqueous colloidal suspensions of composite particles made of a cellulosic material (Sigmacell cellulose) and multiwalled carbon nanotubes (MWCNTs) is reported. These suspensions can be dried and redispersed in water at pH 10.5. Starting with rather crude initial materials, commercial Sigmacell cellulose and MWCNTs, a significant fraction of composite dispersed in water could be obtained. The solid composites and their colloidal suspensions were characterized by electronic microscopy, thermal analyses, FTIR and Raman spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and light scattering. The composite particles consist of tenuous aggregates of CNTs and cellulose, several hundred nanometers large, and are composed of 55 wt % cellulose and 45 wt % CNTs. Such particles were shown to stabilize cyclohexane-in-water emulsions. The adsorption and the elasticity of the layer they form at interface were characterized by the pendant drop method. The stability of the oil-in-water emulsions was attributed to the formation of an elastic network of composite particles at interface. Cyclohexane droplet diameters could be tuned from 20 to 100 µm by adjusting the concentration of composite particles. This behavior was attributed to the limited coalescence phenomenon, just as expected for Pickering emulsions. Interestingly, cyclohexane droplets were stable over time and sustained pH modifications over a wide range, although acidic pH induced accelerated creaming. This study points out the possibility of combining crude cellulose and MWCNTs through a simple process to obtain colloidal systems of interest for the design of functional conductive materials.

MHz Ultrasound Induced Roughness of Fluid Interfaces.

The interface between two fluids is never flat at the nanoscale, and this is important for transport across interfaces. In the absence of any external field, the surface roughness is due to thermally excited capillary waves possessing subnanometric amplitudes in the case of simple liquids. Here, we investigate the effect of ultrasound on the surface roughness of liquid-gas and liquid-liquid interfaces. Megahertz (MHz) frequency ultrasound was applied normal to the interface at relatively low ultrasonic pressures (<0.6 MPa), and the amplitudes of surface fluctuations have been measured by light reflectivity and ellipsometry. We found a dramatic enhancement of surface roughness, roughly linear with intensity, with vertical displacements of the interface as high as 50-100 nm. As a consequence, the effective contact area between two fluids can be increased by ultrasound. This result has a clear impact for enhancing interface based processes such as mass or heat transfer.

Wetting and orientation of catalytic Janus colloids at the surface of water.

Janus colloidal particles show remarkable properties in terms of surface activity, self-assembly and wetting. Moreover they can perform autonomous motion if they can chemically react with the liquid in which they are immersed. In order to understand the self-propelled motion of catalytic Janus colloids at the air-water interface, wetting and the orientation of the catalytic surface are important properties to be investigated. Wetting plays a central role in active motion since it determines the contact between the fuel and the catalytic surface as well as the efficiency of the transduction of the chemical reaction into motion. Active motion is not expected to occur either when the catalytic face is completely out of the aqueous phase or when the Janus boundaries are parallel to the interfacial plane. The design of a Janus colloid possessing two hydrophilic faces is required to allow the catalytic face to react with the fuel (e.g. H2O2 for platinum) in water and to permit some rotational freedom of the Janus colloid in order to generate propulsion parallel to the interfacial plane. Here, we discuss some theoretical aspects that should be accounted for when studying Janus colloids at the surface of water. The free energy of ideal Janus colloidal particles at the interface is modeled as a function of the immersion depth and the particle orientation. Analytical expressions of the energy profiles are established. Energetic aspects are then discussed in relation to the particle's ability to rotate at the interface. By introducing contact angle hysteresis we describe how the effects of contact line pinning modifies the scenario described in the ideal case. Experimental observations of the contact angle hysteresis of Janus colloids at the interface reveal the effect of pinning; and orientations of silica particles half covered with a platinum layer at the interface do not comply with the ideal scenarios. Experimental observations suggest that Janus colloids at the fluid interface behave as a kinetically driven system, where the contact line motion over the defects decorating the Janus faces rules the orientation and rotational diffusion of the particle.

The Influence of Long-Range Surface Forces on the Contact Angle of Nanometric Droplets and Bubbles.

For a droplet or a bubble of dimensions below 100 nm, long-range surface forces such as long-range van der Waals forces can compete with capillarity, which leads to a size dependence of the contact angle. This is discussed in this work, where we also show that the effect cannot simply be described by a normalized line tension. We calculate interfacial profiles for typical values of van der Waals forces and discuss the role of long-range surface forces on the contact angle of nanobubbles and nanodrops.

Enhanced active motion of Janus colloids at the water surface.

We have investigated the active motion of self-propelled colloids confined at the air-water interface and explored the possibility of enhancing the directional motion of self-propelled Janus colloids by slowing down their rotational diffusion. The two dimensional motion of micron-sized silica-platinum Janus colloids has been experimentally measured by particle tracking video-microscopy at increasing concentrations of the catalytic fuel, i.e. H2O2. Compared to the motion in the bulk, a dramatic enhancement of both the persistence length of trajectories and the speed has been observed. The interplay of colloid self-propulsion, due to an asymmetric catalytic reaction occurring on the colloid, surface properties and interfacial frictions controls the enhancement of the directional movement. The slowing down of the rotational diffusion at the interface, also measured experimentally, plays a pivotal role in the control and enhancement of active motion.

In situ assessment of the contact angles of nanoparticles adsorbed at fluid interfaces by multiple angle of incidence ellipsometry.

Here multiple angle of incidence ellipsometry was successfully applied to in situ assess the contact angle and surface coverage of gold nanoparticles as small as 18 nm, coated with stimuli-responsive polymers, at water-oil and water-air interfaces in the presence of NaCl and NaOH, respectively. The interfacial adsorption of the nanoparticles was found to be very slow and took days to reach a fairly low surface coverage. For water-oil interfaces, in situ nanoparticle contact angles agree with the macroscopic equilibrium contact angles of planar gold surfaces with the same polymer coatings, whilst for water-air interfaces, significant differences have been observed.

Entry of microparticles into giant lipid vesicles by optical tweezers.

Entry of micro- or nanosized objects into cells or vesicles made of lipid membranes occurs in many processes such as entry of viruses into host cells, microplastics pollution, drug delivery, or biomedical imaging. Here we investigate the microparticle crossing of lipid membranes in giant unilamellar vesicles in the absence of strong binding interactions (e.g., streptavidin-biotin binding). In these conditions, we observe that organic and inorganic particles can always penetrate inside the vesicles provided an external piconewton force is applied and for relatively low membrane tensions. In the limit of vanishing adhesion, we identify the role of the membrane area reservoir and show that a force minimum exists when the particle size is comparable to the bendocapillary length.

Microparticle Brownian motion near an air-water interface governed by direction-dependent boundary conditions.

HYPOTHESIS: Although the dynamics of colloids in the vicinity of a solid interface has been widely characterized in the past, experimental studies of Brownian diffusion close to an air-water interface are rare and limited to particle-interface gap distances larger than the particle size. At the still unexplored lower distances, the dynamics is expected to be extremely sensitive to boundary conditions at the air-water interface. There, ad hoc experiments would provide a quantitative validation of predictions. EXPERIMENTS: Using a specially designed dual wave interferometric setup, the 3D dynamics of 9 µm diameter particles at a few hundreds of nanometers from an air-water interface is here measured in thermal equilibrium. FINDINGS: Intriguingly, while the measured dynamics parallel to the interface approaches expected predictions for slip boundary conditions, the Brownian motion normal to the interface is very close to the predictions for no-slip boundary conditions. These puzzling results are rationalized considering current models of incompressible interfacial flow and deepened developing an ad hoc model which considers the contribution of tiny concentrations of surface active particles at the interface. We argue that such condition governs the particle dynamics in a large spectrum of systems ranging from biofilm formation to flotation process.

Rotational and translational drags of a Janus particle close to a wall and a lipid membrane.

HYPOTHESIS: Measuring rotational and translational Brownian motion of single spherical particles reveals dissipations due to the interaction between the particle and the environment. EXPERIMENTS: In this article, we show experiments where the in-plane translational and the two rotational drag coefficients of a single spherical Brownian particle can be measured. These particle drags are functions of the particle size and of the particle-wall distance, and of the viscous dissipations at play. We measure drag coefficients for Janus particles close to a solid wall and close to a lipid bilayer membrane. FINDINGS: For a particle close to a wall, we show that according to hydrodynamic models, particle-wall distance and particle size can be determined. For a particle partially wrapped by lipid membranes, in absence of strong binding interactions, translational and rotational drags are significantly larger than the ones of non-wrapped particles. Beside the effect of the membrane viscosity, we show that dissipations in the deformed membrane cap region strongly contribute to the drag coefficients.

Driven Engulfment of Janus Particles by Giant Vesicles in and out of Thermal Equilibrium.

The interaction between Janus colloids and giant lipid vesicles was experimentally investigated to elucidate the dynamics and mechanisms related to microparticle engulfment by lipid vesicles. Janus (Pt-SiO2 and Pt-MF, where MF is melamine formaldehyde) colloids do not spontaneously adhere to POPC or DOPC bilayers, but by applying external forces via centrifugation we were able to force the contact between the particles and the membranes, which may result in a partial engulfment state of the particle. Surface properties of the Janus colloids play a crucial role in the driven particle engulfment by vesicles. Engulfment of the silica and platinum regions of the Janus particles can be observed, whereas the polymer (MF) region does not show any affinity towards the lipid bilayer. By using fluorescence microscopy, we were able to monitor the particle orientation and measure the rotational dynamics of a single Janus particle engulfed by a vesicle. By adding hydrogen peroxide to the solution, particle self-propulsion was used to perform an active transport of a giant vesicle by a single active particle. Finally, we observe that partially engulfed particles experience a membrane curvature-induced force, which pushes the colloids towards the bottom where the membrane curvature is the lowest.