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.

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.

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.

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.

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.

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.

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.

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.

Motion of micro- and nano- particles interacting with a fluid interface.

In this article, we review both theoretical models and experimental results on the motion of micro- and nano- particles that are close to a fluid interface or move in between two fluids. Viscous drags together with dissipations due to fluctuations of the fluid interface and its physicochemical properties affect strongly the translational and rotational drags of colloidal particles, which are subjected to Brownian motion in thermal equilibrium. Even if many theoretical and experimental investigations have been carried out, additional scientific efforts in hydrodynamics, statistical physics, wetting and colloid science are still needed to explain unexpected experimental results and to measure particle motion in time and space scales, which are not accessible so far.

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.

Superhydrophobic capillary coatings: Elaboration, characterization and application to electrophoretic separations.

Separation efficiency is ideally controlled by molecular diffusion in capillary electrophoresis (CE). However, other adverse phenomena, such as solute adsorption on capillary surface, tend to increase the peak dispersion. An interesting alternative to limit the solute adsorption is to avoid as much as possible the contact of the solute with the capillary surface by elaborating superhydrophobic (SH) coatings on fused silica capillary surfaces. This work describes an optimized protocol to get non-wettable SH coating using hydrophobically modified silica nanoparticle suspensions (Glaco™), based on simple capillary flushes and thermal stabilization. In this protocol, the control of the air flushing after the introduction of the Glaco™ suspension in the capillary was found crucial to get optimized coating coverage and reproducibility. The SH coating was characterized by ellipsometry, atomic force microscopy, scanning electron microscopy, contact angle (about 159°) and the observation of the meniscus of water in the coated capillary. The hydrodynamic behavior of the SH coated capillary was investigated by plotting the Poiseuille law. Finally, electrophoretic separations of a peptide mixture in acidic conditions demonstrated the interest of this approach with an increase by a factor 2 of the separation efficiency compared to fused silica capillary.

Rotational diffusion of partially wetted colloids at fluid interfaces.

HYPOTHESIS: Rotational Brownian diffusions of colloidal particles at a fluid interface play important roles in particle self-assembly and in surface microrheology. Recent experiments on translational Brownian motion of spherical particles at the air-water interface show a significant slowing down of the translational diffusion with respect to the hydrodynamic predictions (Boniello et al., 2015). For the rotational diffusions of partially wetted colloids, slowing down of the particle dynamics can be also expected. EXPERIMENTS: Here, the rotational dynamics of Janus colloids at the air-water interface have been experimentally investigated using optical microscopy. Bright field and fluorescent microscopies have been used to measure the in-plane and out-of-plane particle rotational diffusions exploiting the Janus geometry of the colloids we fabricated. FINDINGS: Our results show a severe slowing down of the rotational diffusion Dr,⊥ connected to the contact line motion and wetting-dewetting dynamics occurring on particle regions located at opposite liquid wedges. A slowing down of the particle rotational diffusion about an axis parallel to the interfacial normal Dr,|| was also observed. Contact line fluctuations due to partial wetting dynamics lead to a rotational line friction that we have modelled in order to describe our results.

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.

Multistep building of a soft plant protein film at the air-water interface.

Gliadins are edible wheat storage proteins well known for their surface active properties. In this paper, we present experimental results on the interfacial properties of acidic solutions of gliadin studied over 5 decades of concentrations, from 0.001 to 110 g/L. Dynamic pendant drop tensiometry reveals that the surface pressure Π of gliadin solutions builds up in a multistep process. The series of curves of the time evolution of Π collected at different bulk protein concentrations C can be merged onto a single master curve when Π is plotted as a function of αt where t is the time elapsed since the formation of the air/water interface and α is a shift parameter that varies with C as a power law with an exponent 2. The existence of such time-concentration superposition, which we evidence for the first time, indicates that the same mechanisms govern the surface tension evolution at all concentrations and are accelerated by an increase of the bulk concentration. The scaling of α with C is consistent with a kinetic of adsorption controlled by the diffusion of the proteins in the bulk. Moreover, we show that the proteins adsorption at the air/water interface is kinetically irreversible. Correlated evolutions of the optical and elastic properties of the interfaces, as probed by ellipsometry and surface dilatational rheology respectively, provide a consistent physical picture of the building up of the protein interfacial layer. A progressive coverage of the interface by the proteins occurs at low Π. This stage is followed, at higher Π, by conformational rearrangements of the protein film, which are identified by a strong increase of the dissipative viscoelastic properties of the film concomitantly with a peculiar evolution of its optical profile that we have rationalized. In the last stage, at even higher surface pressure, the adsorption is arrested; the optical profile is not modified while the elasticity of the interfacial layer dramatically increases with the surface pressure, presumably due to the film ageing.

Central Role of Bicarbonate Anions in Charging Water/Hydrophobic Interfaces.

Aqueous interfaces are ubiquitous in Nature and play a fundamental role in environmental or biological processes or modern nanotechnologies. These interfaces are negatively charged, and despite several decades of research, the rationale behind this phenomenon is still under debate. Two main controversial schools of thought argue on this issue; the first relies on the adsorption of hydroxide anions on hydrophobic surfaces, whereas the second one supports a self-rearrangement of water molecules at the interface bearing hydronium ions. Here, we report on two series of independent experimental studies (nanoprecipitation and interfacial tension measurements) that demonstrate that in the pH 5-10 range the negative interfacial charge of the colloids mostly stems from bicarbonate ions, whereas at lower and higher pH, protons and hydroxide ions contribute, with bicarbonate ions, to the interfacial charging. This new interpretation complies with previous studies and opens new perspectives to this striking physical chemical issue.

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.

A comparison between liquid drops and solid particles in partial wetting.

In this critical review we compare two geometries in partial wetting: a liquid drop on a planar substrate and a spherical particle at a planar liquid interface. We show that this comparison is far from being trivial even if the same physical interactions are at play in both geometries. Similarities and differences in terms of free energies and frictions will be discussed. Contact angle hysteresis, the impact of surface roughness and line pinning on wetting will be described and compared to selected experimental findings.