In this research, we study cylindrical microparticles at fluid interfaces. Cylinders orient and assemble with high reliability to form end-to-end chains in dilute surfaces or dense rectangular lattices in crowded surfaces owing to capillary interactions. In isolation, a cylinder assumes one of two possible equilibrium states, the end-on state, in which the cylinder axis is perpendicular to the interface, or the side-on state, in which the cylinder axis is parallel to the interface. A phase diagram relating aspect ratio and contact angle is constructed to predict the preferred state and verified in experiment. Cylinders in the side-on state create distortions that result in capillary interactions. Overlapping deformations by neighboring particles drive oriented capillary assembly. Interferometry, electron microscopy, and numerical simulations are used to characterize the interface shape around isolated particles. Experiments and numerics show that "side-on" cylinders have concentrated excess area near the end faces, and that the interface distortion resembles an elliptical quadrupole a few radii away from the particle surface. To model the cylinder interactions for separations greater than a few radii, an anisotropic potential is derived based on elliptical quadrupoles. This potential predicts an attractive force and a torque, both of which depend strongly on aspect ratio, in keeping with experiment. Particle trajectories and angular orientations recorded by video microscopy agree with the predicted potential. In particular, the analysis predicts the rate of rotation, a feature lacking in prior analyses. To understand interactions near contact, the concentrated excess area near the cylinder ends is quantified and its role in creating stable end-to-end assemblies is discussed. When a pair of cylinders is near contact, these high excess area regions overlap to form a capillary bridge between the particles. This capillary bridge may stabilize the end-to-end chains. Finally, on densely packed surfaces, cylinder-covered colloidosomes form with particles arranged in regular, rectangular lattices in the interface; this densely packed structure differs significantly from assemblies reported for colloidosomes or particle-stabilized droplets in the literature.

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The authors report optical observations of the change in the dynamics of one and the same ultrasound contrast agent microbubble due to the influence of interfaces and neighboring bubbles. The bubble is excited by a 2.25 MHz ultrasound burst and its oscillations are recorded with an ultrahigh-speed camera at 15 million frames per second. The position of an individual bubble relative to a rigid wall or second bubble is precisely controlled using optical tweezers based on Laguerre-Gaussian laser beams [ P. Prentice et al., Opt. Express 12, 593 (2004) ; V. Garbin et al., Jpn. J. Appl. Phys. 44, 5773 (2005) ]. This allows for repeated experiments on the very same bubble and for a quantitative comparison of the effect of boundaries on bubble behavior

While nanoparticle adsorption to fluid interfaces has been studied from a fundamental standpoint and exploited in application, the reverse process, i.e. desorption and disassembly, remains relatively unexplored. Here we demonstrate the forced desorption of gold nanoparticles capped with amphiphilic ligands from an oil-water interface. A monolayer of nanoparticles is allowed to spontaneously form by adsorption from an aqueous suspension onto a drop of oil, and is subsequently compressed by decreasing the drop volume. The surface pressure is monitored by pendant drop tensiometry throughout the process. Upon compression, the nanoparticles are mechanically forced out of the interface into the aqueous phase. An optical method is developed to measure the nanoparticle area density in situ. We show that desorption occurs at a coverage that corresponds to close packing of the ligand-capped particles, suggesting that ligand-induced repulsion plays a crucial role in this process. * kstebe@seas.upenn.edu 2

Coated microbubbles, unlike tissue are able to scatter sound subharmonically. Therefore, the subharmonic behavior of coated microbubbles can be used to enhance the contrast in ultrasound contrast imaging. Theoretically, a threshold amplitude of the driving pressure can be calculated above which subharmonic oscillations of microbubbles are initiated. Interestingly, earlier experimental studies on coated microbubbles demonstrated that the threshold for these bubbles is much lower than predicted by the traditional linear viscoelastic shell models. This paper presents an experimental study on the subharmonic behavior of differently sized individual phospholipid coated microbubbles. The radial subharmonic response of the microbubbles was recorded with the Brandaris ultra high-speed camera as a function of both the amplitude and the frequency of the driving pulse. Threshold pressures for subharmonic generation as low as 5 kPa were found near a driving frequency equal to twice the resonance frequency of the bubble. An explanation for this low threshold pressure is provided by the shell buckling model proposed by Marmottant et al. [ J. Acoust. Soc. Am. 118, 3499-3505 (2005)]. It is shown that the change in the elasticity of the bubble shell as a function of bubble radius as proposed in this model, enhances the subharmonic behavior of the microbubbles. Coated microbubbles, unlike tissue are able to scatter sound subharmonically. Therefore, the subharmonic behavior of coated microbubbles can be used to enhance the contrast in ultrasound contrast imaging. Theoretically, a threshold amplitude of the driving pressure can be calculated above which subharmonic oscillations of microbubbles are initiated. Interestingly, earlier experimental studies on coated microbubbles demonstrated that the threshold for these bubbles is much lower than predicted by the traditional linear viscoelastic shell models. This paper presents an experimental study on the subharmonic behavior of differently sized individual phospholipid coated microbubbles. The radial subharmonic response of the microbubbles was recorded with the Brandaris ultra high-speed camera as a function of both the amplitude and the frequency of the driving pulse. Threshold pressures for subharmonic generation as low as 5 kPa were found near a driving frequency equal to twice the resonance frequency of the bubble. An explanation for this low threshold pressure is provided by the shell buckling model proposed by Marmottant et al. ͓J. Acoust. Soc. Am. 118, 3499-3505 ͑2005͔͒. It is shown that the change in the elasticity of the bubble shell as a function of bubble radius as proposed in this model, enhances the subharmonic behavior of the microbubbles.

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The self-assembly of solid particles at fluid-fluid interfaces is widely exploited to stabilize emulsions and foams, and in materials synthesis. The self-assembly mechanism is very robust owing to the large capillary energy associated with particle adsorption, of the order of millions of times the thermal energy for micrometer-sized colloids. The microstructure of the interfacial colloid monolayer can also favor stability, for instance in the case of particle-stabilized bubbles, which can be indefinitely stable against dissolution due to jamming of the colloid monolayer. As a result, significant challenges arise when destabilization and particle removal are a requirement. Here we demonstrate ultrafast desorption of colloid monolayers from the interface of particle-stabilized bubbles. We drive the bubbles into periodic compression-expansion using ultrasound waves, causing significant deformation and microstructural changes in the particle monolayer. Using high-speed microscopy we uncover different particle expulsion scenarios depending on the mode of bubble deformation, including highly directional patterns of particle release during shape oscillations. Complete removal of colloid monolayers from bubbles is achieved in under a millisecond. Our method should find a broad range of applications, from nanoparticle recycling in sustainable processes to programmable particle delivery in lab-on-achip applications.self-assembly | colloidal interactions | Pickering | interfacial assemblies C olloidal particles can adsorb to fluid-fluid interfaces and confer outstanding stability to emulsions and foams (1, 2). The interfacial self-assembly of colloids has been used to create novel materials, for instance colloidosomes (3) and bijels (4). These applications rely on the large decrease in free energy accompanying particle adsorption, ΔE = −γ 0 πa 2 ð1 − cos θÞ 2 , which depends on the surface tension γ 0 , the particle size a, and the three-phase contact angle θ (5), and ranges from hundreds to millions of times the thermal energy for nanometer-to micrometer-sized particles. The microstructure that the colloidal particles form at the interface has also been shown to enhance stability. For instance, jamming of an interfacial colloid monolayer prevents coarsening in bicontinuous emulsions (4) and can arrest the dissolution of particle-stabilized bubbles (6). Particle removal from fluid-fluid interfaces is a significant challenge in emerging applications of functional nanoparticles in interfacial biocatalysis (7), gas storage (8), and biomass conversion (9), where the ability to recover and regenerate the nanoparticles at the end of the process is a key requirement. The most common approaches to particle removal from fluid interfaces are based on the physicochemical modification of the fluid phases or the interface. Desorption has been obtained for instance by the addition of a surface-active agent (10, 11). In addition, by tuning the strength of electrostatic repulsion between charged particles at an interface through pH and el...