Multiple emulsions, which are widely applied in a myriad of fields because of their unique ability to encapsulate and protect active ingredients, are typically produced by sequential drop-formations and drop-encapsulations using shear-induced emulsification. Here we report a qualitatively novel method of creating highly controlled multiple emulsions from lower-order emulsions. By carefully controlling the interfacial energies, we adjust the spreading coefficients between different phases to cause drops of one fluid to completely engulf other drops of immiscible fluids; as a result multiple emulsions are directly formed by simply putting preformed lower-order emulsion drops together. Our approach has highly controllable flexibility. We demonstrate this in preparation of both double and triple emulsions with a controlled number of inner drops and precisely adjusted shell thicknesses including ultra-thin shells. Moreover, this controllable drop-engulfing-drop approach has a high potential in further investigations and applications of microfluidics. Importantly, this innovative approach opens a window to exploit new phenomena occurring in fluids at the microscale level, which is of great significance for developing novel microfluidics.
Monodisperse poly(dl-lactic acid) (PLA) particles with a diameter in the range from 12 to 100 $μ$m were fabricated in flow focusing glass capillary devices by evaporation of dichloromethane (DCM) from emulsions at room temperature. The dispersed phase was 5% (w/w) PLA in DCM containing a small amount of Nile red and the continuous phase was 5% (w/w) poly(vinyl alcohol) in reverse osmosis water. Particle diameter was 2.7 times smaller than the size of the emulsion droplet template indicating that the particle porosity was very low. SEM images revealed that the majority of particle pores are in the sub-micron region but in some instances these pores can reach 3 $μ$m in diameter. Droplet diameter was influenced by the flow rates of the two phases and the entry diameter of the collection capillary tube; droplet diameters decreased with increasing values of the flow rate ratio of the dispersed to continuous phase to reach constant minimum values at 40–60% orifice diameter. At flow rate ratios less than 5, jetting can occur, giving rise to large droplets formed by detachment from relatively long jets (\textasciitilde10 times longer than droplet diameter).
Double emulsions are useful templates for microcapsules and complex particles, but no method yet exists for making double emulsions with both high uniformity and high throughput. We present a parallel numbering-up design for microfluidic double emulsion devices, which combines the excellent control of microfluidics with throughput suitable for mass production. We demonstrate the design with devices incorporating up to 15 dropmaker units in a two-dimensional or three-dimensional array, producing single-core double emulsion drops at rates over 1 kg day(-1) and with diameter variation less than 6%. This design provides a route to integrating hundreds of dropmakers or more in a single chip, facilitating industrial-scale production rates of many tons per year.
We use confocal microscopy to study the three-dimensional (3D) structure of colloidal crystals formed by poly(N-isopropylacrylamide)-co-(acrylic acid) microgels of diameter 1.0-1.5 mu m. The confocal images are tracked to locate particle positions in 3D, which are used to compute pair-correlation functions g(r), bond order parameters, and structure factors s(q). We find that the structure remains fcc for a range of charge, size, and concentration of the particles. When the particles are weakly attractive and are at low concentrations, polycrystalline solids result. In addition, owing to the compressibility of the colloids, the crystals display remarkable structural stability when subjected to external stress.
We investigate the mechanics of dense packing of very small, colloidal-scale, and larger, granular-scale microgel particles. At low particle concentration, thermally induced Brownian motion of the particles is important for the colloidal-scale systems; in contrast, such Brownian motion is irrelevant at particle packing fractions beyond jamming. As a consequence, colloidal and granular systems behave very similarly under these conditions. At sufficiently high compression of the microgel particles, their polymeric nature sets the scale of the osmotic pressure and shear modulus of the whole packing, in direct analogy with macroscopic, continuous polymer gels. This observation suggests that the particulate nature of microgels is inconsequential for their linear elasticity in a highly packed state. In contrast, the particulate nature of the microgels does become essential when the packed suspensions are forced to yield and flow; here, the differences between colloidal-and granular-scale particles are marked.
We introduce confocal differential dynamic microscopy (ConDDM), a new technique yielding information comparable to that given by light scattering but in dense, opaque, fluorescent samples of micron-sized objects that cannot be probed easily with other existing techniques. We measure the correct wave vector q-dependent structure and hydrodynamic factors of concentrated hard-sphere-like colloids. We characterize concentrated swimming bacteria, observing ballistic motion in the bulk and a new compressed-exponential scaling of dynamics, and determine the velocity distribution; by contrast, near the coverslip, dynamics scale differently, suggesting that bacterial motion near surfaces fundamentally differs from that of freely swimming organisms.
Like charges stabilize emulsions, whereas opposite charges break emulsions. This is the fundamental principle for many industrial and practical processes. Using micrometer-sized pH-sensitive polymeric hydrogel particles as emulsion stabilizers, we prepare emulsions that consist of oppositely charged droplets, which do not coalesce. We observe noncoalescence of oppositely charged droplets in bulk emulsification as well as in microfluidic devices, where oppositely charged droplets are forced to collide within channel junctions. The results demonstrate that electrostatic interactions between droplets do not determine their stability and reveal the unique pH-dependent properties of emulsions stabilized by soft microgel particles. The noncoalescence can be switched to coalescence by neutralizing the microgels, and the emulsion can be broken on demand. This unusual feature of the microgel-stabilized emulsions offers fascinating opportunities for future applications of these systems.
Sample-spanning networks of aggregated colloidal particles have a finite stiffness and deform elastically when subjected to a small shear stress. After some period of creep, these gels ultimately suffer catastrophic failure. This delayed yielding is governed by the association and dissociation dynamics of interparticle bonds and the strand structure of the gel. We derive a model which connects the kinetics of the colloids to the erosion of the strand structure and ultimately to macroscopic failure. Importantly, this model relates time-to-failure of the gel to an applied static stress. Model predictions are in quantitative agreement with experiments. It is predicted that the strand structure, characterized by its mesh size and strand coarseness, has a significant impact on delay time. Decreasing the mesh size or increasing the strand thickness makes colloidal gels more resilient to delayed yielding. The quench and flow history of gels modifies their microstructures. Our experiments show that a slow quenching increases the delay time due to the coarsening of the strands; by contrast, preshear reduces the delay time, which we explain by the increased mesh size as a result of shear-induced fracture of strands.
The commonly accepted description of drops impacting on a surface typically ignores the essential role of the air that is trapped between the impacting drop and the surface. Here we describe a new imaging modality that is sensitive to the behavior right at the surface. We show that a very thin film of air, only a few tens of nanometers thick, remains trapped between the falling drop and the surface as the drop spreads. The thin film of air serves to lubricate the drop enabling the fluid to skate on the air film laterally outward at surprisingly high velocities, consistent with theoretical predictions. Eventually this thin film of air breaks down as the fluid wets the surface via a spinodal-like mechanism. Our results show that the dynamics of impacting drops are much more complex than previously thought, with a rich array of unexpected phenomena that require rethinking classic paradigms.
Colloidal particles with site-specific directional interactions, so called "patchy particles", are promising candidates for bottom-up assembly routes towards complex structures with rationally designed properties. Here we present an experimental realization of patchy colloidal particles based on material independent depletion interaction and surface roughness. Curved, smooth patches on rough colloids are shown to be exclusively attractive due to their different overlap volumes. We discuss in detail the case of colloids with one patch that serves as a model for molecular surfactants both with respect to their geometry and their interactions. These one-patch particles assemble into clusters that resemble surfactant micelles with the smooth and attractive sides of the colloids located at the interior. We term these clusters "colloidal micelles". Direct Monte Carlo simulations starting from a homogeneous state give rise to cluster size distributions that are in good agreement with those found in experiments. Important differences with surfactant micelles originate from the colloidal character of our model system and are investigated by simulations and addressed theoretically. Our new "patchy" model system opens up the possibility for self-assembly studies into finite-sized superstructures as well as crystals with as of yet inaccessible structures.
Droplet microfluidics offers significant advantages for performing high-throughput screens and sensitive assays. Droplets allow sample volumes to be significantly reduced, leading to concomitant reductions in cost. Manipulation and measurement at kilohertz speeds enable up to 10(8) samples to be screened in one day. Compartmentalization in droplets increases assay sensitivity by increasing the effective concentration of rare species and decreasing the time required to reach detection thresholds. Droplet microfluidics combines these powerful features to enable currently inaccessible high-throughput screening applications, including single-cell and single-molecule assays.
We describe droplet microfluidic strategies used to fabricate advanced microparticles that are useful structures for the encapsulation and release of actives; these strategies can be further developed to produce microparticles for advanced drug delivery applications. Microfluidics enables exquisite control in the fabrication of polymer vesicles and thermosensitive microgels from single and higher-order multiple emulsion templates. The strategies used to create the diversity of microparticle structures described in this review, coupled with the scalability of microfluidics, will enable fabrication of large quantities of novel microparticle structures that have potential uses in controlled drug release applications.
We use a perfluorinated-dendrimer-dye complex that stabilizes microbubbles as a novel pore-forming agent. We use microfluidics to produce monodisperse emulsions containing a polymer matrix material, a model active, and the perfluorinated complex; upon drying, the emulsions form porous microspheres. This porosity causes the encapsulated model active to be released faster than from non-porous microspheres. Moreover, because of the fluorous features of the pores, we can also attach an additional guest molecule to the pores which is released with a profile that is distinct from that of the encapsulated active. These porous microspheres can encapsulate and controllably release multiple actives; this makes them valuable for applications such as drug delivery and imaging.
We present a strategy for preparing size-controlled gas-filled microparticles using two aqueous components that chemically react to produce the gas. We use a dual-bore microfluidic device to isolate the reactants of two gas-producing reactions until they are encapsulated in the outer droplet. The reactants in the monodisperse droplets merge and produce the gas bubbles, which are stabilized with a surfactant and form the core of the microparticles. The number and size of the generated gas bubbles are governed by the gas-forming reaction used. Our versatile strategy can be applied to a wide range of gas-producing reactions.
Colloidal capsules can sustain an external osmotic pressure; however, for a sufficiently large pressure, they will ultimately buckle. This process can be strongly influenced by structural inhomogeneities in the capsule shells. We explore how the time delay before the onset of buckling decreases as the shells are made more inhomogeneous; this behavior can be quantitatively understood by coupling shell theory with Darcy's law. In addition, we show that the shell inhomogeneity can dramatically change the folding pathway taken by a capsule after it buckles.
Affinity reagents, such as antibodies, are needed to study protein expression patterns, sub-cellular localization, and post-translational modifications in complex mixtures and tissues. Phage Emulsion, Secretion, and Capture (ESCape) is a novel micro-emulsion technology that utilizes water-in-oil (W/O) emulsions for the identification and isolation of cells secreting phage particles that display desirable antibodies. Using this method, a large library of antibody-displaying phage will bind to beads in individual compartments. Rather than using biopanning on a large mixed population, phage micro-emulsion technology allows us to individually query clonal populations of amplified phage against the antigen. The use of emulsions to generate microdroplets has the promise of accelerating phage selection experiments by permitting fine discrimination of kinetic parameters for binding to targets. In this study, we demonstrate the ability of phage micro-emulsion technology to distinguish two scFvs with a 300-fold difference in binding affinities (100 nM and 300 pM, respectively). In addition, we describe the application of phage microemulsion technology for the selection of scFvs that are resistant to elevated temperatures. (C) 2012 Published by Elsevier Inc.