Muluneh, M. ; Weitz, D. A. Direct visualization of three-dimensional crystallization behavior in microgels. Physical Review E 2012, 85.Abstract
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.
Times Cited: 3 1
Menut, P. ; Seiffert, S. ; Sprakel, J. ; Weitz, D. A. Does size matter? Elasticity of compressed suspensions of colloidal- and granular-scale microgels. Soft Matter 2012, 8 156-164.Abstract
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.
Times Cited: 7
Martino, C. ; Kim, S. - H. ; Horsfall, L. ; Abbaspourrad, A. ; Rosser, S. J. ; Cooper, J. ; Weitz, D. A. Protein expression, aggregation, and triggered release from polymersomes as artificial cell-like structures. Angewandte Chemie-International Edition 2012, 51, 6416-6420. [PDF]
Times Cited: 11
Lu, P. J. ; Giavazzi, F. ; Angelini, T. E. ; Zaccarelli, E. ; Jargstorff, F. ; Schofield, A. B. ; Wilking, J. N. ; Romanowsky, M. B. ; Weitz, D. A. ; Cerbino, R. Characterizing concentrated, multiply scattering, and actively driven fluorescent systems with confocal differential dynamic microscopy. Physical Review Letters 2012, 108.Abstract
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.
Times Cited: 10
Liu, T. ; Seiffert, S. ; Thiele, J. ; Abate, A. R. ; Weitz, D. A. ; Richtering, W. Non-coalescence of oppositely charged droplets in pH-sensitive emulsions. Proceedings of the National Academy of Sciences of the United States of America 2012, 109, 384-389.Abstract
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.
Times Cited: 15
Lindstrom, S. B. ; Kodger, T. E. ; Sprakel, J. ; Weitz, D. A. Structures, stresses, and fluctuations in the delayed failure of colloidal gels. Soft Matter 2012, 8 3657-3664.Abstract
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.
Times Cited: 7
Kolinski, J. M. ; Rubinstein, S. M. ; Mandre, S. ; Brenner, M. P. ; Weitz, D. A. ; Mahadevan, L. Skating on a film of air: Drops impacting on a surface. Physical Review Letters 2012, 108.Abstract
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.
Times Cited: 18
Kraft, D. J. ; Ni, R. ; Smallenburg, F. ; Hermes, M. ; Yoon, K. ; Weitz, D. A. ; van Blaaderen, A. ; Groenewold, J. ; Dijkstra, M. ; Kegel, W. K. Surface roughness directed self-assembly of patchy particles into colloidal micelles. Proceedings of the National Academy of Sciences of the United States of America 2012, 109, 10787-10792.Abstract
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.
Times Cited: 31
Guo, M. T. ; Rotem, A. ; Heyman, J. A. ; Weitz, D. A. Droplet microfluidics for high-throughput biological assays. Lab on a Chip 2012, 12, 2146-2155.Abstract
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.
Times Cited: 56
Duncanson, W. J. ; Lin, T. ; Abate, A. R. ; Seiffert, S. ; Shah, R. K. ; Weitz, D. A. Microfluidic synthesis of advanced microparticles for encapsulation and controlled release. Lab on a Chip 2012, 12, 2135-2145.Abstract
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.
Times Cited: 26
Duncanson, W. J. ; Zieringer, M. ; Wagner, O. ; Wilking, J. N. ; Abbaspourrad, A. ; Haag, R. ; Weitz, D. A. Microfluidic synthesis of monodisperse porous microspheres with size-tunable pores. Soft Matter 2012, 8 10636-10640.Abstract
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.
Times Cited: 9
Duncanson, W. J. ; Abbaspourrad, A. ; Shum, H. C. ; Kim, S. - H. ; Adams, L. L. A. ; Weitz, D. A. Monodisperse gas-filled microparticles from reactions in double emulsions. Langmuir 2012, 28, 6742-6745.Abstract
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.
Times Cited: 8
Datta, S. S. ; Kim, S. - H. ; Paulose, J. ; Abbaspourrad, A. ; Nelson, D. R. ; Weitz, D. A. Delayed buckling and guided folding of inhomogeneous capsules. Physical Review Letters 2012, 109.Abstract
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.
Times Cited: 13
Buhr, D. L. ; Acca, F. E. ; Holland, E. G. ; Johnson, K. ; Maksymiuk, G. M. ; Vaill, A. ; Kay, B. K. ; Weitz, D. A. ; Weiner, M. P. ; Kiss, M. M. Use of micro-emulsion technology for the directed evolution of antibodies. Methods 2012, 58, 28-33.Abstract
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.
Times Cited: 3
Amstad, E. ; Kim, S. - H. ; Weitz, D. A. Photo- and thermoresponsive polymersomes for triggered release. Angewandte Chemie-International Edition 2012, 51, 12499-12503. [PDF]
Times Cited: 6
Adams, L. L. A. ; Kodger, T. E. ; Kim, S. - H. ; Shum, H. C. ; Franke, T. ; Weitz, D. A. Single step emulsification for the generation of multi-component double emulsions. Soft Matter 2012, 8 10719-10724.Abstract
We successfully encapsulate two, three, and four different inner drops inside double emulsions by means of a single-step emulsification technique. The microfluidic device fabrication is simple and the emulsification process highly robust. Optical microscopy images of double emulsion generation and of monodisperse double emulsions with discrete numbers of inner drops indicate the achievement of a high level of control with this technique. When the middle fluid transitions from dripping to jetting, two additional variations of double emulsions are produced: highly packed double emulsions and double emulsions with different sizes of inner drops. Finally, we successfully coalesce inner drops confined in a wax shell by applying heat. This demonstrates that these multi-component double emulsions may be useful as micro-reactors.
Times Cited: 8
Abate, A. R. ; Han, L. ; Jin, L. ; Suo, Z. ; Weitz, D. A. Measuring the elastic modulus of microgels using microdrops. Soft Matter 2012, 8 10032-10035.Abstract
Two microgel particles are encapsulated in a microdrop having a spherical diameter smaller than the sum of the diameters of the microgels; this causes the microgels to be squeezed together by the oil-water interface of the drop, in turn, making the drop ellipsoidal in shape. By modeling the force applied to the microgels by the drop and equating this to the Hertz contact force of their deformation, we are able to estimate their elastic modulus. By varying the surface tension and shape of the drops, we are able to measure the modulus of the microgels under different loads. This provides a simple technique for quantifying the elasticity of small, deformable objects, including liquid drops, microgels, and cells.
Times Cited: 1
Abate, A. R. ; Mary, P. ; van Steijn, V. ; Weitz, D. A. Experimental validation of plugging during drop formation in a T-junction. Lab on a Chip 2012, 12, 1516-1521.Abstract
At low capillary number, drop formation in a T-junction is dominated by interfacial effects: as the dispersed fluid flows into the drop maker nozzle, it blocks the path of the continuous fluid; this leads to a pressure rise in the continuous fluid that, in turn, squeezes on the dispersed fluid, inducing pinch-off of a drop. While the resulting drop volume predicted by this "squeezing'' mechanism has been validated for a range of systems, as of yet, the pressure rise responsible for the actual pinch-off has not been observed experimentally. This is due to the challenge of measuring the pressures in a T-junction with the requisite speed, accuracy, and localization. Here, we present an empirical study of the pressures in a T-junction during drop formation. Using Laplace sensors, pressure probes we have developed, we confirm the central ideas of the squeezing mechanism; however, we also uncover other findings, including that the pressure of the dispersed fluid is not constant but rather oscillates in anti-phase with that of the continuous fluid. In addition, even at the highest capillary number for which monodisperse drops can be formed, pressure oscillations persist, indicating that drop formation in confined geometries does not transition to an entirely shear-driven mechanism, but to a mechanism combining squeezing and shearing.
Times Cited: 7
Shum, H. C. ; Varnell, J. ; Weitz, D. A. Microfluidic fabrication of water-in-water (w/w) jets and emulsions. Biomicrofluidics 2012, 6.Abstract

We demonstrate the generation of water-in-water ( w/w) jets and emulsions by combining droplet microfluidics and aqueous two-phase systems ( ATPS). The application of ATPS in microfluidics has been hampered by the low interfacial tension between typical aqueous phases. The low tension makes it difficult to form w/w droplets with conventional droplet microfluidic approaches. We show that by mechanically perturbing a stable w/w jet, w/w emulsions can be prepared in a controlled and reproducible fashion. We also characterize the encapsulation ability of w/w emulsions and demonstrate that their encapsulation efficiency can be significantly enhanced by inducing formation of precipitates and gels at the w/w interfaces. Our work suggests a biologically and environmentally friendly platform for droplet microfluidics and establishes the potential of w/w droplet microfluidics for encapsulation-related applications. (C) 2012 American Institute of Physics. [doi:10.1063/1.3670365]

Rotem, A. ; Abate, A. R. ; Utada, A. S. ; van Steijn, V. ; Weitz, D. A. Drop formation in non-planar microfluidic devices. Lab on a Chip 2012, 12, 4263-4268.Abstract

Microfluidic devices can be used to produce single or multiple emulsions with remarkably precise control of both the contents and size of the drops. Since each level of a multiple emulsion is formed by a distinct fluid stream, very efficient encapsulation of materials can be achieved. To obtain high throughput, these devices can be fabricated lithographically, allowing many devices to operate in parallel. However, to form multiple emulsions using a planar microfluidic device, the wettability of its surface must switch from hydrophobic to hydrophilic on the scale of micrometers where the drops are formed; this makes the fabrication of the devices very difficult. To overcome this constraint, we introduce non-planar microfluidic devices with graduated thicknesses; these can make drops even when their wetting properties do not favor drop formation. Nevertheless, the dependence of drop formation on the device geometry, the flow rates and the properties of the fluids, particularly in the case of unfavorable wetting, is very complex, making the successful design of these devices more difficult. Here we show that there exists a critical value of flow of the continuous phase above which drop formation occurs; this value decreases by two orders of magnitude as the wetting to the device wall of the continuous phase improves. We demonstrate how this new understanding can be used to optimize device design for efficient production of double or multiple emulsions.