Mechanisms of spontaneous chain formation and subsequent microstructural evolution in shear-driven strongly confined drop monolayers.

It was experimentally demonstrated by Migler and his collaborators [Phys. Rev. Lett., 2001, 86, 1023; Langmuir, 2003, 19, 8667] that a strongly confined drop monolayer sheared between two parallel plates can spontaneously develop a flow-oriented drop-chain morphology. Here we show that the formation of the chain-like microstructure is driven by far-field Hele-Shaw quadrupolar interactions between drops, and that drop spacing within chains is controlled by the effective drop repulsion associated with the existence of confinement-induced reversing streamlines, i.e., the swapping trajectory effect. Using direct numerical simulations and an accurate quasi-2D model that incorporates quadrupolar and swapping-trajectory contributions, we analyze microstructural evolution in a monodisperse drop monolayer. Consistent with experimental observations, we find that drop spacing within individual chains is usually uniform. Further analysis shows that at low area fractions all chains have the same spacing, but at higher area fractions there is a large spacing variation from chain to chain. These findings are explained in terms of uncompressed and compressed chains. At low area fractions most chains are uncompressed (spacing equals lst, which is the stable separation of an isolated pair). At higher area fractions compressed chains (with tighter spacing) are formed in a process of chain zipping along y-shaped structural defects. We also discuss the relevance of our findings to other shear-driven systems, such as suspensions of spheres in non-Newtonian fluids.

Singular dynamics in the failure of soft adhesive contacts.

We characterize the mechanical recovery of compliant silicone gels following adhesive contact failure. We establish broad, stable adhesive contacts between rigid microspheres and soft gels, then stretch the gels to large deformations by pulling quasi-statically on the contact. Eventually, the adhesive contact begins to fail, and ultimately slides to a final contact point on the bottom of the sphere. Immediately after detachment, the gel recoils quickly with a self-similar surface profile that evolves as a power law in time, suggesting that the adhesive detachment point is singular. The singular dynamics we observe are consistent with a relaxation process driven by surface stress and slowed by viscous flow through the porous, elastic network of the gel. Our results emphasize the importance of accounting for both the liquid and solid phases of gels in understanding their mechanics, especially under extreme deformation.

Highly stiff yet elastic microcapsules incorporating cellulose nanofibrils.

Microcapsules with high mechanical stability and elasticity are desirable in a variety of contexts. We report a single-step method to fabricate such microcapsules by microfluidic interfacial complexation between high stiffness cellulose nanofibrils (CNF) and an oil-soluble cationic random copolymer. Single-capsule compression measurements reveal an elastic modulus of 53 MPa for the CNF-based capsule shell with complete recovery of deformation from strains as large as 19%. We demonstrate the ability to manipulate the shell modulus by the use of polyacrylic acid (PAA) as a binder material, and observe a direct relationship between the shell modulus and the PAA concentration, with moduli as large as 0.5 GPa attained. These results demonstrate that CNF incorporation provides a facile route for producing strong yet flexible microcapsule shells.

Soft microcapsules with highly plastic shells formed by interfacial polyelectrolyte-nanoparticle complexation.

Composite microcapsules have been aggressively pursued as designed chemical entities for biomedical and other applications. Common preparations rely on multi-step, time consuming processes. Here, we present a single-step approach to fabricate such microcapsules with shells composed of nanoparticle-polyelectrolyte and protein-polyelectrolyte complexes, and demonstrate control of the mechanical and release properties of these constructs. Interfacial polyelectrolyte-nanoparticle and polyelectrolyte-protein complexation across a water-oil droplet interface results in the formation of capsules with shell thicknesses of a few µm. Silica shell microcapsules exhibited a significant plastic response at small deformations, whereas lysozyme incorporated shells displayed a more elastic response. We exploit the plasticity of nanoparticle incorporated shells to produce microcapsules with high aspect ratio protrusions by micropipette aspiration.

Quantitative measurements and modeling of cargo-motor interactions during fast transport in the living axon.

The kinesins have long been known to drive microtubule-based transport of sub-cellular components, yet the mechanisms of their attachment to cargo remain a mystery. Several different cargo-receptors have been proposed based on their in vitro binding affinities to kinesin-1. Only two of these-phosphatidyl inositol, a negatively charged lipid, and the carboxyl terminus of the amyloid precursor protein (APP-C), a trans-membrane protein-have been reported to mediate motility in living systems. A major question is how these many different cargo, receptors and motors interact to produce the complex choreography of vesicular transport within living cells. Here we describe an experimental assay that identifies cargo-motor receptors by their ability to recruit active motors and drive transport of exogenous cargo towards the synapse in living axons. Cargo is engineered by derivatizing the surface of polystyrene fluorescent nanospheres (100 nm diameter) with charged residues or with synthetic peptides derived from candidate motor receptor proteins, all designed to display a terminal COOH group. After injection into the squid giant axon, particle movements are imaged by laser-scanning confocal time-lapse microscopy. In this report we compare the motility of negatively charged beads with APP-C beads in the presence of glycine-conjugated non-motile beads using new strategies to measure bead movements. The ensuing quantitative analysis of time-lapse digital sequences reveals detailed information about bead movements: instantaneous and maximum velocities, run lengths, pause frequencies and pause durations. These measurements provide parameters for a mathematical model that predicts the spatiotemporal evolution of distribution of the two different types of bead cargo in the axon. The results reveal that negatively charged beads differ from APP-C beads in velocity and dispersion, and predict that at long time points APP-C will achieve greater progress towards the presynaptic terminal. The significance of this data and accompanying model pertains to the role transport plays in neuronal function, connectivity, and survival, and has implications in the pathogenesis of neurological disorders, such as Alzheimer's, Huntington and Parkinson's diseases.

Static-state particle fabrication via rapid vitrification of a thixotropic medium.

Functional particles that respond to external stimuli are spurring technological evolution across various disciplines. While large-scale production of functional particles is needed for their use in real-life applications, precise control over particle shapes and directional properties has remained elusive for high-throughput processes. We developed a high-throughput emulsion-based process that exploits rapid vitrification of a thixotropic medium to manufacture diverse functional particles in large quantities. The vitrified medium renders stationary emulsion droplets that preserve their shape and size during solidification, and energetic fields can be applied to build programmed anisotropy into the particles. We showcase mass-production of several functional particles, including low-melting point metallic particles, self-propelling Janus particles, and unidirectionally-magnetized robotic particles, via this static-state particle fabrication process.

Spatially extended FCS for visualizing and quantifying high-speed multiphase flows in microchannels.

We report the development of spatially extended fluorescence correlation spectroscopy for visualizing and quantifying multiphase flows in microchannels. We employ simultaneous detection with a high-speed camera across the width of the channel, enabling investigation of the dynamics of the flow at short time scales. We take advantage of the flow to scan the sample past the fixed illumination, capturing frames up to 100 KHz. At these rates, we can resolve the motion of sub-micron particles at velocities up to the order of 1 cm/s. We visualize flows with kymographs and quantify velocity profiles by cross-correlations within the focal volume. We demonstrate the efficacy of our approach by measuring the depth-resolved velocity profile of suspensions of sub-micron diameter silica particles flowing up to 1.5 mm/s.

Criteria for drop generation in multiphase microfluidic devices.

A theory is presented for the transition between the coflowing and the drop-generation regimes observed in microfluidic channels with a rectangular cross section. This transition is characterized by a critical ratio of the dispersed- to continuous-phase volume flow rates. At flow-rate ratios higher than this critical value, drop generation is suppressed. The critical ratio corresponds to the fluid cross section where the dispersed-phase fluid is just tangent to the channel walls. The transition criterion is a function of the ratio of the fluid viscosities, the three-phase contact angle formed between the fluid phases and the channel walls, and the aspect ratio of the channel cross section; the transition is independent of interfacial tension. Hysteretic behavior of drop generation with respect to the flow-rate ratio is predicted for partially wetting dispersed-phase fluids. Experimental data are consistent with this theory.

Single-step microfluidic fabrication of soft monodisperse polyelectrolyte microcapsules by interfacial complexation.

Common methods for fabrication of polyelectrolyte microcapsules rely on a multi-step process. We propose a single-step approach to generate polyelectrolyte microcapsules with 1-2 µm shells based on polyelectrolyte complexation across a water/oil droplet interface and study the effect of parameters controlling the polyelectrolyte complexation on shell thickness.

Comparison of monodisperse droplet generation in flow-focusing devices with hydrophilic and hydrophobic surfaces.

A thin flow-focusing microfluidic channel is evaluated for generating monodisperse liquid droplets. The microfluidic device is used in its native state, which is hydrophilic, or treated with OTS to make it hydrophobic. Having both hydrophilic and hydrophobic surfaces allows for creation of both oil-in-water and water-in-oil emulsions, facilitating a large parameter study of viscosity ratios (droplet fluid/continuous fluid) ranging from 0.05 to 96 and flow rate ratios (droplet fluid/continuous fluid) ranging from 0.01 to 2 in one geometry. The hydrophilic chip provides a partially-wetting surface (contact angle less than 90°) for the inner fluid. This surface, combined with the unusually thin channel height, promotes a flow regime where the inner fluid wets the top and bottom of the channel in the orifice and a stable jet is formed. Through confocal microscopy, this fluid stabilization is shown to be highly influenced by the contact angle of the liquids in the channel. Non-wetting jets undergo breakup and produce drops when the jet is comparable to or smaller than the channel thickness. In contrast, partially-wetting jets undergo breakup only when they are much smaller than the channel thickness. Drop sizes are found to scale with a modified capillary number based on the total flow rate regardless of wetting behavior.

Coalescence of drops with tangentially mobile interfaces: effects of ambient flow.

According to the classical theory of film drainage for drops with tangentially immobile interfaces, the ambient flow field has no influence on film drainage aside from the hydrodynamic pushing force that it provides. The current theories of drop coalescence assume that this feature applies also to drops with tangentially mobile interfaces. This assumption is incorrect, except at short times. At long times, ambient flow conditions qualitatively affect film drainage, even under small-deformation conditions. The ambient flow can arrest film drainage, preventing coalescence, or exponentially enhance film drainage. Here, a new axisymmetric thin-film formulation is presented that correctly accounts for the influence of the ambient flow field. The formulation correctly recovers theoretical predictions for the stationary film thickness at long times. An analysis of the long-time behavior under accelerated drainage conditions explains why film thinning occurs exponentially. The numerical predictions of the new thin-film formulation are compared to whole-drop boundary integral simulations and are found to be in good agreement under small-deformation conditions. Thin-film simulations are used to describe offset collisions of drops, under the simplifying assumption that film drainage is unaffected by the tangential relative motion of the drops.