Liquid-based stationary phase for deterministic lateral displacement separation in microfluidics.

Deterministic lateral displacement (DLD) is a promising separation scheme in microfluidic systems. In traditional DLD, a periodic array of solid posts induces the separative migration of suspended particles moving through the system. Here, we present a radical departure from traditional DLD systems and use an array of anchored liquid-bridges as the stationary phase in the DLD device. The liquid-bridges are created between two parallel plates and anchored to the bottom one by cylindrical wells. We show that the non-linear particle dynamics observed in traditional DLD systems is also present in the anchored-liquid case, enabling analogous size-based separation of suspended particles. The use of liquid-bridges as the stationary phase presents additional possibilities in separation technologies, potentially eliminating or significantly reducing clogging, enabling renewable and/or reconfigurable systems, allowing a different set of fabrication methods and providing alternative ways to separate particles based on their interaction with liquid-liquid interfaces. Some of these advantages could also extend to filtration methods based on similar liquid-based stationary phases.

An Aqueous-Based Approach for Fabrication of PVDF/MWCNT Porous Composites.

In this paper, we demonstrate the fabrication of conductive porous polymers based on foaming of an aqueous dispersion of polymeric particles and multi-walled carbon nanotubes (CNT). By tuning the surface energy of the constituents, we direct their preferential adsorption at the air-liquid (bubble) interface or within the liquid film between the bubbles. Sintering this bi-constituent foam yields solid closed-cell porous structure which can be electrically conductive if CNT are able to form a conductive path. We measure transport (electrical and thermal), mechanical, and morphological properties of such porous structures as a function of CNT loading and the method used for their surface functionalization. For a fixed polymer volume fraction, we demonstrate the limit in which increasing CNT results in decreasing the mechanical strength of the sample due to lack of adequate polymer-CNT bond. Such lightweight conductive porous composites are considered in applications including EMI shielding, electrostatic discharge protection, and electrets.

Tilting and Tumbling of Janus Nanoparticles at Sheared Interfaces.

We investigate the response of a single Janus nanoparticle adsorbed at an oil-water interface to imposed shear flows using molecular dynamics simulations. We consider particles of different geometry, including spheres, cylinders, and discs, and tune their degree of amphiphilicity by controlling the affinity of their two sides to the fluid phases. We observe that depending on the shape, amphiphilicity, and the applied shear rate, two modes of rotational dynamics takes place: a smooth tilt or a tumbling motion. We demonstrate that irrespective of this dynamic behavior, a steady-state orientation is eventually achieved as a result of the balance between the shear- and capillary-induced torques, which can be tuned by controlling the surface property and flow parameters. Our findings provide insight on using flow fields to tune particle orientation at an interface and to utilize it to direct their assembly into ordered monolayers.

Molecular simulation of translational and rotational diffusion of Janus nanoparticles at liquid interfaces.

We perform molecular dynamics simulations to understand the translational and rotational diffusion of Janus nanoparticles at the interface between two immiscible fluids. Considering spherical particles with different affinity to fluid phases, both their dynamics as well as the fluid structure around them are evaluated as a function of particle size, amphiphilicity, fluid density, and interfacial tension. We show that as the particle amphiphilicity increases due to enhanced wetting of each side with its favorite fluid, the rotational thermal motion decreases. Moreover, the in-plane diffusion of nanoparticles at the interface becomes slower for more amphiphilic particles, mainly due to the formation of a denser adsorption layer. The particles induce an ordered structure in the surrounding fluid that becomes more pronounced for highly amphiphilic nanoparticles, leading to increased resistance against nanoparticle motion. A similar phenomenon is observed for homogeneous particles diffusing in bulk upon increasing their wettability. Our findings can provide fundamental insight into the dynamics of drugs and protein molecules with anisotropic surface properties at biological interfaces including cell membranes.

Designing patchy particles for optimum interfacial activity.

We study the adsorption of spherical patchy particles to a flat oil-water interface for their potential applications as interface stabilizers. Chemical heterogeneity in form of single and double patches of different sizes is introduced on the surface of a homogeneous particle to induce an amphiphilic character. For a single well-defined patch, we have developed theoretical criteria for designing particles with the maximum degree of surface activity based on any given wettability conditions. We also evaluate the interfacial behavior of spherical particles with two symmetric patches. Depending on the amphiphilicity and size of the patches, our numerical calculations indicate that such particles at equilibrium can orient so their patches are either parallel or normal to the interface. In case of normal-patch orientation, the interface deforms due to heterogeneity along the contact line, leading to quadrupolar capillary interactions between neighboring particles. We demonstrate that the double-patch design can enhance the surface activity for contact angles close to 90°, while a single-patch pattern is preferred in case of highly amphiphilic particles.

Role of geometry and amphiphilicity on capillary-induced interactions between anisotropic Janus particles.

We study the capillary interactions between ellipsoidal Janus particles adsorbed at flat liquid-fluid interfaces. In contrast to spherical particles, Janus ellipsoids with a large aspect ratio or a small difference in the wettability of the two regions tend to tilt at equilibrium. The interface deforms around ellipsoids with tilted orientations and thus results in energetic interactions between neighboring particles. We quantify these interactions through evaluation of capillary energy variation as a function of the spacing and angle between the particles. The complex meniscus shape results in a pair interaction potential which cannot be expressed in terms of capillary quadrupoles as in homogeneous ellipsoids. Moreover, Janus ellipsoids in contact exhibit a larger capillary force at side-by-side alignment compared to the tip-to-tip configuration, while these two are of comparable magnitude for their homogeneous counterparts. We evaluate the role of particles aspect ratio and the degree of amphiphilicity on the interparticle force and the capillary torque. The energy landscapes enable prediction of micromechanics of particle chains, which has implications in predicting the interfacial rheology of such particles at fluid interfaces.

A lipobead microarray assembled by particle entrapment in a microfluidic obstacle course and used for the display of cell membrane receptors.

Platforms which can display cell membrane ligands and receptors as a microarray library of probes for screening against a target are essential tools in drug discovery, biomarker identification, and pathogen detection. Membrane receptors and ligands require their native bilayer environment to retain their selectivity and binding affinity, and this complicates displaying them in a microarray platform. In this study, a design is developed in which the probes are first incorporated in supported lipid bilayers formed around micron-sized particles (lipobeads), and the microbeads themselves are then arrayed on a surface by hydrodynamic capture in a microfluidic obstacle course of traps. The traps are "V" shaped open enclosures, which are arranged in a wide channel of a microfluidic device, and capture the lipobeads (slightly smaller than the channel height) as they are streamed through the course. Screening assays are undertaken directly in the device after assembly, by streaming a fluorescently labeled target through the device and detecting the bead fluorescence. Conditions are first established for which the supported bilayers on the bead surface remain intact during the capture and assay steps, using fluorescent tags in the bilayer to infer bilayer integrity. Numerical calculations of the hydrodynamic drag coefficient on the entrapped beads are presented in conjunction with the stability experiments to develop criteria for the bilayer stability as a function of the screening assay perfusion rate. Simulations of the flow streamlines are also presented to quantify the trapping efficiency of the obstacle course. Screening assays are illustrated, assaying fluorescently labeled NeutrAvidin with biotin, and labeled cholera toxin with its ganglioside binding ligand, GM1. Sequential capturing of sets of lipobeads (one at a time, and with each set bearing a different probe), followed by indexing the bead positions after each set is entrapped, allows for the construction of an indexed array of multiple probes without the need for particle encoding and is illustrated using the NeutrAvidin-biotin pair. Finally, the lipobead platform is used for quantitatively measuring the kinetic rate constants for the binding of a probe (biotin) to a target (NeutrAvidin).

Particle adsorption at polydimethylsiloxane (PDMS)/water interfaces in the presence of a cross-linking reaction.

The adsorption of polymeric particles at the interface of spherical drops of polydimethylsiloxane (PDMS) with water is studied in presence of a cross-linking reaction. Hydrophobic colloidal particles are first uniformly dispersed in water with the help of a nonionic surfactant. The PDMS droplets are then introduced to this dispersion. The particles adsorb to the PDMS-water interface, as the dispersion is being stirred, while the PDMS undergoes a cross-linking reaction at an elevated temperature. The effect of parameters such as particle mass fraction in the dispersion, PDMS cross-linker concentration, and curing temperature on the adsorption behavior and surface coverage of the resulting beads are examined. The surface coverage increases with increasing particle mass fraction, but decreases as the curing temperature or cross-linker concentration is increased. Using an Arrhenius equation, we correlate the adsorption efficiency to the reaction rate and show that the surface coverage of the beads increases logarithmically with the reaction time.

Highly crosslinked poly(dimethylsiloxane) microbeads with uniformly dispersed quantum dot nanocrystals.

This study demonstrates how luminescent semiconductor nanocrystals (quantum dots or QDs) can be dispersed uniformly in a poly(dimethylsiloxane) (PDMS) matrix by polymerizing a mixture of the prepolymer oligomers and the nanocrystals with a relatively large concentration of crosslinking molecules. A microfluidic device is used to fabricate PDMS microbeads embedded with the QDs by using flow focusing to first form monodisperse droplets of the prepolymer/crosslinker/nanocrystal mixture in a continuous aqueous phase. The droplets are subsequently collected, and heated to polymerize them into solid microbead composites. The degree of aggregation of the nanocrystals in the matrix is studied by measuring the nonradiative resonance energy transfer (RET) between the nanocrystals. For this purpose, two quantum dots are used with maxima in their luminescence emission spectrum at 560 nm and 620 nm. When the nanocrystals are within the Förster radius (approximately 10 nm) of each other, exciton energy cascades from the QDs which emit at the shorter wavelength to the QDs which emit at the longer wavelength. This energy transfer is quantified, for two concentration ratios of the prepolmer to the crosslinker, by measuring the deviation of the microbead luminescence spectrum from a reference spectrum obtained by dispersing the QD mixture in a solvent (toluene) in which the nanocrystals do not aggregate. For a low concentration of crosslinking molecules relative to the prepolymer (5:1 by weight prepolymer to crosslinker), strong RET is observed as the emission of the 620 nm QDs is increased and the 560 nm QDs is decreased relative to the reference. In the emission spectrum for a higher concentration of crosslinkers (2:1 by weight prepolymer to crosslinker), the resonance energy transfer is less relative to the case of the low concentration of crosslinkers, and the spectrum more closely resembles the reference. This result indicates that the increase in the crosslinker concentration has reduced the nanocrystal aggregation in the cured polymer. The use of crosslinking can serve as a general paradigm for forming, from a prepolymer/nanoparticle mixture, a composite in which the particles are not aggregated. Under the usual conditions the entropic cost to a linearly growing polymer chain of surrounding nanoparticles forces them to aggregate; crosslinking kinetically entraps the particles and circumvents this aggregation driving force. The QD/polymer composite microbeads fabricated in this study find applications in bead-based platforms for high-throughput, multiplexed screening, where the emission spectrum of the QD luminescence can be used as a spectral barcode to label the beads. For microbeads in which the nanocrystals are uniformly dispersed, this barcode is undistorted by energy transfer, and is easily read.

Role of surface anchoring and geometric confinement on focal conic textures in smectic-A liquid crystals.

A high surface area-to-volume ratio in microchannels increases the importance of surface interactions within them. In layered liquids, such as smectic liquid crystals, surface interactions play an important role in the formation of defect textures. We use 8CB liquid crystal, which is in the smectic-A phase at room temperature, as a model layered liquid. PDMS surfaces can be tuned to be hydrophilic or hydrophobic, and due to the nature of liquid crystalline molecules, we show that this results in planar or homeotropic anchoring conditions, respectively. In a confined system, contrary to the bulk, generated defects cannot grow freely. In the present work, we show that the confinement offered by PDMS microchannels along with the capability of creating mixed anchoring conditions within them results in the formation of particular ordered defect textures through increased surface interactions in smectic-A liquid crystals. Our observations imply that microscale confinement is useful for controlling the size, size distribution, and packing structure of microscale defect structures within these materials. In addition, we show that by placing a droplet of smectic-A liquid crystal on a PDMS surface containing microscale parallel cracks, ordered focal conic defects form between two adjacent cracks. The distance between two adjacent cracks dictates the size of the defects. These observations could lead to useful ideas for exploring new technologies for flexible optical devices or displays that utilize smectic-A liquid crystals.