Thomas E. Kodger

Ultrathin Shell Double Emulsion Templated Giant Unilamellar Lipid Vesicles with Controlled Microdomain Formation

A microfluidic approach is reported for the high-throughput, continuous production of giant unilamellar vesicles (GUVs) using water-in-oil-in-water double emulsion drops as templates. Importantly, these emulsion drops have ultrathin shells; this minimizes the amount of residual solvent that remains trapped within the GUV membrane, overcoming a major limitation of typical microfluidic approaches for GUV fabrication. This approach enables the formation of microdomains, characterized by different lipid compositions and structures within the GUV membranes. This work therefore demonstrates a straightforward and versatile approach to GUV fabrication with precise control over the GUV size, lipid composition and the formation of microdomains within the GUV membrane.

Single step emulsification for the generation of multi-component double emulsions

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.

Reversible assembly of oppositely charged hairy colloids in water

We present an experimental study of the fully reversible assembly of oppositely charged colloidal particles in aqueous solutions. Our polystyrene colloids are charged by a grafted polyelectrolyte brush on their surface and stabilized at all salt concentrations by a neutral adsorbed polymer layer. Below a critical salt concentration oppositely charged colloids form clusters and gels with a fractal nature. The fractal dimension of those aggregates increases with increasing salt concentration. Above the critical salt concentration no aggregation takes place, due to the stabilizing neutral adsorbed polymer. Moreover, the aggregated structures are fully reversible and can be redispersed by simply increasing the salt concentration above the critical concentration. We confirm that time-dependent interaction forces are at the basis of the formation of clusters in the present system by atomic force microscopy measurements as a function of salt concentration and contact time. The force measurements show that the attraction between particles strengthens in time due to interpenetration of the polymer brushes, driven by polyelectrolyte complexation. These particles are a promising step toward a reversible and controlled self-assembling system in water, using colloidal particles as building blocks.

Colloidal gelation of oppositely charged particles

Colloidal gelation has been extensively studied for the case of purely attractive systems, but little is understood about how colloidal gelation is affected by the presence of repulsive interactions. Here we demonstrate the gelation of a binary system of oppositely charged colloids, in which repulsive interactions compete with attractive interactions. We observe that gelation is controlled by varying the total volume fraction, the interaction strength, and the new tuning parameter of the mixing ratio of the two particle types, and present a state diagram of gelation along all these phase-space coordinates. Contrary to commonly studied purely attractive gels, in which weakly quenched gels are more compact and less tenuous, we find that particles in these binary gels form fewer contacts and the gels become more tenuous as we approach the gel point. This suggests that a different mechanism governs gel formation and ultimate structure in binary gelation: particles are unable to form additional favorable contacts through rearrangements, due to the competition of repulsive interactions between similarly charged colloids and attractive interactions between oppositely charged colloids.

Highly Elastic and Self‐Healing Composite Colloidal Gels

Composite colloidal gels are formed by the pH-induced electrostatic assembly of silica and gelatin nanoparticles. These injectable and moldable colloidal gels are able to withstand substantial compressive and tensile loads, and exhibit a remarkable self-healing efficiency. This study provides new, critical insight into the structural and mechanical properties of composite colloidal gels and opens up new avenues for practical application of colloidal gels.

Precise colloids with tunable interactions for confocal microscopy.

Model colloidal systems studied with confocal microscopy have led to numerous insights into the physics of condensed matter. Though confocal microscopy is an extremely powerful tool, it requires a careful choice and preparation of the colloid. Uncontrolled or unknown variations in the size, density, and composition of the individual particles and interactions between particles, often influenced by the synthetic route taken to form them, lead to difficulties in interpreting the behavior of the dispersion. Here we describe the straightforward synthesis of copolymer particles which can be refractive index- and density-matched simultaneously to a non-plasticizing mixture of high dielectric solvents. The interactions between particles are accurately tuned by surface grafting of polymer brushes using Atom Transfer Radical Polymerization (ATRP), from hard-sphere-like to long-ranged electrostatic repulsion or mixed charge attraction. We also modify the buoyant density of the particles by altering the copolymer ratio while maintaining their refractive index match to the suspending solution resulting in well controlled sedimentation. The tunability of the inter-particle interactions, the low volatility of the solvents, and the capacity to simultaneously match both the refractive index and density of the particles to the fluid opens up new possibilities for exploring the physics of colloidal systems.

Microfluidic Fabrication and Micromechanics of Permeable and Impermeable Elastomeric Microbubbles

We use droplet microfluidics to produce monodisperse elastomeric microbubbles consisting of gas encapsulated in a polydimethylsiloxane shell. These microbubbles withstand large, repeated deformations without rupture. We perform μN-scale compression tests on individual microbubbles and find their response to be highly dependent on the shell permeability; during deformation, the pressure inside impermeable microbubbles increases, resulting in an exponential increase in the applied force. Finite element models are used to interpret and extend these experimental results enabling the design and development of deformable microbubbles with a predictable mechanical response. Such microbubbles can be designed to repeatedly transit through the narrow constrictions found in a porous medium functioning as probes of the local pressure.

Transport of charged colloids in a nonpolar solvent

In nonpolar solvents, surfactants stabilize charge through the formation of reverse micelles; this enables the dissociation of charge from the surfaces of particles, thereby charge-stabilizing particle suspensions. We investigate the dynamics of such charged particles by directly visualizing their motion across a microfluidic channel in response to an external electric field. The presence of the reverse micelles has a significant effect on particle motion: in a constant field, the particles initially move, then slow down exponentially, and eventually stop. This is due to the accumulation of reverse micelles at the channel walls, which screens the applied field, leading to the subsequent decay of the internal electric field. The time constant of decay depends on the electrical conductivity of the particle suspension and the width of the channel; this behavior is modeled as an equivalent RC circuit.

Parallelization of microfluidic flow-focusing devices

Microfluidic flow-focusing devices offer excellent control over fluid flow, enabling formation of drops with a narrow size distribution. However, the throughput of microfluidic flow-focusing devices is limited and scale-up through operation of multiple drop makers in parallel often compromises the robustness of their operation. We demonstrate that parallelization is facilitated if the outer phase is injected from the direction opposite to that of the inner phase, because the fluid injection flow rate, where the drop formation transitions from the squeezing into the dripping regime, is shifted towards higher values.

Stable, Fluorescent Polymethylmethacrylate Particles for the Long-Term Observation of Slow Colloidal Dynamics

Suspensions of solid micron-scale colloidal particles in liquid solvents are a foundational model system used to explore a wide range of phase transitions, including crystallization, gelation, spinodal decomposition, and the glass transition. One of the most commonly used systems for these investigations is the fluorescent spherical particles of polymethylmethacrylate (PMMA) suspended in a mixture of nonpolar solvents that match the density and the refractive index of the particles to minimize sedimentation and scattering. However, the particles can swell in these solvents, changing their size and density, and may leak the fluorescent dye over days to weeks; this constrains the exploration of slow and kinetically limited processes, such as near-boundary phase separation or the glass transition. In this paper, we produce PMMA colloidal particles that employ polymerizable and photostable cyanine-based fluorescent monomers spanning the range of visible wavelengths and a polymeric stabilizer prepared from polydimethylsiloxane, PDMS-graft-PMMA. Using microcalorimetry, we characterize the thermodynamics of an accelerated equilibration process for these dispersions in the buoyancy- and refractive-index-matching solvents. We use confocal differential dynamic microscopy to demonstrate that they behave as hard spheres. The suspended particles are stable for months to years, maintaining fixed particle size and density, and do not leak dye. Thus, these particles enable longer term experiments than may have been possible earlier; we demonstrate this by observing spinodal decomposition in a mixture of these particles with a depletant polymer in the microgravity environment of the International Space Station. Using fluorescence microscopy, we observe coarsening over several months and measure the growth of the characteristic length scale to be a fraction of a picometer per second; this rate is among the slowest observed in a phase-separating system. Our protocols should facilitate the synthesis of a variety of particles.