Stimuli responsive Janus microgels with convertible hydrophilicity for controlled emulsion destabilization.

Although the utilization of rigid particles can afford stable emulsions, some applications require eventual emulsion destabilization to release contents captured in the particle-covered droplet. This destabilizing effect is achieved when using stabilizers that respond to controlled changes in environment. Microgels can be synthesized as stimuli responsive polymeric gel networks that adsorb to oil/water interfaces and stabilize emulsions. These particles are commonly hydrogels that swell and collapse in water in response to environmental changes. However, amphiphilic functionality is desired to enhance the adsorption abilities of these hydrogels while maintaining their stimuli responsivity. Microfluidic techniques are used to synthesize Janus microgels with two opposing stimuli responsive hemispheres. The particles have a temperature responsive domain connected to a pH responsive network where each side changes its hydrophilicity in response to a change in temperature or pH, respectively. The Janus microgels are amphiphilic in acidic conditions at 19 °C and alkaline conditions at 40 °C, while the opposite conditions cause a reduction of the amphiphilicity. By stabilizing emulsions with these dual responsive microgels, "smart" droplets that respond to environmental cues are formed. Emulsion droplets remain stable with smaller diameters when aqueous solution conditions favor amphiphilic particles yet, coalesce to larger droplets upon changing pH or temperature. These responsive Janus microgels represent the advancing technology of responsive droplets and demonstrate the applicability of microgels as emulsion stabilizers.

Millimeter-Size Pickering Emulsions Stabilized with Janus Microparticles.

The ability to make stable water-in-oil and oil-in-water millimeter-size Pickering emulsions is demonstrated using Janus particles-particles with distinct surface chemistries. The use of a highly cross-linked hydrophobic polymer network and the excellent water-wetting nature of a hydrogel as the hydrophobic and hydrophilic sides, respectively, permit distinct wettability on the Janus particle. Glass capillary microfluidics allows the synthesis of Janus particles with controlled sizes between 128 and 440 µm and control over the hydrophilic-to-hydrophobic domain volume ratio of the particle from 0.36 to 12.77 for a given size. It is shown that the Janus particle size controls the size of the emulsion drops, thus providing the ability to tune the structure and stability of the resulting emulsions. Stability investigations using centrifugation reveal that particles with the smallest size and a balanced hydrophilic-to-hydrophobic volume ratio (Janus ratio) form emulsions with the greatest stability against coalescence. Particles eventually jam at the interface to form nonspherical droplets. This effect is more pronounced as the hydrogel volume is increased. The large Janus particles permit facile visualization of particle-stabilized emulsions, which result in a better understanding of particle stabilization mechanisms of formed emulsions.

Absorbent-Adsorbates: Large Amphiphilic Janus Microgels as Droplet Stabilizers.

Microgel particles are cross-linked polymer networks that absorb certain liquids causing network expansion. The type of swelling fluid and extent of volume change depends on the polymer-liquid interaction and the network's cross-link density. These colloidal gels can be used to stabilize emulsion drops by adsorbing to the interface of two immiscible fluids. However, to enhance the adsorption abilities of these predominantly hydrophilic gel particles, some degree of hydrophobicity is needed. An amphiphilic Janus microgel with spatially distinct lipophilic and hydrophilic sides is desired. Here, we report the fabrication of poly(ethylene glycol) diacrylate/poly(propylene glycol) diacrylate Janus microgels (JM) using microfluidic drop making. The flow streams of the two separate and immiscible monomer solutions are brought into contact and intersected by a third immiscible fluid in a flow-focusing junction to form Janus droplets. The individual droplets are cross-linked via UV irradiation to form monodispersed microgel particles with opposing hydrophilic and hydrophobic 3D-networked polymer matrices. By combining two chemically different polymer gel networks, an amphiphilic emulsion stabilizer is formed that adsorbs to the oil-water interface while its faces absorb their respective water or hydrocarbon solvents. The resulting water-in-oil emulsions are stabilized and destabilized via a thermal-responsive hydrogel. Stimuli-responsive droplets are demonstrated by adding a short-chain oligo ethylene glycol acrylate molecule to the hydrogel formulation on the Janus microgel particle. Droplets stabilized by these particles experience a sudden increase in droplet diameter around 60 °C. This work with absorbent particles may prove useful for applications in bio catalysis, fuel production, and oil transportation.