Microballoons: Osmotically-inflated elastomer shells for ultrafast release of encapsulants and mechanical energy.

HYPOTHESIS: Microcapsules with osmotically-inflated elastic shells exhibit an ultrafast release of encapsulants while mechanically stimulating the microenvironments, akin to popping balloons. EXPERIMENTS: To prepare elastic shells with uniform thickness and size, monodisperse water-in-oil-in-water (W/O/W) double-emulsion drops are produced in a capillary microfluidic device. The polydimethylsiloxane (PDMS)-containing oil phase is thermally cured to create the elastic shell. The elastic shells are inflated by pumping water into the lumen in hypotonic conditions. The inflated microcapsules produced undergo mechanical compression, and their release properties are studied. FINDINGS: By controlling the osmotic pressure difference, Microballoons are inflated into a diameter of 200 µm - 316 µm and shell thickness of 7.8 µm - 0.7 µm, respectively. The inflated shell pops due to mechanical failure when subjected to mechanical stress above a certain threshold, resembling a balloon. During popping, the stretched shell rapidly retracts to the original uninflated state, resulting in an ultrafast release of encapsulants from the lumen within a millisecond. This process converts elastic potential energy stored in the shell into mechanical energy with substantial power. The microballoons mechanically stimulate the local environment, leading to the direct and rapid release of encapsulants. This has the potential to improve absorption efficiency.

Influence of Sphericity on Surface Termination of Icosahedral Colloidal Clusters.

Colloids self-organize into icosahedral clusters composed of a Mackay core and an anti-Mackay shell under spherical confinement to minimize the free energy. This study explores the variation of surface arrangements of colloids in icosahedral clusters, focusing on the determining factors behind the surface arrangement. To efficiently assemble particles in emulsion droplets, droplet-to-droplet osmotic extraction from particle-laden droplets to salt-containing droplets is used, where the droplets are microfluidically prepared to guarantee a high size uniformity. The icosahedral clusters are optimally produced during a 24-h consolidation period at a 0.04 m salt concentration. The findings reveal an increase in the number of particle layers from 10 to 15 in the icosahedral clusters as the average number of particles increases from 3300 to 11 000. Intriguingly, the number of layers in the anti-Mackay shells, or surface termination, appears to more strongly depend on the sphericity of the clusters than on the deviation in the particle count from an ideal icosahedral cluster. This result suggests that the sphericity of the outermost layer, formed by the late-stage rearrangement of particles to form an anti-Mackay shell near the droplet interface, may play a pivotal role in determining the surface morphology to accommodate a spherical interface.

Recent advances in the microfluidic production of functional microcapsules by multiple-emulsion templating.

Multiple-emulsion drops serve as versatile templates to design functional microcapsules due to their core-shell geometry and multiple compartments. Microfluidics has been used for the elaborate production of multiple-emulsion drops with a controlled composition, order, and dimensions, elevating the value of multiple-emulsion templates. Moreover, recent advances in the microfluidic control of the emulsification and parallelization of drop-making junctions significantly enhance the production throughput for practical use. Metastable multiple-emulsion drops are converted into stable microcapsules through the solidification of selected phases, among which solid shells are designed to function in a programmed manner. Functional microcapsules are used for the storage and release of active materials as drug carriers. Beyond their conventional uses, microcapsules can serve as microcompartments responsible for transmembrane communication, which is promising for their application in advanced microreactors, artificial cells, and microsensors. Given that post-processing provides additional control over the composition and construction of multiple-emulsion drops, they are excellent confining geometries to study the self-assembly of colloids and liquid crystals and produce miniaturized photonic devices. This review article presents the recent progress and current state of the art in the microfluidic production of multiple-emulsion drops, functionalization of solid shells, and applications of microcapsules.

Osmosis-Mediated Microfluidic Production of Submillimeter-Sized Capsules with an Ultrathin Shell for Cosmetic Applications.

There is a demand for submillimeter-sized capsules with an ultrathin shell with high visibility and no tactile sensation after release for cosmetic applications. However, neither bulk emulsification nor droplet microfluidics can directly produce such capsules in a controlled manner. Herein, we report the microfluidic production of submillimeter-sized capsules with a spacious lumen and ultrathin biodegradable shell through osmotic inflation of water-in-oil-in-water (W/O/W) double-emulsion drops. Monodisperse double-emulsion drops are produced with a capillary microfluidic device to have an organic solution of poly(lactic-co-glycolic acid) (PLGA) in the middle oil layer. Hypotonic conditions inflate the drops, leading to core volume expansion and oil-layer thickness reduction. Afterward, the oil layer is consolidated to the PLGA shell through solvent evaporation. The degree of inflation is controllable with the osmotic pressure. With a strong hypotonic condition, the capsule radius increases up to 330 µm and the shell thickness decreases to 1 µm so that the ratio of the thickness to radius is as small as 0.006. The large capsules with an ultrathin shell readily release their encapsulant under an external force by shell rupture. In the mechanical test of single capsules, the threshold strain for shell rupture is reduced from 75 to 12%, and the threshold stress is decreased by two orders for highly inflated capsules in comparison with noninflated ones. During the shell rupture, the tactile sensation of capsules gradually disappears as the capsules lose volume and the residual shells are ultrathin.

Photonic Microbeads Templated by Oil-in-Oil Emulsion Droplets for High Saturation of Structural Colors.

Photonic microbeads containing crystalline colloidal arrays are promising as a key component of structural-color inks for various applications including printings, paintings, and cosmetics. However, structural colors from microbeads usually have low color saturation and the production of the beads requires delicate and time-consuming protocols. Herein, elastic photonic microbeads are designed with enhanced color saturation through facile photocuring of oil-in-oil emulsion droplets. Dispersions of highly-concentrated silica particles in elastomer precursors are microfluidically emulsified into immiscible oil to produce monodisperse droplets. The silica particles spontaneously form crystalline arrays in the entire volume of the droplets due to interparticle repulsion which is unperturbed by the diffusion of the surrounding oil whereas weakened for oil-in-water droplets. The crystalline arrays are permanently stabilized by photopolymerization of the precursor, forming elastic photonic microbeads. The microbeads are transferred into the refractive-index-matched biocompatible oil. The high crystallinity of colloidal arrays increases the reflectivity at stopband and the index matching reduces incoherent scattering at the surface of the microbeads, enhancing color saturation. The colors can be adjusted by mixing two distinctly colored microbeads. Also, low stiffness and high elasticity reduce foreign-body sensation and enhance fluidity, potentially serving as pragmatic structural colorants for photonic inks.

Co-Assembly of Colloids and Eumelanin Nanoparticles in Droplets for Structural Pigments with High Saturation.

Colloidal crystals have been used to develop structural colors. However, incoherent scattering causes the colors to turn whitish, reducing the color saturation. To overcome the problem, light-absorbing additives have been incorporated. Although various additives have been used, most of them are not compatible with a direct co-assembly with common colloids in aqueous suspensions. Here, the authors suggest eumelanin nanoparticles as a new additive to enhance the color chroma. Eumelanin nanoparticles are synthesized to have diameters of several nanometers by oxidative polymerization of precursors in basic solutions. The nanoparticles carry negative charges and do not weaken the electrostatic repulsion among same-charged polystyrene particles when they are added to aqueous suspensions. To prove the effectiveness of eumelanin as a saturation enhancer, the authors produce photonic balls through direct co-assembly of polystyrene and eumelanin using water-in-oil emulsion droplets, while varying the weight ratio of eumelanin to polystyrene. The high crystallinity of colloidal crystals is preserved for the ratio up to at least 1/50 as the eumelanin does not perturb the crystallization. The eumelanin effectively suppresses incoherent scattering while maintaining the strength of structural resonance at an optimum ratio, improving color chroma without compromising brightness.

Elastic Photonic Microcapsules Containing Colloidal Crystallites as Building Blocks for Macroscopic Photonic Surfaces.

Colloidal crystals develop structural colors through wavelength-selective diffraction. Recently, a granular format of colloidal crystals has emerged as building blocks to construct macroscopic photonic surfaces or architectures with high reconfigurability through the secondary assembly. Here, we design elastic photonic microcapsules containing colloidal crystallites along the inner wall as a building block. Water-in-oil-in-water double-emulsion templates are microfluidically prepared to have an aqueous dispersion of polystyrene particles in the inner droplet and polydimethylsiloxane prepolymers in the shell. Colloidal particles are enriched in the presence of depletant and salt by osmotic compression, with the crystallization at the inner interface by depletion attraction. The number of nucleation sites depends on the rate of the enrichment, which enables control over the size and surface coverage of the crystallites with osmotic conditions. The enrichment is ceased by transferring the droplets into an isotonic solution, and the oil shell is cured to form an elastic membrane. As the elastic microcapsules have a large void in the core, they are deformable without structural damage in the crystallites. Therefore, the microcapsules can be closely packed to form macroscopic surfaces while achieving a high quality of structural colors with a collection of crystallites aligned along the flattened membrane.

Composite Microgels Created by Complexation between Polyvinyl Alcohol and Graphene Oxide in Compressed Double-Emulsion Drops.

Microgels, microparticles made of hydrogels, show fast diffusion kinetics and high reconfigurability while maintaining the advantages of hydrogels, being useful for various applications. Here, presented is a new microfluidic strategy for producing polymer-graphene oxide (GO) composite microgels without chemical cues or a temperature swing for gelation. As a main component of microgels, polymers that are able to form hydrogen bonds, such as polyvinyl alcohol (PVA), are used. In the mixture of PVA and GO, GO is tethered by PVA through hydrogen bonding. When the mixture is rapidly concentrated in the core of double-emulsion drops by osmotic-pressure-driven water pumping, PVA-tethered GO sheets form a nematic phase with a planar alignment. In addition, the GO sheets are linked by additional hydrogen bonds, leading to a sol-gel transition. Therefore, the PVA-GO composite remains undissolved when it is directly exposed to water by oil-shell rupture. These composite microgels can be also produced using poly(ethylene oxide) or poly(acrylic acid), instead of PVA. In addition, the microgels can be functionalized by incorporating other polymers in the presence of the hydrogel-forming polymers. It is shown that the multicomponent microgels made from a mixture of polyacrylamide, PVA, and GO show an excellent adsorption capacity for impurities.