Jaewon Yoon

Spontaneous shape reconfigurations in multicompartmental microcylinders

Nature’s particles, such as spores, viruses or cells, are adaptive—i.e., they can rapidly alter major phenomenological attributes such as shape, size, or curvature in response to environmental changes. Prominent examples include the hydration-mediated opening of ice plant seeds, actuation of pine cones, or the ingenious snapping mechanism of predatory Venus flytraps that rely on concave-to-convex reconfigurations. In contrast, experimental realization of reconfigurable synthetic microparticles has been extremely challenging and only very few examples have been reported so far. Here, we demonstrate a generic approach towards dynamically reconfigurable microparticles that explores unique anisotropic particle architectures, rather than direct synthesis of sophisticated materials such as shape-memory polymers. Solely enabled by their architecture, multicompartmental microcylinders made of conventional polymers underwent active reconfiguration including shape-shifting, reversible switching, or three-way toggling. Once microcylinders with appropriate multicompartmental architectures were prepared by electrohydrodynamic cojetting, simple exposure to an external stimulus, such as ultrasound or an appropriate solvent, gives rise to interfacial stresses that ultimately cause reversible topographical reconfiguration. The broad versatility of the electrohydrodynamic cojetting process with respect to materials selection and processing suggests strategies for a wide range of dynamically reconfigurable adaptive materials including those with prospective applications for sensors, reprogrammable microactuators, or targeted drug delivery.

Chemically Orthogonal Three‐Patch Microparticles

Compared to two-dimensional substrates, only a few methodologies exist for the spatially controlled decoration of three-dimensional objects, such as microparticles. Combining electrohydrodynamic co-jetting with synthetic polymer chemistry, we were able to create two- and three-patch microparticles displaying chemically orthogonal anchor groups on three distinct surface patches of the same particle. This approach takes advantage of a combination of novel chemically orthogonal polylactide-based polymers and their processing by electrohydrodynamic co-jetting to yield unprecedented multifunctional microparticles. Several micropatterned particles were fabricated displaying orthogonal click functionalities. Specifically, we demonstrate novel two- and three-patch particles. Multi-patch particles are highly sought after for their potential to present multiple distinct ligands in a directional manner. This work clearly establishes a viable route towards orthogonal reaction strategies on multivalent micropatterned particles.

Amphiphilic Colloidal Surfactants Based on Electrohydrodynamic Co-jetting

A novel synthetic route for the preparation of amphiphilic Janus particles based on electrohydrodynamic cojetting has been developed. In this approach, selective encapsulation of hydrophobic fluorodecyl-polyhedral oligomeric silsesquioxane (F-POSS) in one compartment and a poly(vinyl alcohol) in the second compartment results in colloidal particles with surfactant-like properties including the self-organization at oil-water and air-water interfaces. Successful localization of the respective polymers in different compartments of the same particle is confirmed by a combination of fluorescence microscopy, vibrational spectroscopy, and ζ-potential measurements. We believe that this straightforward synthetic approach may lead to a diverse class of surface-active colloids that will have significant relevance ranging from basic scientific studies to immediate applications in areas, such as pharmaceutical sciences or cosmetics.

Compartmentalized Photoreactions within Compositionally Anisotropic Janus Microstructures

We demonstrate spatially controlled photoreactions within bicompartmental microparticles and microfibers. Selective photoreactions are achieved by anisotropic incorporation of photocrosslinkable poly(vinyl cinnamate) in one compartment of either colloids or microfibers. Prior to photoreaction, bicompartmental particles, and fibers were prepared by EHD co-jetting of two compositionally distinct polymer solutions. Physical and chemical anisotropy was confirmed by confocal laser scanning microscopy, Fourier-transformed infrared spectroscopy, and scanning electron microscopy. The data indicate adjustment of polymer concentrations of the jetting solutions to be the determining factors for particle and fiber structures. Subsequent exposure of poly(vinyl cinnamate)-based particles and fibers to UV light at 254 nm resulted in spatially controlled crosslinking. Treatment of the crosslinked bicompartmental colloids with chloroform produced half-moon shaped objects. These hemishells exhibited a distinct porous morphology with pore sizes in the range of 70 nm. Based on this novel synthetic approach, Janus-type particles and fibers can be prepared by EHD co-jetting and can be selectively photocrosslinked without the need for masks or selective laser writing.

Cardiomyocyte‐Driven Actuation in Biohybrid Microcylinders

Biohybrid microcylinders are fabricated using electrohydrodynamic cojetting followed by a surface chemistry approach to maximize cell-adhesive characteristics. As proper cell alignment and mechanical stiffness are important components of bioactuator design, spatial cell selectivity and stress/strain properties of microcylinders are characterized to demonstrate their capability of response to rat cardio-myocyte contraction. These microcylinders can find applications in a host of micromechanical systems.

Janus-Core and Shell Microfibers

Janus microcylinders composed of different polymers were prepared through coaxial co-jetting with dual-core flows, followed by cross-linking, microsectioning, and shell removal. Uniquely shaped building blocks can be fabricated by photo-patterning of one hemisphere of the microcylinders.

Spatioselective growth of metal-organic framework nanocrystals on compositionally anisotropic polymer particles.

Selective growth of metal organic framework materials on the surface of compartmentalized polymer microparticles is achieved by electro-hydrodynamic co-jetting, selective surface modification, and anisotropic crystal growth.

Controlled microstructuring of Janus particles based on a multifunctional poly(ethylene glycol)

A novel water insoluble, multifunctional poly(ethylene glycol), poly(hydrazide ethylene glycol-co-benzyl glycidyl ether) (P(HZ-co-BnGE)), is synthesized via thiol-ene click reaction of poly(allyl glycidyl ether-co-benzyl glycidyl ether) (P(AGE-co-BnGE)). The base polymer P(AGE-co-BnGE) is previously prepared by anionic ring-opening copolymerization of the corresponding monomers. To demonstrate utility, bicompartmental microspheres and microcylinders containing P(HZ-co-BnGE) in one of the compartments are prepared via electrohydrodynamic (EHD) co-jetting. Next, spatially controlled surface reactivity toward sugars is demonstrated by selective binding of 2α-mannobiose to the P(HZ-co-BnGE) compartment only, as confirmed by a carbohydrate-lectin-binding assay. These sugar-reactive hydrazide-presenting microparticles have potential applications for glyco-targeted drug delivery.

Compartmentalized Microhelices Prepared via Electrohydrodynamic Cojetting

Abstract Anisotropically compartmentalized microparticles have attracted increasing interest in areas ranging from sensing, drug delivery, and catalysis to microactuators. Herein, a facile method is reported for the preparation of helically decorated microbuilding blocks, using a modified electrohydrodynamic cojetting method. Bicompartmental microfibers are twisted in situ, during electrojetting, resulting in helical microfibers. Subsequent cryosectioning of aligned fiber bundles provides access to helically decorated microcylinders. The unique helical structure endows the microfibers/microcylinders with several novel functions such as translational motion in response to rotating magnetic fields. Finally, microspheres with helically patterned compartments are obtained after interfacially driven shape shifting of helically decorated microcylinders.