High-Density Microporous Drainage-Integrating Sheath Flow Generator for Streamlining Microfluidic Cell Sorting Systems.

Tremendous efforts have been made to develop practical and efficient microfluidic cell and particle sorting systems; however, there are technological limitations in terms of system complexity and low operability. Here, we propose a sheath flow generator that can dramatically simplify operational procedures and enhance the usability of microfluidic cell sorters. The device utilizes an embedded polydimethylsiloxane (PDMS) sponge with interconnected micropores, which is in direct contact with microchannels and seamlessly integrated into the microfluidic platform. The high-density micropores on the sponge surface facilitated fluid drainage, and the drained fluid was used as the sheath flow for downstream cell sorting processes. To fabricate the integrated device, a new process for sponge-embedded substrates was developed through the accumulation, incorporation, and dissolution of PMMA microparticles as sacrificial porogens. The effects of the microchannel geometry and flow velocity on the sheath flow generation were investigated. Furthermore, an asymmetric lattice-shaped microchannel network for cell/particle sorting was connected to the sheath flow generator in series, and the sorting performances of model particles, blood cells, and spiked tumor cells were investigated. The sheath flow generation technique developed in this study is expected to streamline conventional microfluidic cell-sorting systems as it dramatically improves versatility and operability.

Pushing the limits of microfluidic droplet production efficiency: engineering microchannels with seamlessly implemented 3D inverse colloidal crystals.

Although droplet microfluidics has been studied for the past two decades, its applications are still limited due to the low productivity of microdroplets resulting from the low integration of planar microchannel structures. In this study, a microfluidic system implementing inverse colloidal crystals (ICCs), a spongious matrix with regularly and densely formed three-dimensional (3D) interconnected micropores, was developed to significantly increase the throughput of microdroplet generation. A new bottom-up microfabrication technique was developed to seamlessly integrate the ICCs into planar microchannels by accumulating non-crosslinked spherical PMMA microparticles as sacrificial porogens in a selective area of a mold and later dissolving them. We have demonstrated that the densely arranged micropores on the spongious ICC of the microchannel function as massively parallel micronozzles, enabling droplet formation on the order of >10 kHz. Droplet size could be adjusted by flow conditions, fluid properties, and micropore size, and biopolymer particles composed of polysaccharides and proteins were produced. By further parallelization of the unit structures, droplet formation on the order of >100 kHz was achieved. The presented approach is an upgrade of the existing droplet microfluidics concept, not only in terms of its high throughput, but also in terms of ease of fabrication and operation.

Preparation of liquid crystal nanocapsules by polymerization of oil-in-water emulsion monomer droplets.

Liquid crystal nanocapsules (LC-Nanocapsules) were prepared by miniemulsion polymerization of the oil-in-water emulsion monomer droplets dissolving the liquid crystal (LC) compounds. In order to establish the preparation conditions of LC-Nanocapsules exhibiting the liquid crystallinity, the effects of the capsule wall-forming monomers and the crosslinking agent concentration on the capsule structure were investigated in detail. The monodisperse colloidal products covered with the robust polymer shell wall was successfully prepared by the polymerization of the emulsion monomer droplets obtained through the phase inversion temperature emulsification technique using the amphiphilic block copolymer as an emulsifier. The endothermic peak was observed at the nematic-isotropic phase transition temperature (TNI) of the LC in the differential scanning calorimetry diagram of LC-Nanocapsules. The bright- and dark-field images of the dried thin films of LC-Nanocapsules spread on a glass substrate were found to appear repeatedly by the temperature change below and above TNI by polarized optical microscopic analysis. These results revealed that the LC-Nanocapsules with a complete engulfing morphology were successfully formed by the spontaneous coacervation phenomena between the crosslinked polymer and the LC with a progression of the polymerization, as theoretically predicted from the viewpoint of the spreading coefficients.

Preparation of photochromic liquid core nanocapsules based on theoretical design.

Photochromic materials have attracted considerable attention for their practical applications in optoelectronic devices. In this study, we developed the photochromic liquid core nanocapsules by polymerization of oil-in-water (O/W) nanoemulsion monomer droplets on the basis of Hansen solubility parameters. The thermoresponsive amphiphilic block copolymers (POEGMAm-b-PStn and POEGMAm-b-PMMAn) were synthesized by sequential reversible addition fragmentation chain transfer (RAFT) polymerization of hydrophilic oligo(ethylene glycol) methyl ether methacrylate and hydrophobic styrene or MMA. The O/W nanoemulsion methyl methacrylate (MMA) droplets, dissolving dipropylene glycol methyl-n-propyl ether (DPMNP) and (E)-3-(adamantan-2-ylidene)-4-[1-(2,5-dimethyl-3-furyl) ethylidene]dihydro-2,5furandione (Aberchrome 670) as a core liquid and a photochromic dye, respectively, were obtained through the phase inversion temperature emulsification technique using POEGMAm-b-PStn as a surfactant. As theoretically predicted in terms of the spreading coefficients, the DPMNP solution of Aberchrome 670 was successfully encapsulated by coacervation of the crosslinked PMMA condensed phase. Aberchrome 670 dissolved in a liquid core was found to photoisomerize twice as fast as that dispersed in the solid polymer matrices.

Does Introduction of a Bent Tail Stabilize Biaxiality and Lateral Switching Behavior of Smectic A Liquid Crystal Phases of Rodlike Molecules?

By introducing an oleyl group at the end of the straight rodlike molecule, the effect of the tail shape on the liquid crystallinity, biaxiality, and lateral switching behavior of the smectic A phase was investigated. Three types of molecules possessing a fluorinated phenyl (pentafluorophenyl, 2,3,4-trifluorophenyl, or 2,3-difluorophenyl) group and a cis-octadec-9-enyl group were synthesized, and their liquid crystallinities were compared with the corresponding molecules with a straight alkyl ( trans-octadec-9-enyl or n-octadecanyl) group. In switching experiments, the molecules with a bent terminal chain showed higher spontaneous polarization ( Ps) values than those with a straight terminal chain. Further, the directional changes of the long molecular axes were suppressed for the molecules possessing a bent terminal chain. These results show that the introduction of a bent terminal chain is highly effective for stabilizing ferroelectric switching behaviors.

Ellipsoidal Artificial Melanin Particles as Building Blocks for Biomimetic Structural Coloration.

Inspired by the structural coloration of anisotropic materials in nature, we demonstrate the preparation of structural color materials by the assembly of anisotropic particles. Spherical artificial melanin particles consisting of a polystyrene core and polydopamine shell were stretched asymmetrically to form uniform-sized ellipsoidal particles with different aspect ratios. The aspect ratio and assembly method of the ellipsoidal particles influence the structural coloration, indicating that the particle shape is one of the important parameters for controlling the structural coloration. The discovery of a method to control the structural color using ellipsoidal particles is useful in basic research on structural colors in nature and provides flexibility in material design and extends the application range of structural color materials.

Melanin Precursor Influence on Structural Colors from Artificial Melanin Particles: PolyDOPA, Polydopamine, and Polynorepinephrine.

Polydopamine (PDA) is of interest as a mimetic material of melanin to produce structural color materials. Herein, to investigate the influence of the material composition of the artificial melanin particles on structural color, we demonstrated the preparation of core-shell particles by polymerization of norepinephrine or 3,4-dihydroxyphenylalanine, which are melanin precursors similar to dopamine, in the presence of polystyrene particles. It was revealed that the arrays of the prepared particles produce high-visibility structural color because of absorption of scattering light. Although poly(3,4-dihydroxyphenylalanine) showed the same tendency as PDA which was previous studied, polynorepinephrine can easily produce a smooth and thick shell layer compared with that of PDA, and pellets consisting of the particles showed angle-dependent structural color. Therefore, the artificial melanin particles that produce angle-dependent structural color became stable than ever before. These results indicated that material compositions of artificial melanin particles have influence on structural color, and an important finding for application as a coloring material was obtained.

Adhesion Control of Branched Catecholic Polymers by Acid Stimulation.

Biomimetic material design is a useful method for producing new functional materials. In recent years, catecholic polymers inspired from the adhesion mechanism of marine organisms have attracted attention. Here, we demonstrated the preparation of catecholic polymers by reversible addition-fragmentation chain transfer (RAFT) polymerization of an acetonide-protected catecholic monomer, that is, N-(2-(2,2-dimethylbenzo-1,3-dioxol-5-yl)ethyl)-acrylamide (DDEA). By selecting the specific RAFT reagents, well-defined branched PDDEA and linear PDDEA were obtained. These PDDEA samples showed stronger adhesion strength after deprotection by acid stimulation compared with that before deprotection. In addition, we demonstrated the adhesion control of synthetic polymers by photoirradiation in the presence of photoacid generators, which decompose under light and release an acid.

Polydopamine-Based 3D Colloidal Photonic Materials: Structural Color Balls and Fibers from Melanin-Like Particles with Polydopamine Shell Layers.

Nature creates beautiful structural colors, and some of these colors are produced by nanostructural arrays of melanin. Polydopamine (PDA), an artificial black polymer produced by self-oxidative polymerization of dopamine, has attracted extensive attention because of its unique properties. PDA is a melanin-like material, and recent studies have reported that photonic materials based on PDA particles showed structural colors by enhancing color saturation through the absorption of scattered light. Herein, we describe the preparation of three-dimensional (3D) colloidal photonic materials, such as structural color balls and fibers, from biomimetic core-shell particles with melanin-like PDA shell layers. Structural color balls were prepared through the combined use of membrane emulsion and heating. We also demonstrated the use of microfluidic emulsification and solvent diffusion for the fabrication of structural color fibers. The obtained 3D colloidal materials, i.e., balls and fibers, exhibited angle-independent structural colors due to the amorphous assembly of PDA-containing particles. These findings provide new insight for the development of dye-free technology for the coloration of various 3D colloidal architectures.

Structural Color Tuning: Mixing Melanin-Like Particles with Different Diameters to Create Neutral Colors.

We present the ability to tune structural colors by mixing colloidal particles. To produce high-visibility structural colors, melanin-like core-shell particles composed of a polystyrene (PSt) core and a polydopamine (PDA) shell, were used as components. The results indicated that neutral structural colors could be successfully obtained by simply mixing two differently sized melanin-like PSt@PDA core-shell particles. In addition, the arrangements of the particles, which were important factors when forming structural colors, were investigated by mathematical processing using a 2D Fourier transform technique and Voronoi diagrams. These findings provide new insights for the development of structural color-based ink applications.

Shape-Assisted Self-Organization in Highly Disordered Liquid Crystal Phases.

In achiral rod-like molecules, a nematic phase is the most disordered liquid crystal phase, which only has one-directional order in the direction of the molecular long axis. A dumbbell-shaped molecule (compound 3: R-C6 H10 -CH=CH-C6 H4 -CH=CH-C6 H10 -R, (R=nC5 H11 )), and its liquid crystal phase (X phase) are reported, which exhibit high scattering without thermal fluctuation between two nematic phases under a polarized light optical microscope. The X phase was investigated by X-ray diffraction, scanning electron microscopy, atomic force microscopy, and molecular dynamics simulation. A layered structure was ascertained for which a molecular self-organization mechanism was postulated in which the super-structure is based on lateral intermolecular interlocking. A second nematic phase above the X phase consisted of "rice grain"-shaped particles.

Full-Color Biomimetic Photonic Materials with Iridescent and Non-Iridescent Structural Colors.

The beautiful structural colors in bird feathers are some of the brightest colors in nature, and some of these colors are created by arrays of melanin granules that act as both structural colors and scattering absorbers. Inspired by the color of bird feathers, high-visibility structural colors have been created by altering four variables: size, blackness, refractive index, and arrangement of the nano-elements. To control these four variables, we developed a facile method for the preparation of biomimetic core-shell particles with melanin-like polydopamine (PDA) shell layers. The size of the core-shell particles was controlled by adjusting the core polystyrene (PSt) particles' diameter and the PDA shell thicknesses. The blackness and refractive index of the colloidal particles could be adjusted by controlling the thickness of the PDA shell. The arrangement of the particles was controlled by adjusting the surface roughness of the core-shell particles. This method enabled the production of both iridescent and non-iridescent structural colors from only one component. This simple and novel process of using core-shell particles containing PDA shell layers can be used in basic research on structural colors in nature and their practical applications.

Polystyrene latex particles containing europium complexes prepared by miniemulsion polymerization using bovine serum albumin as a surfactant for biochemical diagnosis.

Luminescent particles have been attracting significant attention because they can be used in biochemical applications, such as detecting and imaging biomolecules. In this study, luminescent polystyrene latex particles were prepared through miniemulsion polymerization of styrene with dissolved europium complexes in the presence of bovine serum albumin (BSA) and poly(ethylene glycol) monomethoxy methacrylate as surfactants. The solubility of the europium complex in styrene has a strong effect on the yield of the particle. Europium tris(2-thenoyl trifluoroacetonate) di(tri-n-octyl phosphine oxide), which has a high solubility in styrene, was sufficiently incorporated into the polystyrene particles compared to europium tris(2-thenoyl trifluoroacetonate), which has a low solubility in styrene. The luminescence property of the europium complex could remain intact even after its incorporation through the miniemulsion polymerization. In the aqueous dispersion, the resulting particles could emit strong luminescence, which is a characteristic of the europium complex. The antibody fragments were covalently attached to BSA-covered particles after a reaction with a bifunctional linker, N-(6-maleimidocaproyloxy)succinimide. The time-resolved fluoroimmunoassay technique showed that 3.3pg/mL of human α-fetoproteins (AFP) can be detected by using the resulting luminescent particles. An immunochromatographic assay using the resulting particles was also performed as a convenient method to qualitatively detect biomolecules. The detection limit of AFP measured by the immunochromatographic assay was determined to be 2000pg/mL. These results revealed that the luminescent particles obtained in this study can be utilized for the highly sensitive detection of biomolecules and in vitro biochemical diagnosis.

Glycopolymer-Grafted Polymer Particles for Lectin Recognition.

Glycopolymers bearing carbohydrates have an advantage in protein recognition that is attributable to the multivalent effect (cluster effect) of side-chain carbohydrates. A variety of surface-modified polymer particles have been prepared concurrently with the development of new synthetic technology. Here we describe a synthetic method of glycopolymer-grafted polymer particles by surface-initiated living radical polymerization, i.e., atom-transfer radical polymerization (ATRP) and photoiniferter polymerization, for specific lectin recognition.

Simple and efficient chiral dopants to induce blue phases and their optical purity effects on the physical properties of blue phases.

Blue phases (BPs) have received considerable attention as light shutters in the next generation of liquid crystal (LC) displays. However, no simple and efficient chiral dopant for induction of BPs of commercially available rodlike LC compounds has been reported. In this study, both (R) and (S) forms of novel chiral dopants were synthesized, showed extremely high helical twisting power values in nematic LC compounds, and induced stable BPs with a small amount of our chiral dopants (3-5 mol %). In enantiomeric excess controlled experiments, we found novel phenomena in their physical properties, such as generation of a metastable chiral nematic phase between an isotropic state and a BP.

Simple and highly efficient chiral dopant molecules possessing both rod- and arch-like units.

A simple chiral dopant molecule (R)-1 with both rod- and arch-like units was prepared, and extremely large helical twisting powers (+123 to +228 µm(-1)) in nematic liquid crystal phases were achieved. We have demonstrated that the introduction of an arch-like unit in addition to rod-like units is highly effective in controlling the helical molecular alignment. As an application of the dopant, induction of blue phases by addition of a small amount of it was achieved.

Facile synthesis of free-standing polymer brush films based on a colorless polydopamine thin layer.

A free-standing polymer brush film with tailored thicknesses based on a colorless polydopamine (PDA) thin layer is prepared and characterized. The surface-initiated atom transfer radical polymerization (ATRP) of 2-hydroxyethyl methacrylate (HEMA) is performed on a PDA layer with thickness of ca. 6 nm, which generated an optically transparent and colorless free-standing PHEMA brush film (1.5 cm × 1.5 cm). Because the cross-linked PDA layer is used as the base for the polymer brushes, the reported method does not require cross-linking the polymer brushes. The free-standing film thicknesses of ≈16-75 nm are controlled by simply changing the ATRP reaction time. The results show that the free-standing PHEMA brush film transferred onto a plate exhibits a relatively smooth surface and is stable in any solvent.

Preparation of organic/inorganic hybrid and hollow particles by catalytic deposition of silica onto core/shell heterocoagulates modified with poly[2-(N,N-dimethylamino)ethyl methacrylate].

The organic/inorganic hybrid particles PSt/P(St-CPEM)(θ)-g-PDMAEMA/SiO(2) were prepared by catalytic hydrolysis and subsequent polycondensation of tetraethoxysilane in the poly[2-(N,N-dimethylamino)ethyl methacrylate] (PDMAEMA) layers grafted on the PSt/P(St-CPEM)(θ) core/shell heterocoagulates. The micron-sized PSt core and the submicron-sized P(St-CPEM) shell particles bearing ATRP initiating groups were synthesized by dispersion polymerization of styrene (St) and emulsifier-free emulsion polymerization of St with 2-chloropropionyloxyethyl methacrylate (CPEM), respectively. The raspberry-shaped PSt/P(St-CPEM)(θ) heterocoagulates with a controlled surface coverage (θ=0.51, 0.81) were prepared by hydrophobic coagulation between the core and the shell particles in an aqueous NaCl solution near the T(g) of P(St-CPEM). Surface modification of heterocoagulates was carried out by ATRP of DMAEMA from the shell particles adsorbed on the core particles. Silica deposition was performed by simply adding tetraethoxysilane to a water/methanol dispersion of PSt/P(St-CPEM)(θ)-g-PDMAEMA. The SEM and TGA revealed that the resulting PSt/P(St-CPEM)(θ)-g-PDMAEMA/SiO(2) composites maintain a raspberry-like morphology after deposition of silica onto the PDMAEMA layer grafted on heterocoagulates. The micron-sized, raspberry-shaped or the submicron-sized, hole-structured silica hollow particles were obtained selectively by thermal decomposition of the PSt/P(St-CPEM)(θ)-g-PDMAEMA/SiO(2). The oriented particle array was fabricated by dropping anisotropically perforated silica particles onto a glass substrate settled at the bottom of a bottle filled with chloroform.

Photochemical conversion of the o-nitrobenzyl-C-glucoside to a sugar lactone.

A new family of activated glycosidic compounds has been designed and synthesized: (2,3,4,6-tetra-O-acetyl-ß-D-glucopyranosyl)-2-nitrophenylmethane (1). It is stable in conditions commonly used for synthesis, and it can be converted to a sugar lactone derivative merely by photoirradiation (λ=365 nm): 2,3,4,6-tetra-O-acetyl-D-glucono-1,5-lactone (2). A mechanism for the reaction is proposed. The photochemical conversion of 1 in the presence of methanol has also been demonstrated, giving rise to methyl 2,3,4,6-tetra-O-acetyl-D-gluconate (3).

Preparation of organic/inorganic composites by deposition of silica onto shell layers of polystyrene (core)/poly[2-(N,N-dimethylamino)ethyl methacrylate] (shell) particles.

Organic/inorganic composites were prepared by catalytic hydrolysis and subsequent condensation of tetraethoxysilane (TEOS) in a shell layer of core-shell polymer particles. First, core-shell particles were prepared by emulsifier-free emulsion polymerization of styrene (St) with 2-chloropropionyloxyethyl methacrylate (CPEM) using potassium persulfate as an initiator, followed by surface-initiated activator generated electron transfer-atom transfer radical polymerization (AGET-ATRP) of 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA). Dynamic light scattering revealed that hydrodynamic diameter of the particle increased from 482 to 931 nm after AGET-ATRP of DMAEMA. The amount of grafted DMAEMA was determined to be ca. 10 mol% with respect to (wrt) St by (1)H NMR. Second, the composite particles were prepared by adding TEOS into a water/methanol dispersion of the P(St-CPEM)-g-P(DMAEMA). The P(St-CPEM)-g-P(DMAEMA)-SiO(2) composite particles containing ca. 50 wt.% of silica wrt the total weight were obtained. Hollow silica shell particles were also obtained by extraction of polymer components from the composites with tetrahydrofuran.