Microfluidic Generation of All‐Aqueous Double and Triple Emulsions

Higher order emulsions are used in a variety of different applications in biomedicine, biological studies, cosmetics, and the food industry. Conventional droplet generation platforms for making higher order emulsions use organic solvents as the continuous phase, which is not biocompatible and as a result, further washing steps are required to remove the toxic continuous phase. Recently, droplet generation based on aqueous two‐phase systems (ATPS) has emerged in the field of droplet microfluidics due to their intrinsic biocompatibility. Here, a platform to generate all‐aqueous double and triple emulsions by introducing pressure‐driven flows inside a microfluidic hybrid device is presented. This system uses a conventional microfluidic flow‐focusing geometry coupled with a coaxial microneedle and a glass capillary embedded in flow‐focusing junctions. The configuration of the hybrid device enables the focusing of two coaxial two‐phase streams, which helps to avoid commonly observed channel‐wetting problems. It is shown that this approach achieves the fabrication of higher‐order emulsions in a poly(dimethylsiloxane)‐based microfluidic device, and controls the structure of the all‐aqueous emulsions. This hybrid microfluidic approach allows for facile higher‐order biocompatible emulsion formation, and it is anticipated that this platform will find utility for generating biocompatible materials for various biotechnological applications.     

Freeform,Reconfigurable Embedded Printing of All‐Aqueous 3D Architectures

Aqueous microstructures are challenging to create, handle, and preserve since their surfaces tend to shrink into spherical shapes with minimum surface areas. The creation of freeform aqueous architectures will significantly advance the bioprinting of complex tissue‐like constructs, such as arteries, urinary catheters, and tracheae. The generation of complex, freeform, three‐dimensional (3D) all‐liquid architectures using formulated aqueous two‐phase systems (ATPSs) is demonstrated. These all‐liquid microconstructs are formed by printing aqueous bioinks in an immiscible aqueous environment, which functions as a biocompatible support and pregel solution. By exploiting the hydrogen bonding interaction between polymers in ATPS, the printed aqueous‐in‐aqueous reconfigurable 3D architectures can be stabilized for weeks by the noncovalent membrane at the interface. Different cells can be separately combined with compartmentalized bioinks and matrices to obtain tailor‐designed microconstructs with perfusable vascular networks. The freeform, reconfigurable embedded printing of all‐liquid architectures by ATPSs offers unique opportunities and powerful tools since limitless formulations can be designed from among a breadth of natural and synthetic hydrophilic polymers to mimic tissues. This printing approach may be useful to engineer biomimetic, dynamic tissue‐like constructs for potential applications in drug screening, in vitro tissue models, and regenerative medicine.     

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.     

Photonic Multishells Composed of Cholesteric Liquid Crystals Designed by Controlled Phase Separation in Emulsion Drops

Cholesteric liquid crystals (CLCs), also known as chiral nematic LCs, show a photonic stopband, which is promising for various optical applications. In particular, CLCs confined in microcompartments are useful for sensing, lasing, and optical barcoding at the microscale. The integration of distinct CLCs into single microstructures can provide advanced functionality. In this work, CLC multishells with multiple stopbands are created by liquid–liquid phase separation (LLPS) in a simple yet highly controlled manner. A homogeneous ternary mixture of LC, hydrophilic liquid, and co-solvent is microfluidically emulsified to form uniform oil-in-water drops, which undergo LLPS to form onion-like drops composed of alternating CLC-rich and CLC-depleted layers. The multiplicity is controlled from one to five by adjusting the initial composition of the ternary mixture, which dictates the number of consecutive steps of LLPS. Interestingly, the concentration of the chiral dopant becomes reduced from the outermost to the innermost CLC drop due to uneven partitioning during LLPS, which results in multiple stopbands. Therefore, the photonic multishells show multiple structural colors. In addition, dye-doped multishells provide band-edge lasing at two different wavelengths. This new class of photonic multishells will provide new opportunities for advanced optical applications.     

Nanopore Sensing in Aqueous Two‐Phase System: Simultaneous Enhancement of Signal and Translocation Time via Conformal Coating

Nanofluidic resistive pulse sensing (RPS) has been extensively used to measure the size, concentration, and surface charge of nanoparticles in electrically conducting solutions. Although various methods have been explored for improving detection performances, intrinsic problems including the extremely low particle‐to‐pore volume ratio (<0.01%) and fast nanoparticle translocation (10–1000 µs) still induce difficulties in detection, such as low signal magnitudes and short translocation times. Herein, we present an aqueous two‐phase system (ATPS) in a nanofluidic RPS for amplifying translocation signals and decreasing translocation speeds simultaneously. Two immiscible aqueous liquids build a liquid‐liquid interface inside nanopores. As particles translocate from a high‐affinity liquid phase into a lower‐affinity one, the high‐affinity liquid forms a conformal coating on the particles, which increases the effective particle size and amplifies the current‐blockage signal. The translocation time is also increased, as the ATPS interface impedes the particle translocation. For 20 nm particles, 7.92‐fold and 5.82‐fold enhancements of signal magnitude and translocation time can be achieved. To our knowledge, this is the first attempt to improve nanofluidic RPS by treating an interface of solution reservoirs for manipulating target particles rather than nanopores. This direct particle manipulation allows us to solve the two intrinsic problems all at once.     

Conversion Synthesis of Self‐Standing Potassium Zinc Hexacyanoferrate Arrays as Cathodes for High‐Voltage Flexible Aqueous Rechargeable Sodium‐Ion Batteries

Prussian blue analogs exhibit great promise for applications in aqueous rechargeable sodium‐ion batteries (ARSIBs) due to their unique open framework and well‐defined discharge voltage plateau. However, traditional coprecipitation methods cannot prepare self‐standing electrodes to meet the needs of wearable energy storage devices. In this work, a water bath method is reported to grow microcube‐like K₂Zn₃(Fe(CN)₆)₂·9H₂O on carbon cloth (CC) using Zn nanosheet arrays as the zinc source and reducing agent, directly serving as a self‐standing cathode. Benefiting from fast ion diffusion and high conductivity, the cathode delivers a high areal capacity of 0.76 mAh cm^?2 at 0.5 mA cm^?2 and excellent capacity retention of 57.9% as the current density increases to 20 mA cm^?2. By coupling with NaTi₂(PO₄)₃ grown on CC as an anode, a quasi‐solid‐state flexible ARSIB with a high output voltage plateau of 1.6 V is successfully assembled, exhibiting a superior areal capacity of 0.56 mAh cm^?2 and energy density of 0.92 mWh cm^?2. In particular, the device shows admirable mechanical flexibility, maintaining 90.3% of initial capacity after 3000 bending cycles. This work is anticipated to open a new avenue for the rational design of self‐standing electrodes used in high‐voltage flexible ARSIBs.     

Temperature‐Controlled High‐Speed AFM: Real‐Time Observation of Ripple Phase Transitions

With nanometer lateral and Angstrom vertical resolution, atomic force microscopy (AFM) has contributed unique data improving the understanding of lipid bilayers. Lipid bilayers are found in several different temperature‐dependent states, termed phases; the main phases are solid and fluid phases. The transition temperature between solid and fluid phases is lipid composition specific. Under certain conditions some lipid bilayers adopt a so‐called ripple phase, a structure where solid and fluid phase domains alternate with constant periodicity. Because of its narrow regime of existence and heterogeneity ripple phase and its transition dynamics remain poorly understood. Here, a temperature control device to high‐speed atomic force microscopy (HS‐AFM) to observe dynamics of phase transition from ripple phase to fluid phase reversibly in real time is developed and integrated. Based on HS‐AFM imaging, the phase transition processes from ripple phase to fluid phase and from ripple phase to metastable ripple phase to fluid phase could be reversibly, phenomenologically, and quantitatively studied. The results here show phase transition hysteresis in fast cooling and heating processes, while both melting and condensation occur at 24.15 °C in quasi‐steady state situation. A second metastable ripple phase with larger periodicity is formed at the ripple phase to fluid phase transition when the buffer contains Ca²⁺. The presented temperature‐controlled HS‐AFM is a new unique experimental system to observe dynamics of temperature‐sensitive processes at the nanoscopic level.     

High‐Entropy Alloy (HEA)‐Coated Nanolattice Structures and Their Mechanical Properties

Nanolattice structure fabricated by two‐photon lithography (TPL) is a coupling of size‐dependent mechanical properties at micro/nano‐scale with structural geometry responses in wide applications of scalable micro/nano‐manufacturing. In this work, three‐dimensional (3D) polymeric nanolattices are initially fabricated using TPL, then conformably coated with an 80 nm thick high‐entropy alloy (HEA) thin film (CoCrFeNiAl_0.3) via physical vapor deposition (PVD). 3D atomic‐probe tomography (APT) reveals the homogeneous element distribution in the synthesized HEA film deposited on the substrate. Mechanical properties of the obtained composite architectures are investigated via in situ scanning electron microscope (SEM) compression test, as well as finite element method (FEM) at the relevant length scales. The presented HEA‐coated nanolattice encouragingly not only exhibits superior compressive specific strength of ≈0.032 MPa kg^?1 m³ with density well below 1000 kg m^?3, but also shows good compression ductility due to its composite nature. This concept of combining HEA with polymer lattice structures demonstrates the potential of fabricating novel architected metamaterials with tunable mechanical properties.

     

Approaching Ultrastable High‐Rate Li–S Batteries through Hierarchically Porous Titanium Nitride Synthesized by Multiscale Phase Separation

Porous architectures are important in determining the performance of lithium–sulfur batteries (LSBs). Among them, multiscale porous architecutures are highly desired to tackle the limitations of single‐sized porous architectures, and to combine the advantages of different pore scales. Although a few carbonaceous materials with multiscale porosity are employed in LSBs, their nonpolar surface properties cause the severe dissolution of lithium polysulfides (LiPSs). In this context, multiscale porous structure design of noncarbonaceous materials is highly required, but has not been exploited in LSBs yet because of the absence of a facile method to control the multiscale porous inorganic materials. Here, a hierarchically porous titanium nitride (h‐TiN) is reported as a multifunctional sulfur host, integrating the advantages of multiscale porous architectures with intrinsic surface properties of TiN to achieve high‐rate and long‐life LSBs. The macropores accommodate the high amount of sulfur, facilitate the electrolyte penetration and transportation of Li⁺ ions, while the mesopores effectively prevent the LiPS dissolution. TiN strongly adsorbs LiPS, mitigates the shuttle effect, and promotes the redox kinetics. Therefore, h‐TiN/S shows a reversible capacity of 557 mA h g^?1 even after 1000 cycles at 5 C rate with only 0.016% of capacity decay per cycle.     

Enhanced Light Out‐Coupling of OLEDs with Low Haze by Inserting Randomly Dispersed Nanopillar Arrays Formed by Lateral Phase Separation of Polymer Blends

A simple and efficient method to fabricate light extraction layers is demonstrated by utilizing the phase separation of two polymer blends to enhance the light out‐coupling efficiency of OLEDs with low haze. Polystyrene and poly(methyl methacrylate) dissolved in tetrahydrofuran are mixed and spin‐coated over ITO‐coated glass substrates. Nanopores and nanopillar arrays are formed through lateral phase separation of the polymer blend. The shape, size, and distribution of the patterns can be controlled through changes in the composition and thickness of the coated polymer blends. Phosphorescent OLEDs are fabricated using randomly dispersed nanopillar arrays as light extraction layers and they show a 24% enhancement in external quantum efficiency with a Lambertian emission pattern, no spectrum dependence on viewing angles, and only a small increment in the haze. With these advantages, this newly developed method can be adapted to be used for large‐area, flexible substrates for lighting and display applications.