Generation of High‐Order All‐Aqueous Emulsion Drops by Osmosis‐Driven Phase Separation

Droplets containing ternary mixtures can spontaneously phase‐separate into high‐order structures upon a change in composition, which provides an alternative strategy to form multiphase droplets. However, existing strategies always involve nonaqueous solvents that limit the potential applications of the resulting multiple droplets, such as encapsulation of biomolecules. Here, a robust approach to achieve high‐order emulsion drops with an all‐aqueous nature from two aqueous phases by osmosis‐induced phase separation on a microfluidic platform is presented. This technique is enabled by the existence of an interface of the two aqueous phases and phase separation caused by an osmolality difference between the two phases. The complexity of emulsion drops induced by phase separation could be controlled by varying the initial concentration of solutes and is systematically illustrated in a state diagram. In particular, this technique is utilized to successfully achieve high‐order all‐aqueous droplets in a different aqueous two‐phase system. The proposed method is simple since it only requires two initial aqueous solutions for generating multilayered, organic‐solvent‐free all‐aqueous emulsion drops, and thus these multiphase emulsion drops can be further tailored to serve as highly biocompatible material templates.     

Forming Sticky Droplets from Slippery Polymer Zwitterions

Polymer zwitterions are generally regarded as hydrophilic and repellant or “slippery” materials. Here, a case is described in which the polymer zwitterion structure is tailored to decrease water solubility, stabilize emulsion droplets, and promote interdroplet adhesion. Harnessing the upper critical solution temperature of sulfonium‐ and ammonium‐based polymer zwitterions in water, adhesive droplets are prepared by adding organic solvent to an aqueous polymer solution at elevated temperature, followed by agitation to induce emulsification. Droplet aggregation is observed as the mixture cools. Variation of salt concentration, temperature, polymer concentration, and polymer structure modulates these interdroplet interactions, resulting in distinct changes in emulsion stability and fluidity. Under attractive conditions, emulsions encapsulating 50–75% oil undergo gelation. By contrast, emulsions prepared under conditions where droplets are nonadhesive remain fluid and, for oil fractions exceeding 0.6, coalescence is observed. The uniquely reactive nature of the selected zwitterions allows their in situ modification and affords a route to chemically trigger deaggregation and droplet dispersion. Finally, experiments performed in a microfluidic device, in which droplets are formed under conditions that either promote or suppress adhesion, confirm the salt‐responsive character of these emulsions and the persistence of adhesive interdroplet interactions under flow.     

Nanoscale “Noise‐Source Switching” during the Optoelectronic Switching of Phase‐Separated Polymer Nanocomposites

A method is developed to directly map nanoscale “noise‐source switching” phenomena during the optoelectronic switching of phase‐separated polymer nanocomposites of tetrathiafulvalene (TTF) and phenyl‐C₆₁‐butyric acid methyl ester (PCBM) molecules dispersed in a polystyrene (PS) matrix. In the method, electrical current and noise maps of the nanocomposite film are recorded using a conducting nanoprobe, enabling the mapping of a conductivity and a noise‐source density. The results provide evidence for a repeated modulation in noise sources, a “noise‐source switching,” in each stage of a switching cycle. Interestingly, when the nanocomposite is “set” by a high bias, insulating PS‐rich phases shows a drastic decrease in a noise‐source density which becomes lower than that of conducting TTF‐PCBM‐rich phases. This can be attributed to a trap filling by charge carriers generated from a TTF (donor)–PCBM (acceptor) complex. In addition, when the film is exposed to UV, an optical switching occurs due to chemical reactions which lead to irreversible changes on the noise‐source density and conductivity. The method provides a new insight on noise‐source activities during the optoelectronic switching of polymer nanocomposites and thus can be a powerful tool for basic noise research and applications in organic memory devices.     

Edge Segregated Polymorphism in 2D Molybdenum Carbide

Molybdenum carbide (Mo₂C), a class of unterminated MXene, is endowed with rich polymorph chemistry, but the growth conditions of the various polymorphs are not understood. Other than the most commonly observed T‐phase Mo₂C, little is known about other phases. Here, Mo₂C crystals are successfully grown consisting of mixed polymorphs and polytypes via a diffusion‐mediated mechanism, using liquid copper as the diffusion barrier between the elemental precursors of Mo and C. By controlling the thickness of the copper diffusion barrier layer, the crystal growth can be controlled between a highly uniform AA‐stacked T‐phase Mo₂C and a “wedding cake” like Mo₂C crystal with spatially delineated zone in which the Bernal‐stacked Mo₂C predominate. The atomic structures, as well as the transformations between distinct stackings, are simulated and analyzed using density functional theory (DFT)‐based calculations. Bernal‐stacked Mo₂C has a d band closer to the Fermi energy, leading to a promising performance in catalysis as verified in hydrogen evolution reaction (HER).     

Phase Transitions in Confinements: Controlling Solid to Fluid Transitions of Xenon Atoms in an On‐Surface Network

This study reports on “phase” transitions of Xe condensates in on‐surface confinements induced by temperature changes and local probe excitation. The pores of a metal‐organic network occupied with 1 up to 9 Xe atoms are investigated in their propensity to undergo “condensed solid” to “confined fluid” transitions. Different transition temperatures are identified, which depend on the number of Xe atoms in the condensate and relate to the stability of the Xe clustering in the condensed “phase.” This work reveals the feature‐rich behavior of transitions of confined planar condensates, which provide a showcase toward future “phase‐transition” storage media patterned by self‐assembly. This work is also of fundamental interest as it paves the way to real space investigations of reversible solid to fluid transitions of magic cluster condensates in an array of extremely well‐defined quantum confinements.     

Self‐Organized Superlattice and Phase Coexistence inside Thin Film Organometal Halide Perovskite

Organometal halide perovskites have attracted widespread attention as the most favorable prospective material for photovoltaic technology because of their high photoinduced charge separation and carrier transport performance. However, the microstructural aspects within the organometal halide perovskite are still unknown, even though it belongs to a crystal system. Here direct observation of the microstructure of the thin film organometal halide perovskite using transmission electron microscopy is reported. Unlike previous reports claiming each phase of the organometal halide perovskite solely exists at a given temperature range, it is identified that the tetragonal and cubic phases coexist at room temperature, and it is confirmed that superlattices composed of a mixture of tetragonal and cubic phases are self‐organized without a compositional change. The organometal halide perovskite self‐adjusts the configuration of phases and automatically organizes a buffer layer at boundaries by introducing a superlattice. This report shows the fundamental crystallographic information for the organometal halide perovskite and demonstrates new possibilities as promising materials for various applications.     

True Meaning of Pseudocapacitors and Their Performance Metrics: Asymmetric versus Hybrid Supercapacitors

The development of pseudocapacitive materials for energy‐oriented applications has stimulated considerable interest in recent years due to their high energy‐storing capacity with high power outputs. Nevertheless, the utilization of nanosized active materials in batteries leads to fast redox kinetics due to the improved surface area and short diffusion pathways, which shifts their electrochemical signatures from battery‐like to the pseudocapacitive‐like behavior. As a result, it becomes challenging to distinguish “pseudocapacitive” and “battery” materials. Such misconceptions have further impacted on the final device configurations. This Review is an earnest effort to clarify the confusion between the battery and pseudocapacitive materials by providing their true meanings and correct performance metrics. A method to distinguish battery‐type and pseudocapacitive materials using the electrochemical signatures and quantitative kinetics analysis is outlined. Taking solid‐state supercapacitors (SSCs, only polymer gel electrolytes) as an example, the distinction between asymmetric and hybrid supercapacitors is discussed. The state‐of‐the‐art progress in the engineering of active materials is summarized, which will guide for the development of real‐pseudocapacitive energy storage systems.     

Bioinspired Nacre‐Like Alumina with a Metallic Nickel Compliant Phase Fabricated by Spark‐Plasma Sintering

Many natural materials present an ideal “recipe” for the development of future damage‐tolerant lightweight structural materials. One notable example is the brick‐and‐mortar structure of nacre, found in mollusk shells, which produces high‐toughness, bioinspired ceramics using polymeric mortars as a compliant phase. Theoretical modeling has predicted that use of metallic mortars could lead to even higher damage‐tolerance in these materials, although it is difficult to melt‐infiltrate metals into ceramic scaffolds as they cannot readily wet ceramics. To avoid this problem, an alternative (“bottom‐up”) approach to synthesize “nacre‐like” ceramics containing a small fraction of nickel mortar is developed. These materials are fabricated using nickel‐coated alumina platelets that are aligned using slip‐casting and rapidly sintered using spark‐plasma sintering. Dewetting of the nickel mortar during sintering is prevented by using NiO‐coated as well as Ni‐coated platelets. As a result, a “nacre‐like” alumina ceramic displaying a resistance‐curve toughness up to ≈16 MPa m^½ with a flexural strength of ≈300 MPa is produced.     

A digital microfluidic method for in situ formation of porous polymer monoliths with application to solid-phase extraction

We introduce the marriage of two technologies: digital microfluidics (DMF), a technique in which droplets are manipulated by application of electrostatic forces on an array of electrodes coated by an insulator, and porous polymer monoliths (PPMs), a class of materials that is popular for use for solid-phase extraction and chromatography. In this work, circular PPM discs were formed in situ by dispensing and manipulating droplets of monomer solutions to designated spots on a DMF device followed by UV-initiated polymerization. We used PPM discs formed in this manner to develop a digital microfluidic solid-phase extraction (DMF-SPE) method, in which PPM discs are activated and equilibrated, samples are loaded, PPM discs are washed, and the samples are eluted, all using microliter droplets of samples and reagents. The new method has extraction efficiency (93%) comparable to that of pipet-based ZipTips and is compatible with preparative sample extraction and recovery for on-chip desalting, removal of surfactants, and preconcentration. We anticipate that DMF-SPE may be useful for a wide range of applications requiring preparative sample cleanup and concentration.     

Device‐Level Photonic Memories and Logic Applications Using Phase‐Change Materials

Inspired by the great success of fiber optics in ultrafast data transmission, photonic computing is being extensively studied as an alternative to replace or hybridize electronic computers, which are reaching speed and bandwidth limitations. Mimicking and implementing basic computing elements on photonic devices is a first and essential step toward all‐optical computers. Here, an optical pulse‐width modulation (PWM) switching of phase‐change materials on an integrated waveguide is developed, which allows practical implementation of photonic memories and logic devices. It is established that PWM with low peak power is very effective for recrystallization of phase‐change materials, in terms of both energy efficiency and process control. Using this understanding, multilevel photonic memories with complete random accessibility are then implemented. Finally, programmable optical logic devices are demonstrated conceptually and experimentally, with logic “OR” and “NAND” achieved on just a single integrated photonic phase‐change cell. This study provides a practical and elegant technique to optically program photonic phase‐change devices for computing applications.     

Phase-Separated Dielectric Gels Based on Christiansen Effect

Phase separation is a trivial phenomenon but a mature strategy in materials science. The flexible materials are provided toughness and strength by phase separation, yet there are few applications in optics and electronics industry. A novel phase-separated dielectric gel (PSDG) with a strong Christiansen effect is prepared via radical polymerization using hydroxyethyl methacrylate as a monomer, 4-cyano-4′-pentylbiphenyl and tributyl citrate as mixed solvents, and polyethylene glycol as a softener. The solvent ratios and ambient conditions can efficiently change the color of PSDG which makes it strongly selective for the wavelength of transmitted light. Besides, it has a high dielectric constant (10 at 1 kHz), sensitively responding to the electric field. The phase separation degree of PSDG varies with applied electric field, which will induce its transmittance alteration accordingly. The current field sensitive PSDG provides a novel idea for “smart windows”. Additionally, varying the size and shape of the electrodes can precisely control the phase separation in PSDG and also enables the function of free writing on flexible materials. Therefore, the designed PSDG has great application potential for flexible touch and interesting interactions.     

EBSD Study of Microstructural Evolution in a Nickel‐Base Superalloy during Two‐Pass Hot Compressive Deformation

Generally, the high‐temperature deformation characteristics and microstructural evolution of alloys are studied by isothermal compressive experiments at stable strain rates. But, the strain rate is variant during the practice industrial production of components. In this work, isothermal two‐pass hot compression experiments with stepped strain rates are performed to analyze the microstructural evolution of a nickel‐base superalloy with δ phase. Results reveal that the mean grain size decreases, but the percentage of undissolved δ phases increases, as the strain rate of the first pass (SROFP) is increased. However, the mean grain size and the percentage of undissolved δ phases decreases with the increase of inter‐pass time (IPT) or the true strain of the first pass (TSOFP). Meanwhile, the increased deformation temperature easily enlarges the mean grain size, but obviously decreases the percentage of undissolved δ phases. In addition, the evolution of Σ3ⁿ boundaries not only results from the “new twinning mechanism”, but also “Σ3ⁿ regeneration mechanism”. “Σ3ⁿ regeneration mechanism” becomes predominant with decreasing SROFP or increasing IPT/TSOFP. Besides, “new twinning mechanism” plays a major role on Σ3ⁿ boundaries evolution as the temperature is increased from 950 to 980 °C, and then become weaken with further increasing the deformation temperature.

     

3D Probed Lipid Dynamics in Small Unilamellar Vesicles

Single‐molecule fluorescence correlation spectroscopy overcomes the resolution barrier of optical microscopy (10≈–20 nm) and is utilized to look into lipid dynamics in small unilamellar vesicles (SUVs; diameter < 100 nm). The fluorescence trajectories of lipid‐like tracer 1,1′‐dioctadecyl‐3,3,3′,3′‐tetramethylindodicarbocyanine (DiD) in the membrane bilayers are acquired at a single‐molecule level. The autocorrelation analysis yields the kinetic information on lipid organization, oxygen transport, and lateral diffusion in SUVs' membrane. First, the isomerization feasibility may be restricted by the addition of cholesterols, which form structure conjugation with DiD chromophore. Second, the oxygen transport is prevented from the ultrasmall cluster and cholesterol‐rich regions, whereas it can pass through the membrane region with liquid‐disordered phase (L_d) and defects. Third, by analyzing 2D spectra correlating the lipid diffusion coefficient and triplet‐state lifetime, the heterogeneity in lipid bilayer can be precisely visualized such as lipid domain with different phases, the defects of lipid packing, and DiD‐induced “bouquet” ultrasmall clusters.     

Membrane Engineering: Phase Separation in Polymeric Giant Vesicles

Cell membranes exhibit elaborate lipidic patterning to carry out a myriad of functions such as signaling and trafficking. Domain formation in giant unilamellar vesicles (GUVs) is thus of interest for understanding fundamental biological processes and to provide new prospects for biocompatible soft materials. Lipid rearrangements in lipidic GUVs and lipid/polymer GUVs are extensively studied whereas polymer/polymer hybrid GUVs remain evasive. Here, the focus is on the thermodynamically driven phase separation of amphiphilic polymers in GUVs. It is demonstrated that polymer phase separation is entropically dictated by hydrophobic block incompatibilities and that films topology can help to determine the outcome of polymeric phase separation in GUVs. Lastly, Janus‐GUVs are obtained and GUVs exhibit a single large domain by using a compatibilizing hydrophobic block copolymer.     

A Temperature‐Responsive Boronate Core Cross‐Linked Star (CCS) Polymer for Fast and Highly Efficient Enrichment of Glycoproteins

Fast and highly efficient enrichment and separation of glycoproteins is essential in many biological applications, but the lack of materials with high capture capacity, fast, and efficient enrichment/separation makes it a challenge. Here, a temperature‐responsive core cross‐linked star (CCS) polymer with boronate affinity is reported for fast and efficient enriching and separating of glycoproteins from biological samples. The temperature‐responsive CCS polymers containing boronic acid in its polymeric arms and poly(N‐isopropyl acrylamide) in its cross‐linked core are prepared using reversible addition‐fragmentation chain transfer polymerization via an “arm‐first” methodology. The soluble boronate polymeric arms of the CCS polymers provide a homogeneous reaction system and facilitate interactions between boronic acid and glycoproteins, which leads to a fast binding/desorption speed and high capture capacity. Maximum binding capacity of the prepared CCS polymer for horseradish peroxidase is determined to be 210 mg g^?1, which can be achieved within 20 min. More interestingly, the temperature‐responsive CCS polymers exhibit rapid reversible thermal‐induced volume phase transition by increasing the temperature from 15 to 30 °C, resulting in a facile and convenient sample collection and recovery for the target glycoproteins. Finally, the temperature‐responsive CCS polymer is successfully applied to enrichment of low abundant glycoproteins.     

Nanomolar Synthesis in Droplet Microarrays with UV‐Triggered On‐Chip Cell Screening

Miniaturization and parallelization of combinatorial organic synthesis is important to accelerate the process of drug discovery while reducing the consumption of reagents and solvents. This work presents a miniaturized platform for on‐chip solid‐phase combinatorial library synthesis with UV‐triggered on‐chip cell screening. The platform is based on a nanoporous polymer coating on a glass slide, which is modified via photolithography to yield arrays of hydrophilic (HL) spots surrounded by superhydrophobic (SH) surface. The combination of HL spots and SH background enables confinement of nanoliter droplets, functioning as miniaturized reactors for the solid‐phase synthesis. The polymer serves as support for nanomolar solid‐phase synthesis, while a photocleavable linker enables the release of the synthesized compounds into the droplets containing live cells. A 588 compound library of bisamides is synthesized via a four‐component Ugi reaction on the chip and products are detected via stamping of the droplet array onto a conductive substrate and subsequent matrix‐assisted laser desorption ionization mass spectrometry. The light‐induced cleavage shows high flexibility in screening conditions by spatial, temporal, and quantitative control.     

基于相分离制备高分子微孔材料的新探索

对制备聚合物微孔膜的相分离法进行了评述.简介了课题组几种基于相分离制备聚合物微孔材料的新探索,包括热致相分离,冷冻诱导相分离,聚合致相分离,基板诱导共混聚合物的有规相分离.     

Microstructural and Interfacial Designs of Oxygen‐Permeable Membranes for Oxygen Separation and Reaction–Separation Coupling

Mixed ionic–electronic conducting oxygen‐permeable membranes can rapidly separate oxygen from air with 100% selectivity and low energy consumption. Combining reaction and separation in an oxygen‐permeable membrane reactor significantly simplifies the technological scheme and reduces the process energy consumption. Recently, materials design and mechanism investigations have provided insight into the microstructural and interfacial effects. The microstructures of the membrane surfaces and bulk are closely related to the interfacial oxygen exchange kinetics and bulk diffusion kinetics. Therefore, the permeability and stability of oxygen‐permeable membranes with a single‐phase structure and a dual‐phase structure can be adjusted through their microstructural and interfacial designs. Here, recent advances in the development of oxygen permeation models that provide a deep understanding of the microstructural and interfacial effects, and strategies to simultaneously improve the permeability and stability through microstructural and interfacial design are discussed in detail. Then, based on the developed high‐performance membranes, highly effective membrane reactors for process intensification and new technology developments are highlighted. The new membrane reactors will trigger innovations in natural gas conversion, ammonia synthesis, and hydrogen‐related clean energy technologies. Future opportunities and challenges in the development of oxygen‐permeable membranes for oxygen separation and reaction–separation coupling are also explored.     

Understanding the Phase Emergence of Mesoporous Silica

The cylinder‐to‐vesicle phase transition of mesoporous silica and the inter‐dependence of the controlling factors are studied. (3‐Mercaptopropyl)trimethoxylsilane (MPTMS) is used to alter the phase outcome of mesoporous silica from the cylindrical MCM‐41 to the vesicular phase. Exploiting the phase selection at the critical time point of phase emergence allows investigation of the complex interactions among the ingredients. In this system, orderly cylindrical or vesicular phase directly emerges from the “clumps” of randomly mixed surfactant, co‐surfactant, and silica precursor. The phase outcome depends on the exact ratio of the ingredients, provided that enough amounts of MPTMS can diffuse into the clumps before the hardening silica prevents the diffusion.