Soft-Hard Janus Nanoparticles Triggered Hierarchical Conductors with Large Stretchability, High Sensitivity, and Superior Mechanical Properties.

There is a long-standing conflict between the large stretchability and high sensitivity for strain sensors, a strategy of decoupling the mechanical/electrical module by constructing the hierarchical conductor has been developed in this study. The hierarchical conductor, consisting of a mechanically stretchable layer, a conductive network layer, and a strongly bonded interface, can be produced in a simple one-step process with the aid of soft-hard Janus nanoparticles (JNPs). The introduction of JNPs in the stretchable layer can evenly distribute stress and dissipate energy due to forming the rigid-flexible homogeneous networks. Specifically, JNPs can drive graphene nanosheets (GNS) to fold or curl, creating the unique JNPs-GNS building block that can further construct the conductive network. Due to its excellent deformability to hinder crack propagation, the flexible conductive network could be stretched continuously and the local conductive pathways could be reconstructed. Consequently, the hierarchical conductor could detect both subtle strain of 0-2% and large strain of up to 370%, with a gauge factor (GF) from 66.37 to 971.70, demonstrating outstanding stretchability and sensitivity. And it also owns large tensile strength (5.28 MPa) and high deformation stability. This hierarchical design will give graphene-based sensors a major boost in emerging applications.

Interfacial Activity of Janus Particle: Unity of Molecular Surfactant and Homogeneous Particle.

Janus particles with different compositions and properties segmented to different regions on the surface of one objector provide more opportunities for interfacial engineering. As a novel interfacial active material, Janus particles integrate the amphiphilic properties of molecular surfactants and the Pickering effect of homogeneous particles. In this research, the outstanding properties of Janus particles on various interfaces are examined from both theoretical and practical perspectives, and the advantages of Janus particles over molecular surfactants and homogeneous particle surfactants are analyzed. We believe that Janus particles are ideal tools for interface regulation and functionalization in the future.

Anisotropic Multitentacle Janus Particles Synthesized by Selective Asymmetric Growth.

Anisotropic colloidal particles with asymmetric morphology possess functionally rich heterogeneous structures, thus offering potential for intricate superstructures or nanodevices. However, it is a challenge to achieve controlled asymmetric surface partitioned growth. In this work, an innovative strategy is developed based on the selective adsorption and growth of emulsion droplets onto different regions of object which is controlled by wettability. It is found that the emulsion droplets can selectively adsorb on the hydrophilic surface but not the hydrophobic one, and further form asymmetric tentacle by the interfacial sol-gel process along its trajectory. Janus particles with an anisotropic shape and multitentacle structure are achieved via integration of emulsion droplet (soft) and seed (hard) templates. The size and number of tentacles exhibit tunability mediated by soft and hard templates, respectively. This general strategy can be expanded to a variety of planar substrates or curved particles, further confirming the correlation between tentacle growth and Brownian motion. Most interestingly, it can be employed to selectively modify one region of surface partitioned particles to achieve an ABC three-component Janus structure.

Waterproof and Flame-Retardant Fabric Coating with Nail-Tie Structure was Constructed by Janus Particles with Strong Mechanical, Physical, and Chemical Durability.

Oil spills are one of the most dangerous sources that cause serious environmental pollution and fire and explosion. In this work, multifunctional separator silica@polydivinylbenzene/poly 2,6-dimethyl-1, 4-phenyl ether (silica@PDVB/PPE) Janus particles were fabricated via seed emulsion polymerization, causing phase segregation as well as selective modification. The epoxy modified silica is partially covalently bonded to the fabric substrate surface by simple spraying to achieve a strong composite coating. The low surface energy PDVB/PPE forms a micronano rough layered surface, which can achieve a super hydrophobic and lipophile surface (WCA = 155°) and obtain a high flux separation of water and oil at 32,700 L·m-2·h-1. At the same time, the Janus composite fabric coating has the advantages of high heat resistance and flame retardant, which is realized by halogen-free flame-retardant unsaturated polyphosphate (PPE), making Janus fabric have potential value in separating oil-water mixtures and fire protection applications. In addition, the coating shows excellent chemical durability. After soaking in various aqueous solvents and organic solvents for 30 h, it can still maintain superhydrophobicity and flame retardant. The coating still has water repellency and flame retardant after 50 washings and mechanical wear and has good mechanical durability.

Janus Hemispheres through Controlled Polymerization-Induced Phase Separations within Wax Droplets.

A series of Janus hemispheres with a patchy hemispherical surface and a flat undersurface were synthesized through controlled polymerization-induced phase separation within emulsified wax droplets. The hemispherical shape was generated through the polymerization of styrene within wax droplets, followed by the grafting of hydrophilic polymers on the exposed surface. Then, the patchy hemispherical surface was achieved after introducing the hydrophobic acrylate monomers within wax droplets and controlling the polymerization-induced phase separation. The morphological evolution of patches was recorded via the reaction time, followed by their morphological regulation through the type, feeding amount, and cross-linking degree of acrylate monomers. A functional monomer, vinyl benzyl chloride (VBC), was also used to copolymerize the patches for grafting a zwitterionic polymer via surface-initiated atom transfer radical polymerization (SI-ATRP). The as-obtained Janus hemispheres were employed to fabricate robust coatings with wettability tuned from superhydrophobicity to underwater superoleophobicity by the grafted zwitterionic polymers.

Flask-like Janus Colloidal Motors with Explicit Direction and Tunable Speed.

Nanoparticles with an anisotropic morphology and composition are flourishing in various scientific fields. Their morphology has a great impact on their functions, but the precise regulation of their growth and final morphology is still challenging. Here, flask-like Janus particles (FJPs) with different compositions segmented on the inner and outer surfaces were fabricated via a sol-gel process using different silane precursors. The neck length of the flask-like particles can be controllably regulated by employing different silane precursors. The Pt catalyst was selectively loaded in their cavities, and as-formed FJPs@Pt are employed as colloidal motors. Due to the adjustable neck length, the Janus colloidal motors have explicit directionality and tunable speeds (max diffusion coefficient is 18.2 µm2 s-1).

Single-Hole Janus Hollow Sphere.

Cross-linked epoxy resin (EP) single-hole Janus hollow spheres are prepared by cross-linking induced phase separation within an emulsion droplet and selective modification. The droplet is composed of an EP oligomer, toluene, and hexadecane. 2-Ethyl-4-methylimidazole is used as the cross-linker added to the aqueous phase. During the cross-linking, hexadecane forms an eccentric core in the cross-linked EP sphere. A single hole forms across the shell after dissolving the solvents, and a single-hole hollow sphere is achieved. The hole and cavity size are controlled by adjusting the solvent content and cross-linker concentration. Furthermore, frozen wax is used as the core material instead of hexadecane to effectively protect the sphere's interior surface. Selective modification of the exterior and interior surfaces is thus permitted. As an example, a responsive single-hole Janus hollow sphere is prepared by the favorable growth of a silica-polyoxyethylene composite layer onto the exterior surface and a selective grafting of poly(2-diethylaminoethyl methacrylate) (PDEAEMA) by atom-transfer radical polymerization (ATRP) onto the interior. The Janus sphere is water-dispersible and controllably captures and releases oil from the aqueous environment as triggered by the pH value.

Asymmetric ultrathin silica nanonets as a super-performance emulsifier.

HYPOTHESIS: Pickering emulsions have been used in many fields such as catalytic synthesis, pharmaceutics and oilfield chemicals. They usually have good stability, but in some extreme conditions such as at high temperatures or in special liquid-liquid systems, poor stability is often encountered. EXPERIMENTS: Herein, ultrathin silica nanosheets with controllable morphologies were synthesized via a simple interfacial anisotropic self-assembly approach integrated with pore-forming techniques. By regulating the size, density and pattern of the apertures, three types of unique nanosheets including mesoporous nanosheets, meso/macroporous topology-nanosheets and asymmetric nanonets with hollows were obtained. FINDINGS: After a simple hydrophobic modification, the nanonets exhibited super-performance as particulate emulsifiers, owing to their two-dimensional (2D) structures of large pore volume and hierarchical pore/hollow arrangements. As a result, those silica nanonets can stabilize various emulsion systems at considerably high temperatures that are difficult to be stabilized by conventional particulate emulsifiers even at a dose of 100x higher. This work paves a promising way to develop novel 2D asymmetric nanomaterials with tunable compositions, aperture parameters and morphologies for emulsification and potential applications.

An ideal catalyst carrier: patchy nanoparticles with dual functional domains of substrate enrichment and catalysis.

Enriching substrates near catalysts is an effective strategy to improve heterogeneous catalytic performance. The surface of PMMA@PIL-PA patchy nanoparticles is segmented into PMMA and PIL-PA domains. The hydrophobic PMMA domain can enrich water-insoluble substrates, while the hydrophilic PIL-PA one catalyzes the reaction of water-soluble and water-insoluble substrates in close proximity. The special patchy nanoparticles with both a hydrophobic substrate warehouse and catalysis functional divisions can effectively improve the catalytic efficiency. They were employed to catalyze the acetal reaction between water-insoluble benzaldehyde and water-soluble ethylene glycol by phosphotungstic acid (PA). Compared with the homo-nanoparticles, the conversion rate was greatly improved.

Temperature-Sensitive Anti-Inflammatory Organohydrogels Containing Janus Particle Stabilized Phase-Change Microinclusions.

A fabrication strategy for multifunctional organohydrogels is proposed, which combines phase-change microinclusions within a double-network (DN) hydrogel under the stabilization of Janus particles. Janus particles possess reactivity and colloidal stability for more robust organohydrogels, while the interstice among Janus particles enhances the mass transfer between the phase interfaces. Moreover, DN hydrogels are achieved through dynamic cross-linking networks, endowing organohydrogels with injectability and self-healing performance. Phase-change microinclusions are beneficial to the organohydrogels with temperature-responsive mechanical property and temperature-programed shape-memory performance. Organohydrogels can be employed for temperature therapy through the melting-crystallization process of phase-change microinclusions. Simultaneously, the payloads within microinclusions can be released for antibacteria upon melting the encapsulated wax. The organohydrogels can be served as an ideal dressing with temperature-responsive mechanical property, temperature therapy effectiveness, and temperature-triggered antibacterial ability.

Aptamer-based biosensing through the mapping of encoding upconversion nanoparticles for sensitive CEA detection.

A sensitive detection system based on aptamer-based biosensors for the detection of carcinoembryonic antigen (CEA) by mapping encoding upconversion nanoparticles (UCNPs) was constructed. In this sensor, oligonucleotides with CEA aptamer fragments immobilized on magnetic beads (MBs) were hybridized to complementary DNA modified on UCNPs (cDNA-UCNPs); thus, sandwich-structured probes were formed. In the presence of CEA, due to the stronger interaction between the aptamer and CEA than that of the aptamer and complementary DNA on UCNPs, the cDNA-UCNPs were isolated from the MBs, and the number of isolated UCNPs was directly related to the concentration of CEA. Using an inverted fluorescence microscope, the number of target-dependent UCNPs on a glass slide was counted, enabling the accurate determination of CEA in the solution. The dynamic range for CEA detection in PBS buffer was 0.02-6.0 ng mL-1 (0.1-30 pM) and a limit of detection (LOD) of 65 fM was achieved. We envisage that the system we developed can also have many promising applications in the sensitive detection of other biomarkers for early cancer diagnosis.

Poly(lactic acid)/Poly(butylene succinate) (PLA/PBS) Layered Composite Gas Barrier Membranes by Anisotropic Janus Nanosheets Compartibilizers.

Poly(lactic acid) (PLA), one of the most promising biodegradable polymer products, has achieved wide applications for its relatively good mechanical properties and moderate degradability. Here we report an environment-friendly filler, the organic-inorganic composite Janus nanosheets (PLA/PBS JNs), which can jam at the interface of the PLA/PBS blend with a low threshold as the compatibilizer and can simultaneously toughen the composites and improve the gas barrier performance due to better interfacial interaction and tortuous path effect. With 0.3 wt % of PLA/PBS JNs added, the tensile strength and elongation at break of the PLA/PBS blend can be improved by 37% and 224%, respectively. After a further hot-pressing process, the barrier performance of the PLA/PBS composite membranes can be significantly enhanced since PLA, PLA/PBS JNs, and PBS are arranged in a nearly lamellar structure with oxygen permeability of 0.63 × 10-15 cm3 cm·cm-2 s-1 Pa-1 with only 0.5 wt % of PLA/PBS JNs.

Janus Nanoparticle Coupled Double-Network Hydrogel.

For double network (DN) hydrogels, their performance can be tuned by adjusting the interaction between their two networks. A novel DN hydrogel toughening approach is proposed by employing Janus nanoparticles (JNs) as crosslinkers to gain a conjoined-network hydrogel. First, a kind of JNs modified by amino groups and quaternary ammonium salt is synthesized, named R3 N+ -JN-NH2 . The DN hydrogel is fabricated based on ionic coordination between calcium chloride (CaCl2 ) and sodium alginate (Alg), as well as covalent (benzoic imine) between glycol chitosan (GC) and benzaldehyde-capped poly(ethylene oxide) (BzCHO-PEO-BzCHO). Based on the same covalent and ionic dynamic crosslinking mechanism, the added R3 N+ -JN-NH2 interacts with two networks to promote crosslinking to form a dually crosslinked structure. The R3 N+ -JN-NH2 effectively provides more energy dissipation, and the hydrogel with conjoined networks shows better compression resistance.

Preparation of asymmetric particles by controlling the phase separation of seeded emulsion polymerization with ethanol/water mixture.

Alcohols are discovered for the first time to tune the morphology of poly(vinyl benzyl chloride)-poly(3-methacryloxypropyltrimethoxysilane) (PVBC-PMPS) composite particles through seeded emulsion polymerization within the alcohol/water mixture. Here, monodispersed linear PVBC particles was synthesized through the dispersion polymerization and employed as the seeds. The as-obtained PVBC-PMPS composite particles could be dramatically tuned from core-shell structures to snowman-like particles, to dumbbell-shaped particles, to inverse snowman-like particles when the ethanol content in reaction mixtures is only adjusted within a narrow range. The morphology of fresh PMPS bulges was observed after removing the linear PVBC seeds with N,N'-dimethyl formamide, and their formation mechanism was studied by monitoring the free radical polymerization and sol-gel process of 3-methacryloxypropyltrimethoxysilane. It has been confirmed that the sol-gel kinetics were the main factor on the particles' morphology. In addition, morphologies of PVBC-PMPS particles were also varied by the MPS feeding amount, types of the co-solvent and pH values of alcohol/water mixtures.

Zwitterionic Polymer Hairy Coating onto Mesh toward Easy Oil/Water Separation.

A zwitterionic polymeric hair-coated stainless steel mesh membrane is fabricated, which demonstrates efficient separation of oil/water mixtures and emulsions. The hairy coating of poly(divinylbenzene-co-vinylbenzene chloride) is generated by precipitation cationic polymerization, and subsequently grafting a zwitterionic polymer layer by atom transfer radical polymerization of sulfobetaine methacrylate. The microstructure of the hairy coating is tunable from an array of individual nanofibers to porous networks by interweaving of the hairs. The long-range attraction of zwitterionic polymers with water renders the coated mesh with excellent superhydrophilic and underwater superoleophobic performance. The coated mesh is highly antifouling to avoid the prehydration in conventional methods. Moreover, the microstructure is demonstrated to be responsible for the high separation efficiency of oil/water emulsion. Therefore, separation of oil/water mixtures and emulsions becomes easier by the coated mesh, which is promising in industrial oil field sewage treatment.

Efficient recovery and enrichment of rare earth elements by a continuous flow micro-extraction system.

The excessive exploitation of rare earth elements (REEs) has caused major losses of non-renewable resources and damage to the ecosystem. The processes of mining and smelting produce massive amounts of wastewater with low concentrations of REEs. Consequently, the enrichment and recovery of low-concentration REEs from wastewater has significant economic and environmental value. For this purpose, operation under large phase ratios (the flow rate ratio between the aqueous phase and extractant) is more desirable and economically viable. However, the traditional REE extraction process suffers from the uneven dispersion of the extractant and the difficulty of phase separation, which leads to long extraction times and large consumption of extractants. Hence, there is an urgent need to develop a green and efficient technique to extract low concentrations of REEs from wastewater. In this work, a droplet-based microfluidic technique was used to continuously extract and recover low-concentration REEs at large phase ratios. Snowman-shaped magnetic Janus nanoparticles were added to the continuous phase as emulsifiers to facilitate uniform extractant dispersion and rapid phase separation. Several key factors affecting the extraction efficiency, including pH, residence time, and the amount of added Janus nanoparticles, were systematically investigated. Compared to batch extraction, droplet-based microfluidic extraction with the addition of Janus nanoparticles showed the advantages of a large specific surface area and fast phase separation during extraction. Meanwhile, the Janus nanoparticles exhibited good emulsification performance after three extraction cycles. In summary, the Janus nanoparticle-stabilized droplet generated by microfluidic methods provides a feasible path for the efficient enrichment and recovery of low-concentration REEs.

Tadpole-like Janus nanotubes.

Tadpole-like Janus nanotubes with controlled size are fabricated by a sol-gel reaction at the emulsion interface. Pd or Fe3O4 nanoparticles can be selectively captured into their cavities to obtain tadpole-like Janus Pd-nanotubes or tadpole-like Janus Fe3O4-nanotubes. They can be driven directionally by a chemical fuel or near-infrared (NIR) light.

Superhydrophobic Coating Derived from the Spontaneous Orientation of Janus Particles.

A superhydrophobic surface was achieved using a monolayer of the perpendicularly oriented epoxy-silica@polydivinylbenzene (PDVB) Janus particles (JPs) on an epoxy resin substrate. The epoxy-silica@PDVB JPs were synthesized from the silica@PDVB/polystyrene (PS) JPs through selective etching of the PDVB/PS belly and the surface modification of the silica part. The modified silica parts can be covalently bonded with the epoxy resin to make the perpendicular orientation spontaneous as well as the coating more robust. The outward PDVB bellies can constitute the micro-/nanoscale hierarchical structures for the superhydrophobic property. The superhydrophobic coating exhibits water repellence and self-cleaning properties. Moreover, the coating exhibits good chemical durability that it can keep the superhydrophobic property after long-time immersion in various aqueous solutions and organic solvents. The coating is still superhydrophobic after water flushing and mechanical wearing, showing the perfect mechanical durability.

Facile Approach to Fabricate a High-Performance Superhydrophobic Mesh.

When superhydrophobic meshes are used for oil/water separation, high flux and high intrusion pressure are usually compromised. Herein, a high-performance superhydrophobic stainless steel mesh membrane with a hairy-like poly(divinylbenzene) (PDVB) coating is fabricated by precipitated cationic polymerization. The synthesis is facile, which is completed in one step at ambient temperature within a short time, i.e., less than 90 s. The unique hair-like microstructure of PDVB is responsible for the superhydrophobic performance with less blockage for the pores. A higher flux for oil is achieved while keeping a high intrusion pressure. Especially, the ellipsoidal pore texture with two sharp tips can give additional high intrusion pressure. In the case of 2800 mesh, the superhydrophobic mesh displays an unprecedentedly high value of up to 22 kPa while maintaining a high flux of 2.0 × 104 L·m-2·h-1. The high intrusion pressure enables further increment of flux to 4.2 × 104 L·m-2·h-1 under a reduced pressure at a higher loading. The current high-performance superhydrophobic mesh realizes higher efficiency in separating oil/water mixtures, which is promising for practical applications, for example, in industrial extraction.

Semi-IPNs Reinforced with Silica Janus Nanoparticles and Their Stress Sensing with Mechanoluminescent Probe.

A series of nanocomposite elastomers are prepared by dispersing surface-modified silica Janus nanoparticles into semi-interpenetrating network (Semi-IPN) of polyurethane/polyethyl methacrylate. Benefiting from the hierarchically crosslinked structures that consist of physical interlocking mediated by hydrogen-bond-rich silica Janus nanoparticles and permanent crosslinking by Semi-IPN, these elastomers exhibit excellent mechanical properties. Moreover, the Janus nanosheet is found more effective in strengthening and toughening the Semi-IPN, in comparison to Janus hollow sphere. Since 1,2-dioxetane is covalently embedded in these elastomers as a mechanoluminescent stress probe, stress transfer between the polymer and Janus nanoparticles and the toughening mechanism can be illuminated, which offer exciting opportunities to study the failure process of complex polymer nanocomposites with high spatial and temporal resolution.