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.

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.

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.

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.

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.

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.

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.

A novel super thermal insulation material: bamboo-like polymer nanotubes.

One-dimensional nanomaterials have widely applied in the fields of energy conversion and storage due to their exceptional performance because of the nano-size effect. Herein, we synthesized bamboo-like polymer nanotubes based on cationic polymerization using immiscible initiator nanodroplets that results in a hollow structure. The suspended microelectrode is fabricated to measure the axial thermal conductivity of a single polymer nanotube, which demonstrates that this hollow structure can reduce its effective thermal conductivity. The experimental results show that its effective thermal conductivity is close to 0.03 W m-1 K-1, and decreases to 0.02 W m-1 K-1 with increasing temperature of the heating microelectrode, which may be due to the increasing lattice vibration and inelastic scattering between phonons. Its effective thermal conductivity is smaller than that of air, indicating that the synthetic method is an effective way to fabricate thermal insulating polymer nanotubes by significantly lowering the effective thermal conductivity. Hence, the method offers a new strategy in the fields of thermal insulation and protection.

Stabilizing Polymeric Interface by Janus Nanosheet.

A strategy is proposed to stabilize the polymeric interface by using the irregular Janus nanosheet (JNS). The poly(vinylidene fluoride) (PVDF)/poly(l-lactic acid) (PLLA) at 60/40 (wt/wt) with a bi-continuous structure is selected as the model melt blend, and the PMMA/epoxy JNS is synthesized and used as the compatibilizer. The JNS is preferentially located at the interface. The interfacial coverage by the JNS reaches a saturated state forming the interconnected jamming structure at 0.5 wt% of the JNS. The interface is thus stabilized which is well preserved after annealing at high temperature. After selectively etching PLLA, the robust PVDF porous material is derived with the JNS armored at the pore skeleton surface. The porous material provides a universal scaffold to achieve stable functional materials after filling the pores.

Emulsion Interfacial Synthesis of Polymer/Inorganic Janus Particles.

We report a method to prepare polymer/inorganic Janus particles by transferring self-assembled membranes of copolymers such as PS- b-PAA at an emulsion interface when the amine-capped particles such as paramagnetic Fe3O4@SiO2 core/shell particles are preferentially adsorbed by specific interactions. While the particles are protected, the exposed side can be further modified to conjugate aldehyde-capped polyethylene oxide (PEO). Both connections become robust by covalent bonds. The hydrophilic PEO and hydrophobic PS chains are distinctly compartmentalized onto the opposite sides of the Fe3O4@SiO2 particles. As a magnetic responsive solid surfactant, the stabilized emulsions can be driven with a magnet for directional movement and coalescence with increasing magnetic strength. This method can be extended to other Janus particles with tunable organic materials and solid particles.

Poly(ionic liquid)-Modified Magnetic Janus Particles for Dye Degradation.

The Fe3O4@SiO2 paramagnetic Janus particles with phenyl groups and amino groups segmented on two different sides were fabricated by the Pickering emulsion method. Then, the poly(ionic liquid)s were selectively modified onto the amino side via in situ induced ATRP polymerization. Different anions were introduced onto the poly(ionic liquid)s region by exchanging anions to adjust the wettability of the side. Meanwhile, after the PW12O403- anions were employed, the poly(ionic liquid)-modified Fe3O4@SiO2 Janus particles can be used as a catalytic solid emulsifier and degraded water-soluble dyes with the aid of stabilizing emulsion.

Particle Mold Synthesis of Block Copolymer Janus Nanomaterials.

A particle mold synthesis of 2D Janus nanomaterials is proposed by crosslinking of copolymer self-assembled monolayers confined within the mold domains. Onto the silica (SiO2 ) particle surface, mold domains with functional groups such as imidazole are generated. The model copolymer of polyacrylic acid-block-polystyrene (PAA-b-PS) can be preferentially absorbed onto the domains via electrostatic interactions, forming a self-assembled monolayer. In a cosolvent such as tetrahydrofuran (THF), the crosslinking occurs within the whole of the PAA side. A Janus disc is thus achieved after detachment from the particle upon breaking the specific interaction. In a poor solvent, the crosslinking slowly occurs from the periphery, giving Janus nanorings. The rings evolve into discs with further crosslinking. The mold particles can be recycled to synthesize the same 2D Janus materials.

Janus Composite Nanorod from a Molecular Bottlebrush Containing a Block Copolymer.

The asymmetric ABC-type Janus polymer composite nanorods are synthesized by the in situ preferential growth of functional materials against the molecular bottlebrush containing a triblock copolymer of poly(ethylene oxide)-b-poly(2-methacryloyloxyethyl pentynoate-g-poly(acrylic acid))-b-polystyrene. PEO and PS single chains are terminated onto the opposite ends of the composite nanorods. The two polymer chains are responsible for amphiphilic performance, while the composite nanorod is responsible for the functionality. The Janus nanorods can stand vertically at an emulsion interface, making the interfaces easily functionalized and manipulated. Protection of the PAA molecular bottlebrush via electrostatic interaction is important to obtaining individual nanorods at high solid contents. A huge family of Janus composite nanorods is expected by changing the compositions of the two polymer chains and the nanorod.

Janus Colloids toward Interfacial Engineering.

Janus colloids are functional particles consisting of two surfaces (or internal materials) with distinct physical or chemical properties in the same particle. Owing to their amphiphilic nature, Janus colloids composed of both hydrophilic and hydrophobic faces provide a powerful tool to generate functional surfaces and to manipulate the properties of interfaces. Amphiphilic Janus colloids have shown promising applications as particulate surfactants in oil/water separation, as interfacial compatibilizers in polymer blends, and as assembly blocks in robust coatings with unique wettability. In this Feature Article, we summarize recent advances in engineering interfaces by using Janus colloids.

Liquid Crystals under Confinement in Submicrometer Capsules.

Liquid crystal (LC) ordering and phase transition behavior under confined conditions have attracted extensive attention and enabled many applications. However, the ordering and phase transition behavior of LCs in submicrometer capsules have seldom been studied, primarily due to the lack of proper capsulizing and visualization approaches to such small LC microcapsules. Herein, we achieve submicrometer LC capsules with the sizes down to 100 nm by using emulsion-based interfacial sol-gel reaction. The behavior of LCs under the submicrometer confinement conditions is investigated while the sizes and chemical composition of the microcapsule shell surface are tuned in a controllable way. The phase transition temperatures of LCs in the submicrometer capsules shift from those of bulk LCs due to the surface-induced ordering of LCs under the strong confinement conditions, which causes formation of topological defects and alters the order parameter. Using nonlinear optical imaging technology, we explore the structures of director field of LCs that arise as a result of the competition between the surface boundary conditions and LC elasticity. The results show that the nanoscale encapsulation can significantly influence the structural configurations of the director and phase transitions of LCs under various confinement conditions.

Construction of Injectable Double-Network Hydrogels for Cell Delivery.

Herein we present a unique method of using dynamic cross-links, which are dynamic covalent bonding and ionic interaction, for the construction of injectable double-network (DN) hydrogels, with the objective of cell delivery for cartilage repair. Glycol chitosan and dibenzaldhyde capped poly(ethylene oxide) formed the first network, while calcium alginate formed the second one, and in the resultant DN hydrogel, either of the networks could be selectively removed. The moduli of the DN hydrogel were significantly improved compared to that of the parent single-network hydrogels and were tunable by changing the chemical components. In situ 3D cell encapsulation could be easily performed by mixing cell suspension to the polymer solutions and transferred through a syringe needle before sol-gel transition. Cell proliferation and mediated differentiation of mouse chondrogenic cells were achieved in the DN hydrogel extracellular matrix.

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.

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.

Shaping functional nano-objects by 3D confined supramolecular assembly.

Nano-objects are generated through 3D confined supramolecular assembly, followed by a sequential disintegration by rupturing the hydrogen bonding. The shape of the nano-objects is tunable, ranging from nano-disc, nano-cup, to nano-toroid. The nano-objects are pH-responsive. Functional materials for example inorganic or metal nanoparticles are easily complexed onto the external surface, to extend both composition and microstructure of the nano-objects.

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.