Facile fabrication of magnetic MoO2–Salen‐modified graphene‐based catalyst for epoxidation of alkenes

A facile, green and efficient method for the immobilization of MoO₂–Salen onto graphene hybridized with glucose‐coated magnetic Fe₃O₄ nanoparticles is proposed to fabricate a magnetic organic–inorganic hybrid heterogeneous RGO/Fe₃O₄@C‐Salen‐MoO₂ catalyst for the epoxidation of cyclooctene and geraniol using tert ‐butyl hydroperoxide or H₂O₂ as oxidant. Carbon‐coated Fe₃O₄ can improve the stability and add functional ─OH groups on the surface of Fe₃O₄. The fabricated composite exhibited good performance due to good dispersion of MoO₂–Salen active sites. The catalyst can be easily separated from the reaction system using a permanent magnet and used three times without significantly losing its catalytic activity and selectivity.     

A Carbon‐Sulfur Hybrid with Pomegranate‐like Structure for Lithium‐Sulfur Batteries

A carbon‐sulfur hybrid with pomegranate‐like core–shell structure, which demonstrates a high rate performance and relatively high cyclic stability, is obtained through carbonization of a carbon precursor in the presence of a sulfur precursor (FeS₂) and a following oxidation of FeS₂ to sulfur by HNO₃. Such a structure effectively protects the sulfur and leaves enough buffer space after Fe³⁺ removal and, at the same time, has an interconnected conductive network. The capacity of the obtained hybrid is 450 mA h g^?1 under the current density of 5 C. This work provides a simple strategy to design and prepare various high‐performance carbon‐sulfur hybrids for lithium‐sulfur batteries.     

Preparation of hollow composite spheres with raspberry‐like structure based on hydrogen‐bonding interaction

The hollow composite spheres with a raspberry‐like structure were prepared by a self‐assemble heterocoagulation based on the inter‐particle hydrogen‐bonding interaction between the amide groups of hollow poly (N,N′‐methylenebisacrylamide‐co‐N‐isopropyl acrylamide) (P(MBA‐co‐NIPAAm)) microspheres and the carboxylic acid groups of poly(ethyleneglycol dimethacrylate‐co‐methacrylic acid) (P(EGDMA‐co‐MAA)) nanoparticles, in which P(EGDMA‐co‐MAA) nanoparticle acted as the corona and the hollow P(MBA‐co‐NIPAAm) microsphere behaved as the core. The control coverage of the corona particles on the surface of hollow core microspheres of P(MBA‐co‐NIPAAm)/P(EGDMA‐co‐MAA) hollow composite sphere was studied in detail through adjustment of the mass ratio between the core and corona particles. The effect of the pH on the stability of the raspberry‐like hollow spheres was investigated. The polymer particles and the resultant heterocoagulated raspberry‐like hollow spheres were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Copyright © 2008 John Wiley & Sons, Ltd.     

Films from soft‐core/hard‐shell hydrophobic latexes: Structure and thermomechanical properties

Structured latexes provide a promising route to hard coatings without the use of coalescing aids. We studied the thermomechanical properties of films from structured soft‐core/hard‐shell hydrophobic latexes. We found that the mechanical properties of these films were closely related to their very particular organization. When the rigid phase was continuous, whatever its volume fraction, the films exhibited a high elastic modulus. An analysis of the viscoelastic properties of the films provided a good method for obtaining information about the interphase between the hard shell and soft core of the latex particles. By varying the film structure through annealing or the particle composition (core/shell ratio, core crosslinking, etc.), we were able to tune the mechanical properties of the films. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2989–3000, 2000     

Near‐Infrared Triggered Decomposition of Nanocapsules with High Tumor Accumulation and Stimuli Responsive Fast Elimination

A near‐infrared (NIR) induced decomposable polymer nanocapsule is demonstrated. The nanocapsules are fabricated based on layer‐by‐layer co‐assembly of azobenzene functionalized polymers and up/downconversion nanoparticles (U/DCNPs). When the nanocapsules are exposed to 980 nm light, ultraviolet/visible photons emitted by the U/DCNPs can trigger the photoisomerization of azobenzene groups in the framework. The nanocapsules could decompose from large‐sized nanocapsule to small U/DCNPs. Owing to their optimized original size (ca. 180 nm), the nanocapsules can effectively avoid biological barriers, provide a long blood circulation (ca. 5 h, half‐life time) and achieve four‐fold tumor accumulation. It can fast eliminate from tumor within one hour and release the loaded drugs for chemotherapy after NIR‐induced dissociation from initial 180 nm capsules to small 20 nm U/DCNPs.     

Cube‐in‐Cube Hollow Cu9S5 Nanostructures with Enhanced Photocatalytic Activities in Solar H2 Evolution

Hydrogen produced from water under solar energy is an ideal clean energy source, and the efficiency of hydrogen production usually depends on the catalytic systems based on new compounds and/or a unique nanostructure. Herein, well‐defined cube‐in‐cube hollow Cu₉S₅ nanostructures have been successfully prepared with Cu₂O nanocubes and CS₂ as precursors, and single‐shell hollow Cu₉S₅ nanocubes could be obtained by replacing CS₂ with Na₂S. The formation mechanism of cube‐in‐cube hollow nanostructures has been proposed based on the Kirkendell effect and an outward self‐assembly process. Further studies revealed that the cube‐in‐cube hollow Cu₉S₅ nanostructures exhibited better photocatalytic activity toward solar H₂ evolution and would be a promising photocatalyst in the solar hydrogen industry.     

Rare‐Earth‐Based Nanoparticles with Simultaneously Enhanced Near‐Infrared (NIR)‐Visible (Vis) and NIR‐NIR Dual‐Conversion Luminescence for Multimodal Imaging

Multifunctional NaGdF₄:Yb³⁺,Er³⁺,Nd³⁺@NaGdF₄:Nd³⁺ core–shell nanoparticles (called Gd:Yb³⁺,Er³⁺,Nd³⁺@Gd:Nd³⁺ NPs) with simultaneously enhanced near‐infrared (NIR)‐visible (Vis) and NIR‐NIR dual‐conversion (up and down) luminescence (UCL/DCL) properties were successfully synthesized. The resulting core–shell NPs simultaneously emitted enhanced UCL at 522, 540, and 660 nm and DCL at 980 and 1060 nm under the excitation of a 793 nm laser. The enhanced UCL and DCL can be explained by complex energy‐transfer processes, Nd³⁺→Yb³⁺→Er³⁺ and Nd³⁺→Yb³⁺, respectively. The effects of Nd³⁺ concentration and shell thickness on the UCL/DCL properties were systematically investigated. The UCL and DCL properties of NPs were observed under the optimal conditions: a shell Nd³⁺ content of 20 % and a shell thickness of approximately 5 nm. Moreover, the Gd:Yb³⁺,Er³⁺,Nd³⁺@Gd:20 % Nd³⁺ NPs exhibited remarkable magnetic resonance imaging (MRI) properties similar to that of a clinical agent, Omniscan. Thus, the core–shell NPs with excellent UCL/DCL/magnetic resonance imaging (MRI) properties have great potential for both in vitro and in vivo multimodal bioimaging.     

Preparation and characterization of pH‐responsive and thermoresponsive hybrid microgel particles with gold nanorods

We report on pH‐responsive and thermoresponsive hybrid materials based on the assembly of gold nanorods, Au NRs, into multiresponsive, crosslinked copolymer microgel particles. These microgel particles were prepared by the surfactant‐free emulsion polymerization of N‐isopropylacrylamide and acrylic acid using N, N′‐methylene bis‐acrylamide as a crosslinker, which produces particles measuring approximately 160 nm that are interconnected to one other. Cetyltrimethyl ammonium bromide‐stabilized Au NRs were also prepared independently using a seed‐mediated growth method and then loaded into swollen, deprotonated, acrylic acid‐containing microgel particles using the electrostatic interactions between the oppositely charged particles. Transmission electron micrographs of the as‐prepared hybrid Au NR–microgel particles confirmed that the Au NRs were attached to the surface of the microgel particles. The size‐dependent temperature‐responsive characteristics of the hybrid microgel particles were studied by dynamic light scattering, and it was found that as the temperature increased across the phase transition temperature, the particle size decreased to 56% of the original volume. The thermoresponsive and pH‐responsive optical properties of the hybrid microgel particles were also systematically investigated. The thermo‐ and pH‐induced shrinkage of the microgel led to an increase in the UV–vis absorption intensity and caused a significant blue shift in the longitudinal surface plasmon bands of the Au NRs. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Microgel Capsules Tailored by Droplet‐Based Microfluidics

Microgel capsules are micrometer‐sized particles that consist of a cross‐linked, solvent‐swollen polymer network complexed with additives. These particles have various applications, such as drug delivery, catalysis, and analytics. To optimize the performance of microgel capsules, it is crucial to control their size, shape, and content of encapsulated additives with high precision. There are two classes of microgel‐capsule structures. One class comprises bulk microcapsules that consist of a polymer network spanning the entire particle and entrapping the additive within its meshes. The other class comprises core–shell structures; in this case, the microgel polymer network just forms the shell of the particles, whereas their interior is hollow and hosts the encapsulated payload. Both types of structures can be produced with exquisite control by droplet‐based microfluidic templating followed by subsequent droplet gelation. This article highlights some early and recent achievements in the use of this technique to tailor soft microgel capsules; it also discusses applications of these particles. A special focus is on the encapsulation of living cells, which are very sensitive and complex but also very useful additives for immobilization within microgel particles.     

l‐Arginine‐Triggered Self‐Assembly of CeO2 Nanosheaths on Palladium Nanoparticles in Water

Pd@CeO₂ core–shell nanostructures with a tunable Pd core size, shape, and nanostructure as well as a tunable CeO₂ sheath thickness were obtained by a biomolecule‐assisted method. The synthetic process is simple and green, as it involves only the heating of a mixture of Ce(NO₃)₃, l ‐arginine, and preformed Pd seeds in water without additives. Importantly, the synthesis is free of thiol groups and halide ions, thus providing a possible solution to the problem of secondary pollution by Pd nanoparticles in the sheath‐coating process. The Pd/CeO₂ nanostructures can be composited well with γ‐Al₂O₃ to create a heterogeneous catalyst. In subsequent tests of catalytic NO reduction by CO, Pd@CeO₂/Al₂O₃ samples based on Pd cubes (6, 10, and 18 nm), Pd octahedra (6 nm), and Pd cuboctahedra (9 nm) as well as a simply loaded Pd cube (6 nm)–CeO₂/Al₂O₃ sample were used as catalysts to investigate the effects of the Pd core size and shape and the hybrid nanostructure on the catalytic performance.     

Functional Polymer‐Opals from Core–Shell Colloids

Colloidal photonic crystals were prepared from monodisperse core–shell particles. The shell is hereby formed from a functional monomer, such as glycidylmethacrylate or different reactive ester monomers, which can perform chemical reactions and the core from a standard monomer, which yields highly monodisperse colloids. It was possible to crystallize the core–shell particles into artificial opals with excellent optical properties. Reactions on the functional surface of the colloids were carried out, which lead to a dramatic rise in the mechanical stability or to a functionalization of His‐tagged silicatein, which acts as nanoreactor to synthesize and immobilize gold nanoparticles from auric acid onto the core–shell colloids.

     

Synthesis and characterization of fluorine‐containing polyacrylate latex with core–shell structure by UV‐initiated seeded emulsion polymerization

A core–shell fluorine‐containing polyacrylate emulsion was successfully prepared by UV‐initiated seeded emulsion polymerization in two stages in the presence of two photoinitiators. The water‐soluble photoinitiator for the core polymerization and the oil‐soluble photoinitiator was used for the shell polymerization. Both of the two stage polymerizations could be completed within 15 min and displayed a conversion above 94%. The emulsion and the films were characterized by Fourier transformed infrared spectrometry, transmission electron microscopy, dynamic light scattering, X‐ray photoelectron spectroscopy (XPS), contact angle (CA), and thermogravimetry analysis, respectively. The analysis results indicated that the fluorine‐containing latex particles had very small particle size (40 nm) with a core–shell structure and a narrow particle size distribution. XPS analysis revealed that a gradient concentration of fluorine excited in fluorine‐containing emulsion film from the film–air interface to the film–glass interface. In addition, the film formed from the fluorine‐containing emulsion exhibited not only higher thermal stability but also better hydrophobicity than that of the fluorine‐free emulsion. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis of polymer particles possessing radical initiating sites on the surface by emulsion copolymerization and construction of core–shell structures by a photoinduced atom transfer radical polymerization approach

The crosslinked polystyrene particles possessing photofunctional N,N‐diethyldithiocarbamate groups on their surface were prepared by free‐radical emulsion copolymerization of a mixture of styrene, divinylbenzene and 4‐vinylbenzyl N,N‐diethyldithiocarbamate with redox system as an initiator under UV irradiation. In this copolymerization, the inimer 4‐vinylbenzyl N,N‐diethyldithiocarbamate acted the formation of hyperbranched structures by living radical photopolymerization. The particle sizes (number‐average particle diameter = 214–523 nm) were controlled by varying the feed amount of surfactant and size distributions were relatively narrow. Subsequently, core–shell particles were synthesized by photoinduced atom transfer radical polymerization approach of methyl methacrylate initiated by photofunctional polystyrene particles as a macroinitiator. Such core–shell particles were stabilized sterically by grafted chains in organic solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1771–1777, 2007     

Selected‐Control Fabrication of Multifunctional Fluorescent–Magnetic Core–Shell and Yolk–Shell Hybrid Nanostructures

The selected‐control preparation of uniform core–shell and yolk–shell architectures, which combine the multiple functions of a superparamagnetic iron oxide (SPIO) core and europium‐doped yttrium oxide (Y₂O₃:Eu) shell in a single material with tunable fluorescence and magnetic properties, has been successfully achieved by controlling the heat‐treatment conditions. Furthermore, the shell thickness and interior cavity of SPIO@Y₂O₃:Eu core–shell and yolk–shell nanostructures can be precisely tuned. Importantly, as‐prepared SPIO@Y₂O₃:Eu yolk–shell nanocapsules (NCs) modified with amino groups as cancer‐cell fluorescence imaging agents are also demonstrated. To the best of our knowledge, this is the first report on the selected‐control fabrication of uniform SPIO@Y₂O₃:Eu core–shell nanoparticles and yolk–shell NCs. The combined magnetic manipulation and optical monitoring of magnetic–fluorescent SPIO@Y₂O₃:Eu yolk–shell NCs will open up many exciting opportunities in dual imaging for targeted delivery and thermal therapy.     

Bioreduction of Precious Metals by Microorganism: Efficient Gold@N‐Doped Carbon Electrocatalysts for the Hydrogen Evolution Reaction

The uptake of precious metals from electronic waste is of environmental significance and potential commercial value. A facile bioreductive synthesis is described for Au nanoparticles (ca. 20 nm) supported on N‐doped carbon (Au@NC), which was derived from Au/Pycnoporus sanguineus cells. The interface and charge transport between Au and N‐doped carbon were confirmed by HRTEM and XPS. Au@NC was employed as an electrocatalyst for the hydrogen evolution reaction (HER), exhibiting a small onset potential of ?54.1 mV (vs. RHE), a Tafel slope of 76.8 mV dec^?1, as well as robust stability in acidic medium. Au@NC is a multifunctional electrocatalyst, which demonstrates high catalytic activity in the oxygen reduction reaction (ORR), as evidenced by an onset potential of +0.97 V, excellent tolerance toward methanol, and long‐term stability. This work exemplifies dual recovery of precious Au and fabrication of multifunctional electrocatalysts in an environmentally benign and application‐oriented manner.     

One‐Pot Fabrication of Rattle‐Like Capsules with Multicores by Pickering‐Based Polymerization with Nanoparticle Nucleation

Rattle‐like polymer capsules with multicores in one shell are facilely fabricated by oil‐in‐water Pickering emulsion polymerization for the first time. The oil phase contains hydrophobic silica nanoparticles dispersed in polymerizable monomer, styrene, and unpolymerizable solvent, hexadecane. The multicore rattle‐like capsules are facilely produced after the polymerization of monomers in the oil droplets. The key point of this one‐pot method lies in the nucleation of hydrophobic silica and the phase separation between the resulting polystyrene and hexadecane. The influences of the contents of silica, hexadecane, cross‐linker, and stabilizer on the structure and morphology of rattle‐like capsules are systematically investigated. Moreover, functionalization of the rattle‐like capsules can be developed easily by varying hydrophobic nucleation nanoparticles in the oil phase. This work opens up a new route to fabricate multilevel capsules or spheres.

     

Shape‐Controlled Surface‐Coating to Pd@Mesoporous Silica Core–Shell Nanocatalysts with High Catalytic Activity and Stability

Cubic Pd nanocrystals with shape‐controlled mesoporous silica shells have been theoretically designed and successfully synthesized for investigating the effect of a porous nanoshell on catalytic performance of the core. Cubic Pd@cubic mesoporous silica keeps activity of all facets and shows highest catalytic activity and enhanced reusability in the hydrogenation of nitrobenzene.