Thermally Conductive and Electrically Insulating Epoxy Composites Filled with Network-like Alumina In Situ Coated Graphene.

With the rapid development of the electronics industry, there is a growing demand for packaging materials that possess both high thermal conductivity (TC) and low electrical conductivity (EC). However, traditional insulating fillers such as boron nitride, aluminum nitride, and alumina (Al2O3) have relatively low intrinsic TC. When graphene, which exhibits both superhigh TC and EC, is used as a filler to fill epoxy resin, the TC of blends can be much higher than that of blends containing more traditional fillers. However, the high EC of graphene limits its application in cases where electrical insulation is required. To address this challenge, a method for coating graphene sheets with an in situ grown Al2O3 layer has been proposed for the fabrication of epoxy-based composites with both high TC and low EC. In the presence of a cationic surfactant, a dense Al2O3 layer with a network structure can be formed on the surface of graphene sheets. When the total content of Al2O3 and graphene mixed filler reached 30 wt%, the TC of the epoxy composite reached 0.97 W m-1 K-1, while the EC remained above 1011 Ω·cm. Finite element simulations accurately predicted TC and EC values in accordance with experimental results. This material, with its combination of high TC and good insulation properties, exhibits excellent potential for microelectronic packaging applications.

Visible-light-induced C(sp3)-H thiocyanation of pyrazolin-5-ones: a practical synthesis of 4-thiocyanated 5-hydroxy-1H-pyrazoles.

A direct, aerobic and visible light photocatalytic approach to synthesize 4-thiocyanated 5-hydroxy-1H-pyrazoles via cross-coupling of pyrazolin-5-ones with ammonium thiocyanate is described. Under redox-neutral and metal-free conditions, a series of 4-thiocyanated 5-hydroxy-1H-pyrazoles could be easily and efficiently obtained in good to high yields by using low-toxicity and inexpensive ammonium thiocyanate as the thiocyanate source.

Vertical Alignment of Anisotropic Fillers Assisted by Expansion Flow in Polymer Composites.

Orientation control of anisotropic one-dimensional (1D) and two-dimensional (2D) materials in solutions is of great importance in many fields ranging from structural materials design, the thermal management, to energy storage. Achieving fine control of vertical alignment of anisotropic fillers (such as graphene, boron nitride (BN), and carbon fiber) remains challenging. This work presents a universal and scalable method for constructing vertically aligned structures of anisotropic fillers in composites assisted by the expansion flow (using 2D BN platelets as a proof-of-concept). BN platelets in the silicone gel strip are oriented in a curved shape that includes vertical alignment in the central area and horizontal alignment close to strip surfaces. Due to the vertical orientation of BN in the central area of strips, a through-plane thermal conductivity as high as 5.65 W m-1 K-1 was obtained, which can be further improved to 6.54 W m-1 K-1 by combining BN and pitch-based carbon fibers. The expansion-flow-assisted alignment can be extended to the manufacture of a variety of polymer composites filled with 1D and 2D materials, which can find wide applications in batteries, electronics, and energy storage devices.

Highly Anisotropic Thermal Conductivity of Three-Dimensional Printed Boron Nitride-Filled Thermoplastic Polyurethane Composites: Effects of Size, Orientation, Viscosity, and Voids.

Extrusion-based three-dimensional (3D) printing techniques usually exhibit anisotropic thermal, mechanical, and electric properties due to the shearing-induced alignment during extrusion. However, the transformation from the extrusion to stacking process is always neglected and its influence on the final properties remains ambiguous. In this work, we adopt two different sized boron nitride (BN) sheets, namely, small-sized BN (S-BN) and large-sized BN (L-BN), to explore their impact on the orientation degree, morphology, and final anisotropic thermal conductivity (TC) of thermoplastic polyurethane (TPU) composites by fused deposition modeling. The transformation from one-dimensional axial alignment in the extruded filament to two-dimensional alignment (horizontal and vertical alignment) in the stacking filament of BN sheets is observed, and its impact on anisotropic TC in three directions is clarified. It is found that L-BN/TPU composites show a high TC of 6.45 W m-1 K-1 at 60 wt % BN content along the printing direction, while at a lower content (<40 wt %), S-BN/TPU composites exhibit a higher TC than L-BN/TPU composites. Effects of orientation, viscosity, and voids are comprehensively considered to elucidate such differences. Finally, heat dissipation tests demonstrate the great potential of 3D printed BN/TPU composites to be used in thermal management applications.

Highly Thermally Conductive 3D Printed Graphene Filled Polymer Composites for Scalable Thermal Management Applications.

Efficient thermal transportation in a preferred direction is highly favorable for thermal management issues. The combination of 3D printing and two-dimensional (2D) materials such as graphene, BN, and so on enables infinite possibilities for hierarchically aligned structure programming. In this work, we report the formation of the asymmetrically aligned structure of graphene filled thermoplastic polyurethane (TPU) composites during 3D printing process. The as-printed vertically aligned structure demonstrates a through-plane thermal conductivity (TC) up to 12 W m-1 K-1 at 45 wt % graphene content, which is ∼8 times of that of a horizontally printed structure and surpasses many of the traditional particle reinforced polymer composites. The superior TC is mainly attributed to the anisotropic structure design that benefited from the preferable degree of orientation of graphene and the multiscale dense structure realized by finely controlling the printing parameters. Finite element method (FEM) confirms the essential impact of anisotropic TC design for highly thermal conductive composites. This study provides an effective way to develop 3D printed graphene-based polymer composites for scalable thermal-related applications such as battery thermal management, electric packaging, and so on.

Reduced graphene oxide-GelMA-PCL hybrid nanofibers for peripheral nerve regeneration.

Graphene oxide is currently used in peripheral nerve engineering but has certain limitations, such as cytotoxicity and lack of electrical conductivity, both of which are crucial in regulating nerve-associated cell behaviors. In this work, we engineered reduced graphene oxide-GelMA-PCL nanofiber nerve guidance conduits via electrospinning. rGO incorporated into the GelMA/PCL matrix significantly enhanced the electrical conductivity and biocompatibility of the hybrid materials. In addition, hybrid nanofibers with low concentrations of rGO (0.25 and 0.5 wt%) could significantly improve the proliferation of Schwann cells (RSC96). More importantly, rGO/GelMA/PCL hybrid nanofibers could activate the epithelial-mesenchymal transition (EMT)-related gene expression of Schwann cells (RSC96). From the in vivo study, it was observed that rGO/GelMA/PCL nerve guidance conduits could promote both sensory/motor nerve regeneration and functional recovery in rats. Our composite strategy of combining rGO within a biocompatible nanofiber scaffold is simple but effective in improving tissue engineering outcomes. The rGO/GelMA/PCL hybrid nanofibers have great potential in peripheral nerve tissue engineering. They will also provide an experimental basis for the development of further electrical stimulation in peripheral nerve regeneration.

Conductive conduit small gap tubulization for peripheral nerve repair.

Despite advances in surgical techniques, functional recovery following epineurial neurorrhaphy of transected peripheral nerves often remains quite unsatisfactory. Small gap tubulisation is a promising approach that has shown potential to traditional epineurial neurorrhaphy in the treatment of peripheral nerve injury. Thus, the goal of this study is to evaluate sciatic nerve regeneration after nerve transection, followed by small gap tubulization using a reduced graphene oxide-based conductive conduit. In vitro, the electrically conductive conduit could promote Schwann cell proliferation through PI3K/Akt signaling pathway activation. In vivo, the results of electrophysiological and walking track analysis suggest that the electrically conductive conduit could promote sensory and motor nerve regeneration and functional recovery, which is based on the mechanisms of selective regeneration and multiple-bud regeneration. These promising results illustrate electrically conductive conduit small gap tubulization as an alternative approach for transected peripheral nerve repair.

Preparation of sub-microspherical Fe3O4@PDA-Pd NPs catalyst and application in catalytic hydroreduction reaction of halogenated aromatic nitro compounds to prepare halogenated aromatic amines.

BACKGROUND: The side reactions of dehalogenation or C-N coupling tend to occur when halogenated aromatic amines are prepared by catalytic hydrogenation reduction of halogenated aromatic nitro compounds. In this paper, we prepared the sub-microspherical Fe3O4@PDA-Pd NPs catalyst apply it efficiently in the hydrogenation reduction of halogenated aromatic nitro compounds to prepare the halogenated aromatic amines under atmospheric pressure. The catalyst shows a high selectivity of greater than 96% and can effectively inhibit the occurrence of the side reactions of dehalogenation and C-N coupling. RESULTS: The optimum condition of the hydroreduction reaction is when tetrahydrofuran is used as solvent and the reaction happens at 50 °C for 5 h. The selectivity of the chlorinated aromatic amine and the fluorinated aromatic amine products exceed 99% and the yield exceeds 90%. Only a small amount of dehalogenated products and C-N coupling by-products were produced in the brominated aromatic compound and the iodinated aromatic compound. CONCLUSION: We developed a promising method for preparing the superparamagnetic and strongly magnetic Fe3O4@PDA core-shell sub-microsphere-supported nano-palladium catalyst for catalyzing the hydrogenation reduction of halogenated aromatic nitro compounds. The halogenated aromatic amines were efficiently and highly selectively prepared under atmospheric pressure, with the side reactions of dehalogenation and C-N coupling effectively inhabited simultaneously.

Preparation of Large-Size, Superparamagnetic, and Highly Magnetic Fe3O4@PDA Core⁻Shell Submicrosphere-Supported Nano-Palladium Catalyst and Its Application to Aldehyde Preparation through Oxidative Dehydrogenation of Benzyl Alcohols.

Large-size, superparamagnetic, and highly magnetic Fe3O4@PDA core-shell submicrosphere-supported nano-palladium catalysts were prepared in this study. Dopamine was encapsulated on the surface of Fe3O4 particles via self-polymerization and then protonated to positively charge the microspheres. PdCl42- was dispersed on the surface of the microspheres by positive and negative charge attraction and then reduced to nano-palladium. With air as oxidant, the catalyst can successfully catalyze the dehydrogenation of benzyl alcohols to produce the corresponding aldehydes at 120 °C.

Ruthenium-catalyzed decarboxylative C-S cross-coupling of carbonothioate: synthesis of allyl(aryl)sulfide.

A novel ruthenium-catalyzed decarboxylative cross-coupling of carbonothioate is disclosed. This method provides straightforward access to the corresponding allyl(aryl)sulfide derivatives in generally good to excellent yields under mild conditions and features a broad substrate scope, wide group tolerance and in particular, no need to use halocarbon precursors.

(E)-N'-(5-Bromo-2-hy-droxy-benzyl-idene)-3-methyl-benzohydrazide.

In the title mol-ecule, C(15)H(13)BrN(2)O(2), an intra-molecular O-H⋯N hydrogen bond influences the mol-ecular conformation; the two benzene rings form a dihedral angle of 13.6 (3)°. In the crystal, inter-molecular N-H⋯O hydrogen bonds link the mol-ecules into chains along the a axis and weak inter-molecular C-H⋯O hydrogen bonds further link these chains into layers parallel to the ac plane.

3-Methyl-4-oxo-2-phenyl-4H-chromene-8-carboxylic acid.

In the title compound, C(17)H(12)O(4), the chromene unit is approximately planar, the maximum deviation from the mean plane being 0.0166 Å. The attached phenyl ring makes a dihedral angle of 53.2 (1)° with the fused ring system. The packing of the mol-ecules in the crystal structure is governed by C-H⋯O and O-H⋯O hydrogen-bonding inter-actions.