Molecular Clogging Organogels with Excellent Solvent Maintenance, Adjustable Modulus, and Advanced Mechanics for Impact Protection.

Inspired by mechanically interlocking supramolecular materials, exploiting the size difference between the bulky solvent and the cross-linked network mesh, a molecular clogging (MC) effect is developed to effectively inhibit solvent migration in organogels. A bulky solvent (branched citrate ester, BCE) with a molecular size above 1.4 nm is designed and synthesized. Series of MC-Gels are prepared by in situ polymerization of crosslinked polyurea with BCE as the gel solvent. The MC-Gels are colorless, transparent, and highly homogeneous, show significantly improved stability than gels prepared with small molecule solvents. As solvent migration is strongly inhibited by molecular clogging, the solvent content of the gels can be precisely controlled, resulting in a series of MC-Gels with continuously adjustable mechanics. In particular, the modulus of MC-Gel can be regulated from 1.3 GPa to 30 kPa, with a variation of 43 000 times. The molecular clogging effect also provides MC-Gels with unique high damping (maximum damping factor of 1.9), impact resistant mechanics (high impact toughness up to 40.68 MJ m-3 ). By applying shatter protection to items including eggs and ceramic armor plates, the potential of MC-Gels as high strength, high damping soft materials for a wide range of applications is well demonstrated.

Facile synthesis of hyperbranched magnetic nanomaterials for selective adsorption of proteins.

The separation and purification of proteins is an essential precondition for proteomics research because of the intricate matrix environment. Hence, a facile method has been developed to synthesize hyperbranched polyethyleneimine modified magnetic nanomaterials (Fe3O4-NH2-BPEI) with dendritic structure, unique electrostatic effect, and abundant functional groups for the selective adsorption of proteins which greatly avoids the drawbacks of time consumption and leakage of metal ions in traditional pre-treatment. The preparation conditions, physical and chemical properties, and adsorption performance of Fe3O4-NH2-BPEI have been fully studied. The obtained materials have stable crystal shape, adequate superparamagnetism, fast adsorption kinetics, high adsorption amount, and admirable reusability. In addition, the as-prepared Fe3O4-NH2-BPEI exhibits good selective adsorption ability for electronegative proteins in the neutral solution, exhibiting a potential value for special adsorption for proteins with different pI.

3D ordered mesoporous TiO2@CMK-3 nanostructure for sodium-ion batteries with long-term and high-rate performance.

Sodium ion battery is abundant in resources and costs low, making it very competitive in the large-scale energy storage devices. The anatase TiO2 electrode material with insertion/extraction mechanism shows stable cycling performance, which is more in line with the technical requirements of large-scale energy storage batteries. To improve the electrical conductivity and stability of the TiO2 electrode materials, we have synthesized anatase TiO2 and CMK-3 composite. TiO2 nanoparticles were deposited on the surface of CMK-3 by hydrothermal reaction, and the anode material of the SIBs with 3D network structure was prepared. With the CMK-3, the structure stability, conductivity and reaction kinetics of TiO2@CMK-3 composite is improved. The electrochemical behavior is dominated by pseudocapacitance, which gives the material excellent high-rate performance. It delivers a reversible specific capacity of 186.3 mA h g-1 after 100 cycles at the current density of 50 mA g-1, 124.5 mA h g-1 after 500 long-term cycles, meanwhile it shows an outstanding rate performance, a reversible specific capacity of 105.9 mA h g-1 at 1600 mA g-1, 177.3 mA h g-1 when the current density drops to 50 mA g-1.

Phosphine-Catalyzed Activation of Vinylcyclopropanes: Rearrangement of Vinylcyclopropylketones to Cycloheptenones.

We report a phosphine-catalyzed activation of electron-deficient vinylcyclopropanes (VCPs) to generate an ambident C5 synthon that is poised to undergo consecutive reactions. The utility of the activation is demonstrated in a phosphine-catalyzed rearrangement of vinylcyclopropylketones to cycloheptenones in good yields with a broad substrate scope. Mechanistic investigations support a stepwise process comprising homoconjugate addition, water-assisted proton transfer, and 7-endo-trig SN 2' ring closure.

Highly selective and efficient imprinted polymers based on carboxyl-functionalized magnetic nanoparticles for the extraction of gallic acid from pomegranate rind.

With the combined surface imprinting technique and immobilized template strategy, molecularly imprinted magnetic nanoparticles were successfully prepared and coupled with high-performance liquid chromatography to selectively separate and determine gallic acid from the pomegranate rind. On the surface of carboxyl-functionalized magnetic nanospheres, thin imprinting shells were formed using dopamine as monomer and crosslinker. The characteristics, polymerization conditions, and adsorption performances of the resultant nanomaterials were investigated in detail. In addition of good crystallinity, satisfactory magnetism, and uniform morphology of the obtained polymers, they had rapid binding kinetics, high adsorption capacity, and favorable reusability. In the mixed solution of four hydroxybenzoic acids, the prepared nanomaterials have an excellent selectivity to gallic acid with an imprinting factor of as high as 17.5. Therefore, the polymers have great potentials in specific extraction and enrichment of gallic acid from the complex natural resources.

Organocatalytic Cloke-Wilson Rearrangement: DABCO-Catalyzed Ring Expansion of Cyclopropyl Ketones to 2,3-Dihydrofurans.

An organocatalytic Cloke-Wilson rearrangement of cyclopropyl ketones to 2,3-dihydrofurans is exploited utilizing the homoconjugate addition process. With 1,4-diazabicyclo[2.2.2]octane as the catalyst, the rearrangement in DMSO at 120 °C proceeded in generally high yields, exclusive regioselectivity, and a broad substrate scope. An examination of the mechanism including stereochemical analysis and intermediate isolation supports an SN1-type ring opening of the mechanism.

Study on mechanical and ablative properties of EPDM/OMMT thermal insulating nanocomposites.

In order to enhance the elongation at break, the ablation resistant properties as well as the tensile strength of the thermal insulating materials, organo-montmorillonite (OMMT) was introduced into the short aramid fibers reinforced Ethylene-Propylene-Diene Monomer (EPDM) based nanocomposites. The effects of OMMT content on the mechanical and ablative properties of the nanocomposites were investigated systematically. X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirm that EPDM-matrix has been intercalated into OMMT interlayers after a mixing process on a two-roll mill. The brittle fracture of nanocomposites also indicates that OMMT can lubricate aramid fiber to weaken the interfacial adhesive strength between the fibers and the matrix. As a result, the tensile strength and elongation at break are both improved sharply with OMMT content increasing from 1 phr to 7 phr. However, thanks to the inevitable agglomeration of OMMT with high loading inside the nanocomposites, the tensile strength and elongation at break reduce gently once OMMT is over 7 phr. Furthermore, the ablation resistant properties are improved greatly by increasing OMMT from 1 phr to 11 phr. Therefore, the optimal content of OMMT is 7-11 phr for the thermal insulating nanocomposites with big elongation and excellent ablation resistant properties.