BF3-catalyzed oxidative tandem annulation-aromatization of naphthols with terminal aryl alkenes

A metal-free oxidative arene/alkene annulation-aromatization has been realized, which enables efficient synthesis of 2-arylnaphtho[2,1-b]furans from readily available terminal aryl alkenes and 2-naphthols. Mechanistic study suggests that this reaction proceeds via free-radical initiated tandem cyclization, dehydrogenative rearomatization and aromatization.     

Highly Ordered Mesoporous Cobalt-Copper Composite Oxides for Preferential CO Oxidation

Highly ordered mesoporous cobalt-copper composite oxides were prepared by the nanocasting method with various Co and Cu ratios. The catalysts obtained were characterized by X-ray diffraction, N₂ adsorption–desorption, H₂-temperature programmed reduction, CO-temperature programmed desorption and X-ray photoelectron spectroscopy. All of the catalysts had uniform mesopores and high surface areas. The distinct catalytic properties of these well-characterized mesoporous materials were demonstrated for preferential CO oxidation. It is found that the mesoporous cobalt-copper composite oxides, exhibited the higher catalytic activity for CO conversion and selectivity compared with the mesoporous Co₃O₄ and mesoporous CuO. Among these catalysts the mesoporous cobalt-copper catalyst with Co:Cu molar ratio of 70:30, shows the best catalytic activity and the broadest operating temperature “window” for the high CO conversion in the range of 125–200^oC. The higher catalytic activity was attributed to the higher CO adsorption and oxygen vacancies.     

In-tip nanoreactors for cancer cells proteome profiling

Mass spectrometry (MS)-based proteome profiling is essential for molecular diagnostics in modern biomedical study. To date, sample preparation including protein extraction and proteolysis is still very challenging and lack of efficiency. Recently tips-based sample preparation protocols exhibit strong potentials to achieve the goal of “a proteome in an hour”. However, in-tip proteolysis is still rarely reported and far from ideal for dealing with complex bio-samples. In this work, nanoreactors encapsulated micropipette tips were demonstrated as high performance devices for fast (∼minutes) and multiplexing proteolysis to assist the profiling of cancer cells proteome. Nanoporous silica materials with controlled pore size and surface chemistry were prepared as nanoreactors and encapsulated in micropipette tips for efficient in situ proteolysis. The as-constructed device showed desirable sensitivity (LOD of 0.204 ± 0.008 ng/μL and LOQ of 0.937 ± 0.055 ng/μL), selectivity, stability (two months under −20 °C), reusability (at least 10 times), and little memory effect in MS based bottom-up proteomic analysis. It was used for comprehensive protein mapping from cancer cell lines. The number of identified proteins was increased by 18%, 22%, 52%, and 52% dealing with HepG2, F56, MCF7, and HCCLM3 cancer cells, compared to traditional in-solution proteolysis based bottom-up proteomic strategy. With the enhanced performance, our work built a novel, efficient and miniaturized platform for facile proteomic sample preparation, which is promising for advanced biomarkers discovery in biomedical study.     

Ultra-high surface area and mesoporous N-doped carbon derived from sheep bones with high electrocatalytic performance toward the oxygen reduction reaction

A nitrogen (N)-doped mesoporous carbon material exhibiting ultra-high surface area was successfully synthesized from sheep bones via a facile and low-cost method. The obtained carbon material had an ultra-high specific surface area of 1961 m² g^?1 and provided rich active sites for the oxygen reduction reaction (ORR), which in turn resulted in high electrocatalytic activity. It was found that the pore size distribution for the newly prepared carbonaceous material fell in the range of 1–4 nm. Benefiting from its high surface area and the presence of pyridine-N and quaternary-N species, the as-prepared carbon material exhibited excellent ORR activity in an oxygen-saturated 0.1 M KOH solution, compared to commercial Pt/C (10 wt%). Due to its high ORR catalytic activity, stability and low-cost, using sheep bone as C and N precursors to produce N-doped carbon provides an encouraging step toward the goal of replacing commercial Pt/C as fuel cell cathode electrocatalyst.     

A universal blown film apparatus for <Emphasis Type="Italic">in situ</Emphasis> X-ray measurements

A setup of blown film machine combined with in situ synchrotron radiation X-ray diffraction measurements and infrared temperature testing is reported to study the structure evolution of polymers during film blowing. Two homemade auto-lifters are constructed and placed under the blown machine at each end of the beamline platform which move up and down with a speed of 0.05 mm/s bearing the 200 kg weight machine. Therefore, structure development and temperature changes as a function of position on the film bubble can be obtained. The blown film machine is customized to be conveniently installed with precise servo motors and can adjust the processing parameters in a wide range. Meanwhile, the air ring has been redesigned in order to track the structure information of the film bubble immediately after the melt being extruded out from the die exit. Polyethylene (PE) is selected as a model system to verify the feasibility of the apparatus and the in situ experimental techniques. Combining structure information provided by the WAXD and SAXS and the actual temperature obtained from the infrared probe, a full roadmap of structure development during film blowing is constructed and it is helpful to explore the molecular mechanism of structure evolution behind the film blowing processing, which is expected to lead to a better understanding of the physics in polymer processing.     

Ionic liquid functionalized graphene oxide for enhancement of styrene‐butadiene rubber nanocomposites

Ionic liquid 1‐allyl‐3‐methyl‐imidazolium chloride (AMICl) is used to fine‐tune the surface properties of graphene oxide (GO) sheets for fabricating ionic liquid functionalized GO (GO‐IL)/styrene‐butadiene rubber (SBR) nanocomposites. The morphology and structure of GO‐IL are characterized using atomic force microscope, X‐ray diffraction, differential scanning calorimetry, X‐ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, UV‐vis spectra and Raman spectra. The interaction between GO and AMICl molecules as well as the effects of GO‐IL on the mechanical properties, thermal conductivity and solvent resistance of SBR are thoroughly studied. It is found that AMICl molecules can interact with GO via the combination of hydrogen bond and cation–π interaction. GO‐IL can be well‐dispersed in the SBR matrix, as confirmed by X‐ray diffraction and scanning electron microscope. Therefore, the SBR nanocomposites incorporating GO‐IL exhibit greatly enhanced performance. The tensile strength, tear strength, thermal conductivity and solvent resistance of GO‐IL/SBR nanocomposite with 5 parts per hundred rubber GO‐IL are increased by 505, 362, 34 and 31%, respectively, compared with neat SBR. This method provides a new insight into the fabrication of multifunctional GO‐based rubber composites. Copyright © 2016 John Wiley & Sons, Ltd.     

Block copolymer micelles with enzyme molecules at the interfaces

This research provides an efficient method for the fabrication of hybrid micelles with enzyme molecules at the interfaces. Amphiphilic block copolymer is synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization, and thiol‐modified porcine pancreatic lipase (PPL‐SH) is obtained by treatment of native PPL with Traut's reagent. PPL‐SH is conjugated to the block copolymer chains by thiol‐disulfide exchange reaction. In phosphate buffered saline, the bioconjugate self‐assembles into micelles with enzyme molecules at the interfaces between hydrophobic cores and hydrophilic coronae. The bioactivity of the enzyme molecules on the micelles are compared with the native enzyme. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2047–2052     

Nanofibers prepared by electrospinning from solutions of biobased polyamide 4

A successful preparation of polyamide 4 nanofibers via electrostatic spinning with diameters close to 100 nm is described. Polyamide 4 was prepared by the anionic ring‐opening polymerization of 2‐pyrrolidone and characterized. The effect of the system parameters (i.e., molar mass of the polymer, the solvent system) and the process parameters (i.e., the electrode‐to‐collector distance) during the electrostatic spinning have been studied. The morphology of the polyamide 4 fiber layers is given except molar mass of the polymer and the concentration of its solution primarily by the conformation of polyamide chains due to polyelectrolyte effect which was confirmed by viscosity measurements. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2203–2210