Solvent‐free ring‐opening polymerization of lactones with hydrogen‐bonding bisurea catalyst

Development of effective organocatalysts for the living ring‐opening polymerization (ROP) of lactones is highly desired for the preparation of biocompatible and biodegradable polyesters with controlled microstructures and physical properties. Herein, a new class of hydrogen‐bond donating bisurea catalysts is reported for the ROP of lactones under solvent‐free conditions. ROP of lactones mediated by the bisurea/7‐methyl‐1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (MTBD) catalyst exhibits a living/controlled manner, affording the polymers and copolymers with the well‐defined structure, predictable molecular weight, narrow molecular weight distribution, and high selectivity for monomer at low catalyst loadings at ambient temperature. The possible mechanism of bisurea/MTBD‐catalyzed ROP of lactones is proposed, in which the bisurea activates the carbonyl group of lactones while MTBD facilitates the nucleophilic attack of the initiating/propagating alcohol by hydrogen bonding. Moreover, the poly(ε‐caprolactone‐co‐δ‐valerolactone) [P(CL‐co‐VL)] random copolymers with various compositions were synthesized using the bisurea/MTBD catalyst. The measurements of thermal properties and crystalline structure demonstrate that the CL and VL units are cocrystallized in the crystalline phase of P(CL‐co‐VL) copolymers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 90–100     

Effects of vanadium oxide coating on the performance of LiFePO4/C cathode for lithium-ion batteries

Journal of Solid State Electrochemistry - LiFePO4 cathode material is considered as prospective materials for lithium-ion batteries and attracted great interest because of excellent cyclic...     

Mössbauer Study of the Effect of Cation Substitutions on the Magnetic Phase Transitions in BiFe1 – xCrxO3 and (1 – x)BiFeO3–xPbFe0.5Sb0.5O3 Solid Solutions

Crystallography Reports - The concentration dependences of the magnetic phase transition temperature TN, determined based on the changes in Mössbauer spectra, were investigated for a BiFeO3...     

Simultaneous chemical fingerprint and quantitative analysis of Rhizoma Smilacis Glabrae by accelerated solvent extraction and high‐performance liquid chromatography with tandem mass spectrometry

Rhizoma Smilacis Glabrae (RSG) is a well‐known herbal medicine with the homology of medicine and food. In this study, simultaneous chemical fingerprint and quantitative analysis of the bioactive flavonoid components of RSG were developed using accelerated solvent extraction and high‐performance liquid chromatography coupled with ion trap tandem mass spectrometry. The operational parameters of accelerated solvent extraction including extraction solvent, extraction temperature, static extraction time, solid‐to‐liquid ratio, and extraction cycles were optimized. Hierarchical cluster analysis, similarity analysis, and principal component analysis were performed to evaluate the similarity and variation of the samples collected from several provinces in China. Subsequently, high‐performance liquid chromatography fingerprints were established for the discrimination of 16 batches of RSG samples, and the major six flavonoids, namely, toxifolin, neoastilbin, astilbin, neoisoastilbin, isoastilbin, and engeletin were then quantitatively determined. The calibration curves for all the six analytes showed good linearity (r² > 0.999), and the limits of detection and quantification were less than 0.10 and 0.27 μg·mL^?1, respectively. Therefore, the proposed extraction and determination methods were proved to be robust and reliable for the quality control of RSG.     

Vacuum Ultraviolet Free-Electron Laser Photoionization Mass Spectrometry of Alpha-pinene Ozonolysis

\begin{document}$\alpha$\end{document}-pinene is the most abundant monoterpene that represents an important family of volatile organic compounds. Molecular identification of key transient compounds during the \begin{document}$\alpha$\end{document}-pinene ozonolysis has been proven to be a challenging experimental target because of a large number of intermediates and products involved. Here we exploit the recently developed hybrid instruments that integrate aerosol mass spectrometry with a vacuum ultraviolet free-electron laser to study the \begin{document}$\alpha$\end{document}-pinene ozonolysis. The experiments of \begin{document}$\alpha$\end{document}-pinene ozonolysis are performed in an indoor smog chamber, with reactor having a volume of 2 m\begin{document}$^3$\end{document} which is made of fluorinated ethylene propylene film. Distinct mass spectral peaks provide direct experimental signatures of previously unseen compounds produced from the reaction of \begin{document}$\alpha$\end{document}-pinene with O\begin{document}$_3$\end{document}. With the aid of quantum chemical calculations, plausible mechanisms for the formation of these new compounds are proposed. These findings provide crucial information on fundamental understanding of the initial steps of \begin{document}$\alpha$\end{document}-pinene oxidation and the subsequent processes of new particle formation.     

Coumarin Sulfonamides and Amides Derivatives: Design,Synthesis, and Antitumor Activity In Vitro

Coumarins possesses immeasurable antitumor potential with minimum side effects depending on the substitutions on the basic nucleus, which exhibits great prospects for antitumor drug development. In an attempt to develop novel antitumor candidates, a series of coumarin sulfonamides and amides derivatives were designed and synthetized. The majority of these derivatives showed good cytotoxic activity against MDA-MB-231 and KB cell lines, among which compound 9c was the most potent against MDA-MB-231 cells, with IC₅₀ value of 9.33 μM, comparable to 5-fluorouracil. Further investigation revealed that compound 9c had versatile properties against tumors, including inhibition of cell migration and invasion as well as inducing apoptosis. Reactive oxygen species (ROS) assay and western blotting analysis suggested that compound 9c promoted cancer cell apoptosis by increasing ROS levels and upregulating the expression of caspase-3 in MDA-MB-231 cells. These results indicated that compound 9c could be promising lead compound for further antitumor drug research.     

ANALYSIS ON ACOUSTICAL SCATTERING BY A CRACKED ELASTIC STRUCTURE

The acoustical scattering by a cracked elastic structure is studied. The mixed method of boundary element and fractal finite element is adopted to solve the cracked structure-acoustic coupling problem. The fractal two-level finite element method is employed for the cracked structure, which can reduce the degree of freedoms (DOFs) greatly, and the boundary element method is used for the exterior acoustic field which can automatically satisfy Sommerfeld‘s radiation condition. Numerical examples show that the resonance frequency is lower with the crack‘s depth increase, and that the effect on the acoustical field by the crack is particularly pronounced in the vicinity of the crack tip. This mixed method of boundary element and finite element is effective in solving the scattering problem by a cracked structure.     

RAFT polymerization of a novel allene‐derived asymmetrical divinyl monomer: A facile strategy to alkene‐functionalized hyperbranched vinyl polymers with high degrees of branching

Hyperbranched vinyl polymers with high degrees of branching (DBs) up to 0.43 functionalized with numerous pendent allene groups have been successfully prepared via reversible addition fragmentation chain transfer polymerization of a state‐of‐art allene‐derived asymmetrical divinyl monomer, allenemethyl methacrylate (AMMA). The gelation did not occur until high monomer conversions (above 90%), as a result of the optimized reactivity difference between the two vinyl groups in AMMA. The branched structure was confirmed by a combination of a triple‐detection size exclusion chromatography (light scattering, refractive index, and viscosity detectors) and detailed ¹H NMR analyses. A two‐step mechanism is proposed for the evolution of branching according to the dependence of molecular weight and DB on monomer conversion. Controlled radical polymerization proceeds until moderate conversions, mainly producing linear polymers. Subsequent initiation and propagation on the polymerizable allene side chains as well as the coupling of macromolecular chains generate numerous branches at moderate‐to‐high monomer conversions, dramatically increasing the molecular weight of the polymer. AMMA was also explored as a new branching agent to construct poly(methyl methacrylate)‐type hyperbranched polymers by its copolymerization with methyl methacrylate. The DB can be effectively tuned by the amount of AMMA, showing a linear increase trend. The pendent allene groups in the side chains of the copolymers were further functionalized by epoxidation and thiol‐ene chemistry in satisfactory yields. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2959–2969     

CdS Reinforced with CoSX/NiCo-LDH Core-shell Co-catalyst Demonstrate High Photocatalytic Hydrogen Evolution and Durability in Anhydrous Ethanol

At present, inefficient charge separation of single photocatalyst impedes the development of photocatalytic hydrogen evolution. In this work, the CoS_X/NiCo-LDH core-shell co-catalyst was cleverly designed, which exhibit high activity and high stability of hydrogen evolution in anhydrous ethanol system when coupled with CdS. Under visible light (λ≥420 nm) irradiation, the 3 %Co/NiCo/CdS composite photocatalyst exhibits a surprisingly high photocatalytic hydrogen evolution rate of 20.67 mmol g⁻¹ h⁻¹, which is 59 times than that of the original CdS. Continuous light for 20 h still showed good cycle stability. In addition, the 3 %Co/NiCo/CdS composite catalyst also shows good hydrogen evolution performance under the Na₂S/Na₂SO₃ and lactic acid system. The fluorescence (PL), ultraviolet-visible diffuse reflectance (UV-vis) and photoelectrochemical tests show that the coupling of CdS and CoS_X/NiCo-LDH not only accelerates the effective transfer of charges, but also greatly increases the absorption range of CdS to visible light. Therefore, the hydrogen evolution activity of the composite photocatalyst has been significantly improved. This work will provide new insights for the construction of new co-catalysts and the development of composite catalysts for hydrogen evolution in multiple systems.