The Divergent Synthesis of Nitrogen Heterocycles by Rhodium(II)‐Catalyzed Cycloadditions of 1‐Sulfonyl 1,2,3‐Triazoles with 1,3‐Dienes

The first rhodium(II)‐catalyzed aza‐[4+3] cycloadditions of 1‐sulfonyl 1,2,3‐triazoles with 1,3‐dienes have been developed, and enable the efficient synthesis of highly functionalized 2,5‐dihydroazepines from readily available precursors. In some cases, the reaction pathway could divert to formal aza‐[3+2] cycloadditions, thus leading to 2,3‐dihydropyrroles. In this context, the titled reaction represents a capable tool for the divergent synthesis of two types of synthetically valuable aza‐heterocycles from common rhodium(II) iminocarbene intermediates.     

ZnO添加量对Pd/Zr0.5Al0.5O1.75催化剂净化稀燃天然气汽车尾气性能的影响

以掺杂不同含量ZnO的Zr_0.5Al_0.5O_1.75为载体,制备了系列1.5%Pd催化剂.在模拟稀燃天然气汽车尾气条件下,测试了催化剂的活性和抗水性,并用N₂吸附-脱附、X射线衍射、H₂程序升温还原和X射线光电子能谱等手段对催化剂进行了系统表征.研究结果表明,ZnO的添加及添加量对催化剂的活性和抗H₂O性有明显影响,其中以ZnO添加量为15%时制备的复合氧化物为载体的催化剂活性最佳.当模拟尾气中不含H₂O时,该催化剂对甲烷的起燃温度（T₅₀）和完全转化温度（T₉₀）分别为278和314℃;在含H₂O时,该催化剂的T₅₀和T₉₀分别为342和371℃.     

制备方法对Pd-MnOx/γ-Al2O3催化剂分解地表O3性能的影响（英文）

分别用溶胶凝胶法和分步沉淀法制备了MnOx+γ-Al2O3和MnOx/γ-Al2O3,用等体积浸渍法将等量的Pd(NO3)2分别浸渍于其上,再将它们分别涂覆于堇青石上,得到不同物理化学性质的整体式催化剂,并采用X射线衍射、X射线光电子能谱、程序升温还原和低温N2吸附-脱附等技术对催化剂进行表征.结果表明,制备方法和MnOx焙烧温度明显影响催化剂中MnOx的物相、表面Mn物种和表面活性氧物种的分布及织构性质.活性测试结果表明,两种制备方法得到的催化剂于16–90 oC,380000–580000 h–1条件下均可将0.6μL·L–1 O3完全分解;尤其是溶胶凝胶法制备的Pd/γ-Al2O3+MnOx/γ-Al2O3催化剂分解O3活性较好,催化剂表面Mn2+:Mn3+:Mn4+=1.7:1:3(mol).     

Nd,Ce和La改性对Ni/SBA-15催化剂在CH4/CO2重整反应中性能的影响

以稀土金属Nd,Ce或La的氧化物为助剂,采用β-环糊精浸渍法对Ni/SBA-15催化剂进行了改性,并运用X射线衍射、N₂吸附-脱附、程序升温还原和热重等手段考察了改性的催化剂在CO₂重整CH₄制合成气反应中的催化性能. 结果表明,Nd等稀土金属氧化物的添加对催化剂孔结构和晶相结构等性质影响不大,但可影响NiO的还原; Nd的添加使NiO与载体之间以Ni-Nd-O形式相互作用,促进了活性组分NiO的还原. 其中,Nd的添加量为5-10 wt%时所制备的催化剂在重整反应中的催化活性最高,且具有很强的抗积碳性能. La和Ce氧化物促进的Ni催化剂也表现出类似的性质和催化性能.     

Investigations in annealing effects on structure and properties of β-isotactic polypropylene with X-ray synchrotron experiments

The influence of annealing on the microstructure and mechanical properties of β-form isotactic polypropylene (iPP) was investigated via in situ synchrotron small-angle X-ray scattering (SAXS), wide-angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC). Transition of β-iPP to α-iPP was investigated via recrystallization at high annealing temperatures (T _a?>?120 °C). And crystallinity, crystal sizes, and long period of ordered structure increased with increasing annealing temperature. Abrupt changes were found in both mechanical properties and structural features at the same T _a range (～120 °C). The in situ synchrotron SAXS and WAXD shows that the destruction of b phase at yielding and after yielding should account for the ductility of β-iPP. The thermodynamics and kinetics of annealing were investigated with DSC and X-ray synchrotron experiments. A characteristic annealing time was investigated, which measures the rate of phase evolution in annealing of β-iPP. Eventually, a hypothesized model can be used to describe the property/structure relations during this process.     

超级电容器石墨烯-聚苯胺复合材料的研究进展

超级电容器具有功率密度高、充放电速度快、循环寿命长和维护成本低的特点,在电动车动力电池领域具有潜在的应用前景。超级电容器性能主要由其电极材料所决定。聚苯胺易合成、理论比容量高,而且导电性能优异,作为超级电容器电极材料有很高的应用价值。但是,在长期使用过程中,它的体积容易发生膨胀或收缩,循环寿命差。为了解决这个问题,将聚苯胺与石墨烯复合可以扬长避短,充分利用两者之间的协同效应,赋予复合材料优异电化学电容性能。本文综述了超级电容器用石墨烯-聚苯胺复合材料的制备方法,包括原位聚合法、油水界面合成法、电化学合成法、层层自组装法等;提出了三维网状石墨烯和对石墨烯-聚苯胺复合材料进行改性来提高复合材料的电化学电容性能的思路。     

真空离心浓缩/气相色谱-质谱联用法测定白酒中6种邻苯二甲酸酯类增塑剂

建立了测定白酒中6种邻苯二甲酸酯类增塑剂的真空离心浓缩/气相色谱-质谱联用(GC-MS)分析方法。样品经真空离心浓缩,正己烷提取,取上层正己烷,4000r/min离心5min,采用GC-MS测定,外标法定量。在0.10～5.00μg/mL范围内,相关系数r20.992,样品在0.10～2.00 mg/kg范围内加标,平均回收率在88.83%～111.67%之间,相对标准偏差(RSD)为4.85%～11.35%,检出限(LOD)在0.02～0.05 mg/kg之间。采用该方法对16个白酒样品进行测定,结果表明该法简便、快速、结果准确可靠、灵敏度高,能够满足白酒中6种邻苯二甲酸酯增塑剂检测需求。     

一个各向异性磁稀释杂化钙钛矿系列[CH3NH3][CoxZn1-x(HCOO)3]

Inorganic-organic or hybrid perovskite materials, which are the complementary counterparts of pure inorganic perovskites, can provide many new opportunities in the researches of phase transitions, critical phenomena, and relevant properties, as they combine the characteristics of inorganic and organic components. Therefore, the hybrid perovskites of ammonium metal formate framework are very promising, and their properties have been found to be strongly dependent on the characteristics of the constituent metal ions and/or ammonium ions. Herein, we used solid solution strategies, borrowed from solid state chemistry, to investigate the anisotropic diluted magnetic hybrid perovskite system of [CH₃NH₃][Co_xZn_1-x(HCOO)₃], wherein the B-sites are occupied by the mixed metal ions of Co²⁺ and Zn²⁺. The solid solution compounds of this series in the range x = 0–1 (or the molar percent Co% = 0–100%) were successfully prepared using conventional solution chemistry methods. The resulting compounds were demonstrated to be iso-structural by using both single-crystal and powder X-ray diffraction analyses. The solid solution crystals belong to the orthorhombic space group Pnma, with the cell parameters being a = 8.3015(2)–8.3207(3) Å, b = 11.6574(4)–11.6811(5) Å, c = 8.1315(3)–8.1427(4) Å, and V = 787.89(5)–790.98(7) ų. The perovskite structure consists of a simple cubic anionic metal-formate framework and CH₃NH₃⁺ cations which are located in the framework cavities, with N―H···O hydrogen bonds formed between the framework and the cation. The members of this series showed negligible changes (< 0.4%) in their respective lattice and structural parameters. Thus, the prepared solid solution compounds constitute good molecule-based examples for the study of magnetic dilution under almost the same structural parameters and molecular geometries. Upon dilution, the magnetization per mole of Co at low temperatures and low fields was suppressed by the magnetic anisotropy of Co²⁺ and gradual destruction of the large spin canting between coupled Co²⁺ ions, in contrast to the magnetization enhancement observed in the isotropic diluted system of [CH₃NH₃][Mn_xZn_1-x(HCOO)₃] with the same perovskite structure. The percolation limit was estimated as (Co%)_P = 27(1)% (or x_P = 0.27(1)) from the magnetic data, which was slightly lower than that predicted by the percolation theory for a simple cubic lattice (31%); this trend was due to the strong magnetic anisotropy of the present system. In addition, rare incommensurate phase transitions were primarily detected below ~120 K for the pure Co and Zn members, which may also affect the magnetic properties of the materials.     

Autocatalytic polymerization of selenium/polypyrrole nanocomposites as functional theranostic agents for multi-spectral photoacoustic imaging and photothermal therapy of tumor

The synchronization of diagnosis and treatment is a new trend in cancer treatment. Photoacoustic imaging (PAI) and photothermal therapy (PTT) are recognized as one of the perfect combinations. The autocatalytic polymerization of selenium/polypyrrole (Se@PPy) nanocomposites with a wide-absorption band at near-infrared region (NIR, 800 nm) has been developed in this paper. The wide optical absorption characteristics enable Se@PPy nanocomposites to achieve multi-spectral PAI. Ex vivo experiments show desirable photoacoustic ability of the Se@PPy nanocomposites at wavelengths ranging from 700 nm to 900 nm, which is better than that of commercial indocyanine green (ICG). Se@PPy nanocomposites have high photothermal conversion efficiency up to 36.3% as well as excellent photo-thermal stability. In vitro cytotoxicity test demonstrates that the Se@PPy nanocomposites have good bio-safety. Furthermore, the feasibility of Se@PPy nanocomposites for enhancing multi-spectral PAI guided PTT was verified on 4T1 tumor-bearing nude mice. Our results indicate that Se@PPy nanocomposites could be used as an effective theranostic agent for near-infrared light-mediated PAI and PTT of tumor.     

Cascade One‐Pot Synthesis of Orange‐Red‐Fluorescent Polycyclic Cinnolino[2,3‐f]phenanthridin‐9‐ium Salts by Palladium(II)‐Catalyzed C−H Bond Activation of 2‐Azobiaryl Compounds and Alkenes

Quaternary ammonium salts were synthesized in moderate to good yields through double oxidative C?H bond activation on azobenzenes. The mechanism of the highly regioselective reaction of 2‐azobiaryls with alkenes to give orange‐red‐fluorescent cinnolino[2,3‐f]phenanthridin‐9‐ium salts and 15H‐cinnolino[2,3‐f]phenanthridin‐9‐ium‐10‐ide is proposed to involve ortho C?H olefination of the 2‐azobiaryl compound with the alkene, intramolecular aza‐Michael addition, concerted metalation–deprotonation (CMD), reductive elimination, and oxidation.