超细钙钛矿型PrMnO3制备、表征及光催化

以Pr6O11和Mn(NO3)2为主要原料,采用"溶胶-凝胶"法结合"真空干燥"技术制备超细钙钛矿型PrMnO3;用TG-DTA,TEM,XRD,FT-IR等手段进行表征;以紫外灯为光源,用超细PrMnO3光催化降解甲基橙溶液.结果显示:170 ℃真空干燥制得的Pr-Mn干凝胶为无定形的疏松土黄色粉末,由大量直径介于10～20 nm的球形小颗粒组成;Pr-Mn干凝胶热处理过程中,500 ℃时出现晶相Pr6O11,700 ℃时产生晶相Mn2O3,Pr影响了Pr-Mn干凝胶中Mn的晶化,900 ℃时得到粒径小于100nm结晶度较好的纯晶相钙钛矿PrMnO3;以300 W紫外灯为光源,用0.50 g超细PrMnO3处理10 mg·L-1甲基橙溶液1000 ml,2 h即可完全降解,该降解过程属动力学一级反应.     

A series of dithienobenzodithiophene based small molecules for highly efficient organic solar cells

Three acceptor-donor-acceptor (A-D-A) small molecules DCAODTBDT, DRDTBDT and DTBDTBDT using dithieno[2,3-d:2′,3′-d′]benzo[1,2-b:4,5-b′]dithiophene as the central building block, octyl cyanoacetate, 3-octylrhodanine and thiobarbituric acid as the end groups were designed and synthesized as donor materials in solution-processed photovoltaic cells (OPVs). The impacts of these different electron withdrawing end groups on the photophysical properties, energy levels, charge carrier mobility, morphologies of blend films, and their photovoltaic properties have been systematically investigated. OPVs device based on DRDTBDT gave the best power conversion efficiency (PCE) of 8.34%, which was significantly higher than that based on DCAODTBDT (4.83%) or DTBDTBDT (3.39%). These results indicate that rather dedicated and balanced consideration of absorption, energy levels, morphology, mobility, etc. for the design of small-molecule-based OPVs (SM-OPVs) and systematic investigations are highly needed to achieve high performance for SM-OPVs.     

Fabrication of polymeric-Laponite composite hollow microspheres via LBL assembly

Hollow structure microspheres with composite polymeric-Laponite shells were prepared by electrostatic self-assembly of Laponite on the polymeric hollow microspheres in this work. The multilayer hydrophilic core/hydrophobic shell polymer latex particles containing carboxyl groups inside were first synthesized via seeded emulsion polymerization, followed by alkali treatment, generating polymeric hollow microspheres. Then, polyethyleneimine (PEI) and Laponite were alternately electrostatic adsorbed on the prepared polymeric hollow microspheres to form polymeric-Laponite composite hollow microspheres. It was indicated that the morphology of alkali-treated microspheres could be tuned through simply altering the dosage of alkali used in the post-treatment process. Along with the increasing of the coating layers, the zeta potential of microspheres absorbed PEI or Laponite approximately tended to be constant respectively, and the thickness of Laponite layer around the hollow microspheres increased clearly, getting more uniform and homogenous. Furthermore, the corresponding polymeric-Laponite hollow microspheres showed high pressure resistance ability compared to the polymeric hollow microspheres.     

社会互动,投资者情绪传染与资产泡沫——基于股票论坛发帖的实证研究

在资本市场中,投资者并不是相互独立的个体,而是相互学习、相互交流的。随着互联网的迅猛发展,这种社会互动变得更为频繁和普遍,因此社会互动对资产价格的影响也不容小觑。本文先通过理论建模提出理论假设:社会互动存在条件下,投资者互动会加剧市场情绪的传染,进而增加资产泡沫;当投资者情绪高涨时,投资者互动强度显著正向影响泡沫;当投资者情绪低落时,投资者互动强度显著负向影响泡沫;受社会互动影响,投资者活跃的交易会加剧市场情绪的传染,进而增加资产泡沫。之后本文基于股票论坛发帖构建社会互动、投资者情绪指标,验证了中国股票市场中本文理论假设的正确性。     

一般型三维簇的三典范映射

研究了一般型三维射影代数簇的三典范映射性质.当几何亏格p_g≥2时,整数m≥4的多典范映射结构已经比较清晰,但是三典范映射的结构还有很多未知问题.如果三典范映射φ_3不是双有理的,本文证明了φ_3的映射次数(如果φ_3是一般有限映射)或者一般纤维中一般不可约分支的几何亏格(如果φ_3是纤维型)有一个上界.     

The role of low levels of water in the electrochemical oxidation of α-tocopherol (vitamin E) and other phenols in acetonitrile

The phenol, α-tocopherol, can be electrochemically oxidised in a -2e(-)/-H(+) process to form a diamagnetic cation that is long-lived in dry organic solvents such as acetonitrile and dichloromethane, but in the presence of water quickly reacts to form a hemiketal. Variable scan rate cyclic voltammetry experiments in acetonitrile with carefully controlled amounts of water between 0.010 M-0.6 M were performed in order to determine the rate of reaction of the diamagnetic cation with water. The water content of the solvent was accurately determined by Karl Fischer coulometric titrations and the voltammetric data were modelled using digital simulation techniques. The oxidation peak potential of α-tocopherol measured during cyclic voltammetry experiments was found to shift to less positive potentials as increasing amounts of water (0.01-0.6 M) were added to the acetonitrile, which was interpreted based on hydrogen-bonding interactions between the phenolic hydrogen atom and water. Several other phenols were examined and they displayed similar voltammetric features to α-tocopherol, suggesting that interactions of phenols with trace amounts of water were a common occurrence in acetonitrile. The H-bonding interactions of α-tocopherol with water were also examined via NMR and UV-vis spectroscopies, with the voltammetric and spectroscopic studies extended to include other coordinating solvents (dimethyl sulfoxide and pyridine).     

Chemical constituents from the roots of Xanthium sibiricum

Xanthium sibiricum patrin ex Widder (Compositae) is an annual herb which grows all around China. Chemical investigations of its roots resulted in the identification of 15 compounds: stigmast-4-en-6β-ol-3-one (1), β-sitostenone (2), β-sitosterol (3), nonadecanoic acid (4), 5α,8α-epidioxy-22E-ergosta-6,22-dien-3β-ol (5), scopoletin (6), Jatrocin B (7), (±)syringaresinol (8), 9,9'-O-di-(E)-feruloyl-(-)-secoisolariciresinol (9), cleomiscosin A (10), cleomiscosin C (11), N-trans-feruloyl tyramine (12), daucosterol (13), 5-methyluracil (14) and uracil (15). Structures were elucidated by spectroscopic (NMR and MS) methods and confirmed by comparing with reference samples and literature data. Compounds 1-2, 4-12, 14, and 15 were isolated from this genus for the first time, while this is the first report of coumarinolignoids in the Compositae family, and coumarinoligoids could be considered as valuable chemotaxonomic markers for the plant.     

Stereocontrolled synthesis of (+)-methoxyphenylkainic acid and (+)-phenylkainic acid

The efficient total syntheses of (+)-methoxyphenylkainic acid (3) and (+)-phenylkainic acid (4) were achieved using a rhodium carbenoid-mediated intermolecular C-H insertion reaction. Complete stereoselective construction of the kainoid skeleton was accomplished by utilizing the stereochemistry at the C-4 position as a pivotal stereogenic center.     

Enantioselective total synthesis of aperidine

An efficient total synthesis of aperidine was accomplished using a Rh-catalyzed C-H insertion of a cis-dihydrobenzofuran ring. To circumvent the facile epimerization of the cis-dihydrobenzofuran ring, we designed and prepared the C-H insertion precursor diazoamide by Raines' protocol. Finally, the efficient incorporation of a guanidine group and mild deprotection conditions yielded this labile natural product.     

The effect of the distance between acidic site and basic site immobilized on mesoporous solid on the activity in catalyzing aldol condensation

Acid-base bifunctional heterogeneous catalysts containing carboxylic and amine groups, which were immobilized at defined distance from one another on the mesoporous solid were synthesized by immobilizing lysine onto carboxyl-SBA-15. The obtained materials were characterized by X-ray diffraction (XRD), N₂ adsorption, Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron micrographs (SEM), transmission electron micrographs (TEM), elemental analysis, and back titration. Proximal-C-A-SBA-15 with a proximal acid-base distance was more active than maximum-C-A-SBA-15 with a maximum acid-base distance in aldol condensation reaction between acetone and various aldehydes. It appears that the distance between acidic site and basic site immobilized on mesoporous solid should be an essential factor for catalysis optimization.