Direct synthesis, characterization of Cu-SBA-15 and its high catalytic activity in hydroxylation of phenol by H2O2

Transition metal copper substituted mesoporous silica (Cu-SBA-15) was synthesized using triblock copolymers surfactant as template agent under acidic condition. The result Cu-SBA-15 was characterized with XRD, ICP-AES, FT-IR and N₂ adsorption–desorption measurements, which prove that Cu(II) was mainly incorporated into the framework of Cu-SBA-15. Its catalytic activity was studied for phenol hydroxylation using H₂O₂ (30%). The substituting element (Cu²⁺) is incorporated into the framework position forming a new type of active site which raises the phenol conversion to 62.4% and the diphenol (the mixture of catechol (CAT) and hydroquinone (HQ)) selectivity to 97%. The Cu-SBA-15 has very high selectivity for catechol (about 71% selectivity), which is completely different from that of the microporous titanium silicalite zeolites (47.1% phenol conversion and about 50% selectivity to CAT under same reaction conditions). The results obtained indicate that the selective oxidation of phenol with H₂O₂ by a radical substitution mechanism.     

IClO2异构化反应机理及电子密度拓扑研究

利用密度泛函理论方法研究了IClO2异构化反应机理. 优化得到了七种异构体, 其中OIClO和IClOO还未见报道, 对各异构体的热力学稳定性进行了比较. 找到了异构化过程的过渡态, 并通过内禀反应坐标(IRC)计算确认了各个异构体之间的相互转化关系. 从量子拓扑学的角度, 对典型异构化反应通道IRC途径上的各点进行了电子密度拓扑分析, 讨论了反应过程中化学键的断裂、生成以及化学键的变化规律, 找到了反应途径上的能量过渡态(ETS)和结构过渡态(STS).     

Determination and Differentiation of Two Seemingly Identical Medicinal Herbs by Capillary Electrophoresis with Electrochemical Detection

A high-performance capillary electrophoresis with electrochemical detection (CE-ED) method has been employed for the determination of six bioactive ingredients in traditional Chinese herbs, Herba cepbalanoplosis segeti and Herba cirsii japonici. The effects of several factors such as the acidity and concentration of running buffer, the separation voltage, the applied potential and the injection time on CE-ED were investigated. Under the optimum conditions, the six analytes could be well separated within 21 min in a 75 cm length capillary at the separation voltage of 15 kV in a 50 mmol L^–1 borax running buffer (pH 8.4). A 300 m diameter carbon disk electrode was used as the working electrode positioned carefully opposite the outlet of the capillary in a wall-jet configuration at potential of +950 mV (vs. SCE). Good linear relationship was established between peak current and concentration of analytes over two orders of magnitude with detection limits (S/N=3) ranged from 1.5×10^–7 to 6.0×10^–7 g mL^–1 for all six analytes. This proposed method has been successfully applied for the analysis of traditional Chinese herbs after a relatively simple extraction procedure, further on, for the differentiation of these above two seemingly identical herbs based on their electropherograms or characteristic electrochemical profiles.     

Copper-exchanged LTA zeolite membranes with enhanced water flux for ethanol dehydration

Phase-pure and well-intergrown Cu-LTA membranes are developed through copper ions exchange of sodium ions in Na-LTA framework. For pervaporation of 90.0 wt% ethanol/10.0 wt% water mixtures, the Cu-LTA membrane shows much higher water flux than Na-LTA membranes due to the enhancement of the pore size after ions exchange.     

松干蚧性信息素Matsuone C(7)～C(13)片段的合成

以甾体皂甙元降解工业废弃物中获取的(R)-5-溴-4-甲基戊酸甲酯为原料, 通过三步反应合成了松干蚧性信息素Matsuone的C(7)～C(13)片段-(R)-4,6-二甲基庚醛, 三步合成的总收率为41.6%.     

Synthesis, Crystal Structure and Inhibition of the K562 Cell Proliferation of N＇-Tertbutylaminocarbonyl-N-2-chlorophenoxyacetylthiourea

The title compound N'-tert-butylaminocarbonyl-N-2-chlorophenoxyacetylthiou- rea has been synthesized for the first time. Complete assignments were achieved by IR, 1H NHR and single-crystal X-ray diffraction analyses. The inhibitory rate of the cellular growth of K562 cells (chronic myeloid 1eukemic cells) was measured using MTT [3-(4,5-dimethylthiazo-2-y1)-2,5-di- phenyltetra-zolium bromide] assay. The cell apoptosis was assessed by agarose gel electrophoresis to find that the title compound has antiproliferation and apoptosis inducing effects on K562 cells. In order to investigate the relationship between structure and activity of the target compound, we report its crystal structure and biological behavior in the present paper. Crystallographic data: C14H18- ClN3O3S, Mr = 343.82, orthorhombic, space group Pnma, a = 19.786(6), b = 6.789(2), c = 12.938(4) , V = 1738.0(9) 3, Z = 4, Dc = 1.314 g/cm3, F(000) = 720, μ(MoKα) = 0.354 mm-1, R = 0.0378 and wR = 0.0941. The molecule is a planar structure.     

水分子团簇分子力场方法的比较研究

采用传统水分子力场模型(SPC, TIPnP(n=3-5))和极化模型(POL3, AMOEBA, SPC-FQ, TIP4P-FQ)对水分子二聚体团簇性质进行了比较和研究. 以从头计算和实验数据为依据, 分析水分子在外场作用下体系的静电极化, 电荷转移和分子结构变化. 通过水分子二聚体结合能和各分解能量项评价极化静电势能在双分子结合能中的地位和作用, 以及各水分子力场的适用性. 通过水分子团簇多体相互作用能的计算,展示不同极化水分子力场定量计算极化能量的实际能力. 通过对力场模型结果的对比和分析, 为进一步发展极化力场模型, 并应用到其他体系提供借鉴和依据.     

Effective removal of chlorinated organic pollutants by bimetallic iron-nickel sulfide activation of peroxydisulfate

Chlorinated organic pollutants(COPs) have caused serious contaminants in soil and groundwater,hence developing methods to remove these pollutants is necessary and urgent.By a simple hydrothermal method,we synthesized the bimetallic iron-nickel sulfide(FeNiS) particles which exhibited excellent catalytic property of COPs removal.FeNiS was chosen as the peroxydisulfate(PDS) activator to removal COPs including 4-chlorophenol(4-CP),1,4-dichlorophenol(1,4-DCP) and 2,4,6-trichlorophenol(2,4,6-TCP).The results show that FeNiS can efficiently activate PDS to produce sulfate radical(SO_4~(·-)) which plays major role in the oxidative dechlorination and degradation due to its strong oxidizing property and the ability of producing hydroxyl radicals(~·OH) in the alkaline condition.Meanwhile,the Cl-abscised from COPs during the dechlorination can turn into the chlorine radicals and enhance the degradation and cause further mineralization of intermediate products.This bimetallic FeNiS catalyst is a promising PDS activator for removal of chlorinated organics.     

利用天然生物分子合成导电聚苯胺的研究

本文综述了利用多种不同的天然生物分子如蛋白质(包括酶和氨基酸)、糖类、核酸、多巴胺和柠檬汁等为模板合成导电聚苯胺的研究进展。本文首先介绍了这些天然生物分子对产物聚苯胺的手性、导电率、形态以及其它方面性质的影响,归纳了利用天然生物分子合成导电聚苯胺的研究进展,然后分析了导电聚苯胺合成过程中面临的问题并对该领域的未来发展进行了展望,以期为制备性质优良和环境友好的新型导电聚苯胺材料提供有益的参考。     

Two new compounds derived from bufalin

The biotransformation of bufalin by cell suspension cultures of Platycodon grandiflorus was investigated and two new biotransformed products were obtained,which was 3-epi-telocinobufagin and 3-epi-bufalin-3-O-β-D-glucoside.