阳离子改性HZSM-5沸石上低碳醇反应历程的TPSR-MS研究

用ＴＰＳＲ－ＭＳ技术研究了Ｃｕ，Ｚｎ和Ｇａ改性Ｈ－ＺＳＭ－５沸石的活性中心性质及Ｃ１～Ｃ４醇的反应历程。结果表明，Ｚｎ－和Ｇａ－ＺＳＭ－５有两种芳构化活性中心，即Ｂ酸和Ｚｎ，Ｇａ活性物种；甲醇在Ｃｕ－ＺＳＭ－５上只生成二甲醚、ＣＯ和ＣＯ２，而在Ｚｎ－ＺＳＭ－５上芳构化反应历程为：（１）醇经由醚脱水生成烯烃，Ｃ２～Ｃ４醇学可单分子脱水生成烯烃；（２）烯烃中间物齐聚，齐聚物通过氢转移和脱氢途径环化、芳     

Synthesis and Crystal Structure of a New Quinazolinone Compound 2,3-Dihydro-2-（2-hydroxyphenyl）-3-phenyl-quinazolin-4（1H）-one

A new quinazolinone compound 2,3-dihydro-2-(2-hydroxyphenyl)-3-phenylquinazolin-4(IH)-one 3 ([C2oH16O2N2]-C2H5OH, Mr = 362.42) and compound 2-(2-hydroxybenzylidene-amino)-N-phenyl-benzamide 2 (C2oH16O2N2, Mr = 316.34) were prepared from a precursor of 2-amino-N-phenyl-benzamide 1 (C13H12ON2, Mr = 212.25). Compound 3 was characterized by single-crystal X-ray diffraction analysis. The crystal belongs to orthorhombic,space group Pbca with a = 1.2889(11), b = 1.6170(14), c = 1.7729(15) nm, V= 3.695(6) nm^3, Z= 8, F(000) = 1536, Mr = 362.42, Dc = 1.303 g/cm^3, μ(MoKa) = 0.087 mm^-1, R = 0.0447 and wR= 0.0879. The crystal structure analysis indicates that the title compound has a two-dimensional network structure formed by hydrogen bonds and electrostatic interactions.     

Anodic behavior of nickel-based alloys in the electrolytic production of NF3

The Ni-based alloys, such as Ni-Co, Ni-Mn, Ni-Ag, Ni-Cu, Ni-Al and Ni-Si, prepared by hot isostatic pressing (HIP) at 1000 °C under 2 × 10⁸ Pa for 2 h were employed as the anodes for electrolytic production of NF₃. The current efficiencies for NF₃ formation were 42-38, 52-40, 52-47, 63-62, 50 and 41% for Ni-Co, Ni-Mn, Ni-Ag, Ni-Cu, Ni-Al and Ni-Si alloys, respectively. The current efficiencies only on Ni-Cu alloys with Cu concentrations lower than 10 mol% were almost the same as those on Ni sheet and HIPed Ni anodes, whereas those on the other alloys used in this study were smaller compared with those on both Ni anodes. On the other hand, the current losses caused by anodic dissolution of Ni-Co, Ni-Mn, Ni-Ag, Ni-Cu, Ni-Al and Ni-Si alloy electrodes were 7.95-4.42, 6.40-7.02, 5.60-6.30, 3.34-6.33, 5.10 and 0.18%, respectively. The anode consumptions of Ni-5 mol% Cu and Ni-5 mol% Si alloys were almost the same or smaller compared with those of Ni sheet and HIPed Ni electrodes, though those of other alloys used were large compared with those of both Ni anodes. Consequently, addition of Cu to the nickel matrix is available for a cheaper cost of anode with keeping a same current efficiency as that on the Ni anode and addition of Si to the nickel matrix is effective for decreasing anode consumption largely. A Ni sheet electrode containing a trace of impurities, such as Co, Mn, Ag and Al, is also favorable as the anode for electrolytic production of NF₃.     

Factors affecting propagating fronts of addition polymerization: Velocity,front curvature,temperatue profile,conversion, and molecular weight distribution

Several properties of propagating fronts of addition polymerization were studied. A power function could be fit to the velocity dependence on initiator concentration, but not with the exponents predicted by current models or in agreement with other published work. Bubbles from the volatile by-products of initiator decomposition were found to affect the front velocity and curvature. The front velocity for triethylene glycol dimethacrylate polymerization was found to depend linearly on temperature over a moderate range. The conversion of methacrylic acid in fronts varied greatly with initiator type and concentration. Benzoyl peroxide produced much lower conversion than t-butyl peroxide, but fronts with tBPO propagated slower. A dual initiator system of BPO and tBPO produced rapidly propagating fronts with good conversion but the contribution of each initiator to the velocity was not additive. The possibility of chain branching was considered. The apparent molecular weight distributions were very broad, often trimodal, and found to depend on initiator type and concentration as well as the tube diameter. The temperature profiles were measured and found to be very sharp for BPO and broader for tBPO but both had front temperatures in excess of 200°C, indicating a high ceiling temperature. © 1995 John Wiley & Sons, Inc.     

Rapid determination of desorption efficiency, and analysis of solvent mixtures for occupational exposure studies

Summary An analytical procedure has been developed for simultaneous determination of solvent mixture vapors to enable evaluation of occupational exposure. To determine the desorption efficiency the volatile components of the solvent mixtures were generated from a glass tube filled with glass wool. This device is easy to prepare and use. These vapors were then collected in activated charcoal tubes and analyzed by capillary gas chromatography. The method was tested with a mixture of 22 solvents, including aliphatic and aromatic hydrocarbons, alcohols, ethers, esters, and ketones, all at low concentrations. All the components were detected. When a 99∶1 mixture of carbon disulfide-dimethylformamide was used for desorption the efficiency was>75% for most of the solvents.     

Conversion of phosphogypsum to potassium sulfate

Summary Solubility of calcium sulfate in concentrated aqueous chloride solutions is of particular significance in chloride hydrometallurgy and various crystallization processes, such as the production of potassium sulfate from phosphogypsum and potassium chloride. This paper examines an example of the second type of application in which gypsum and potassium chloride are reacted to form K₂SO₄. The solubility of phosphogypsum in aqueous solutions of KCl, HCl, and mixtures of both has first been measured at various temperatures and concentrations. The parameters investigated are HCl concentration up to 6M, KCl concentration up to 180 g L^-1 and temperature from 25 to 80°C. In addition, the influence of co-existing chloride salts, such as (HCl+KCl), on the solubility of calcium sulfate is estimated from 25 to 80°C. The solubility increases obviously with the temperature increment as it does initially with acid concentration, reaching a maximum of about 3M HCl, 130 g L^-1 KCl and then drops. At the same time, the solubility of CaSO₄·2H₂O decreases with increasing KCl concentration.     

Reverse fragment based drug discovery approach via simple estimation of fragment contributions

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高荧光量子效率的分子分散型聚芴衍生物的放大自发发射特性

通过将掺杂剂单元用化学键接到聚芴的侧链上,实现了掺杂剂单元在高分子主体中的分子水平分散,开发了一种新型的基于掺杂剂/主体材料体系的分子分散型蓝光聚芴衍生物.与纯聚芴相比,这种新的分子分散型蓝光聚芴衍生物具有很高的荧光量子效率.以这种新的分子分散型蓝光聚芴衍生物为增益介质的激光器件,在Nd:YAG 355 nm脉冲激光泵浦下,获得了较好的放大自发发射光谱,阈值达到0.25 m J/(pulse cm2).从光物理的角度对薄膜的光学增益和光学损耗进行了定量运算和分析,经过拟合发现,当泵浦能量为0.06m J/pulse时,该聚芴衍生物增益系数可达23.08 cm-1,损耗系数为6.96 cm-1.优良的放大自发发射特性表明该聚芴衍生物是非常好的有机激光增益介质材料.     

紫外光引发甲基丙烯酸甲酯乳液聚合

以60W高压汞灯为光源,以偶氮二异丁氰(AIBN)为主要光引发剂,以甲基丙烯酸甲酯(MMA)为单体进行乳液聚合,考察了光照时间、单体浓度、光引发剂浓度等因素对单体转化率的影响;采用透射电镜观察了乳胶粒的形态,并测定了其尺寸.结果表明,转化率随光照时间和单体浓度的增加而上升;当光引发剂质量分数为3%时单体转化率最高.     

Synthesis and photovoltaic properties of main chain polymeric metal complexes containing 1,10‐phenanthroline metal complexes conjugating alkyl fluorene or alkoxy benzene by C═C bridge for dye‐sensitized solar cells

Four main chain polymeric metal complexes (P1–P4) based on 1,10‐phenanthroline metal complexes via the Heck coupling have been synthesized and characterized by Fourier transform infrared spectroscopy, ¹H NMR, UV–Vis absorption, photoluminescence spectroscopy, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, elemental analysis, and cyclic voltammetry. To investigate their photovoltaic properties, the dye‐sensitized solar cells based on these polymers dyes are studied, under the illumination of AM 1.5G, 100 mW/cm². The study results show the four polymers exhibit good thermally stable and the solar cells based on them have good device performance, and the maximum power conversion efficiency is up to 0.735% for the solar cells based on P3 with a short‐circuit current (J_sc) of 1.68 mA/cm² and an open‐circuit voltage (V_oc) of 0.62 V. Copyright © 2012 John Wiley & Sons, Ltd.