CexTi1-xO2复合氧化物的结构及负载CuO对NO还原性能研究

采用共沉淀法制备了不同摩尔比(x=0,0.1,0.2～0.9,1.0)的CexTi1-xO2复合氧化物,考察了CuO/CexTi1-xO2对NO+CO反应的活性,并用BET,TPR和XRD等技术对各试样进行了表征。结果表明,试样的结构和还原特性随焙烧温度变化而变化。XRD检测表明,x值从0.1增加到0.5时,650℃焙烧的试样已形成了CeTi2O6物相,且主要以无定形状态存在;试样经800℃焙烧后晶化完全;x>0.6时,一些TiO2已经进入了CeO2晶格,形成了Ce Ti固溶体。催化剂活性评价表明CuO/CexTi1-xO2(650℃)对NO+CO反应具有较好的活性,其活性随x值变化而变化。TPR及XRD结果表明CuO与CeTi2O6之间存在很强的相互作用,CeTi2O6物相的形成使CuO的还原峰温由380℃提前到200℃,而CuO的存在又促进CeTi2O6的还原峰温从600℃提前至200～300℃。     

Reaction kinetics of the selective liquid phase hydrogenation of styrene oxide to β-phenethyl alcohol

Liquid phase hydrogenation of styrene oxide using 1% Pd/C and NaOH as a promoter was found to give selectively β-phenethyl alcohol (PEA) under very mild conditions (313–333 K; 0.68–5.5 MPa). The kinetics of this system was investigated by collecting initial rate data in a batch slurry reactor. Rate of hydrogenation was found to decrease beyond a certain concentration of both hydrogen (>3 MPa) and styrene oxide (>0.5 kmol/m³). A Langmuir–Hinshelwood type rate equation has been proposed based on the initial rate data in the kinetic regime. The model predictions agree very well with the experimentally observed concentration–time data indicating the applicability of the proposed rate model.     

Friedel-crafts acylation of 2-methoxynaphthalene over h-beta catalysts: effect of Si/Al ratio

The acylation of 2-methoxynaphthalene with acetic anhydride was carried out over zeolite beta catalysts having various Si/Al ratios. It was found that the reaction performance is strongly dependent on the Si/Al ratio of the catalyst. The catalytic reaction features were elucidated in terms of the acidic properties of the catalysts. This revised version was published online in June 2006 with corrections to the Cover Date.     

Recent Progress in Direct Partial Oxidation of Methane to Methanol

The direct conversion of methane to methanol has attracted a great deal of attention for nearly a century since it was first found possible in 1902, and it is still a challenging task. This review article describes recent advancements in the direct partial oxidation of methane to methanol. The history of direct oxidation of methane and the difficulties encountered in the partial oxidation of methane to methanol are briefly summarized. Recently reported developments in gas-phase homogeneous oxidation, heterogeneous catalytic oxidation and liquid phase homogeneous catalytic oxidation of methane axe reviewed.     

Total synthesis of the marine alkaloid halitulin

The structure of the strongly cytotoxic marine alkaloid halitulin (1) has been confirmed by total synthesis and its absolute configuration determined as (15S). The synthesis follows a strategy previously reported by one of us and uses an efficient preparation of the quinoline-7,8-diol unit by modified Baeyer-Villiger and Skraup reactions. The O-benzyl protecting groups were removed in the last step of the synthesis by transfer hydrogenolysis without concomitant reduction of the quinoline ring. The method can be applied for the synthesis of halitulin analogues.     

Molecule-Responsive Fluorescent Sensors of α-Helix Peptides Bearing α-Cyclodextrin, Pyrene and Nitrobenzene Units in Their Side Chains

-Helix peptides bearing one unit of -cyclodextrin (-CD), one unit of pyrene and one unit of nitrobenzene (NB) in their side chains have been designed and synthesized as novel molecule-responsive devices.In both the CD-peptides, -PR17 and -PL17, the NB unit is separated from the CD unit by two turns of the helix. Two reference peptides (PL17, and -P17,) have also been synthesized. The circular dichroism studies in the peptide absorption region (200–250 nm)of -PR17 and -PL17 suggestthat the CD-peptides form stable-helixstructures (83–77%), which was destabilized by accommodating guest molecules (e.g., n-pentanol) into the CD cavity. It suggests that formation of intramolecular host–guest(CD–NB) complex stabilized thehelical structure and exogenous guest molecule excluded the appending NB moiety from inside to outside of the CD cavity, thereby causing destabilization of the helical structure and increasing the random coil content. The ICD spectra of the peptides in the pyrene and nitrobenzene absorption region (250–40 nm) suggest that NB forms inclusion complex with CD. The fluorescence studies revealed that the fluorescence of the pyrene unit is quenched by the NB unit in -PR17 and -PL17. The fluorescence intensity increases with increasing guest concentration for the CD-peptides.This guest-responsiveenhancement in the fluorescence intensity can be explained in terms of increased distance between the pyrene and NB moieties, which is caused by exclusion of the NB moiety from the CD cavity by guest accommodation. Using the guest-responsive fluorescence quenching properties of the CD-peptides, we have obtained binding constants for various short chain alkanols. -PL17 has higher binding affinity to the guest molecules than its isomer, -PR17, indicating that the location of functional groups on the peptide scaffold is important in molecule detection.     

Trace level analysis of volatile and semi-volatile organic compounds in water using a membrane/jet separator interfaced to an ion trap mass spectrometer

An ion trap mass spectrometer, equipped with a membrane/jet separator interface, is used for the direct detection of volatile and semi-volatile organic compounds in aqueous solutions. Aqueous sample is passed through a capillary membrane, the outside surface of which is continuously purged by helium. The permeate is pneumatically transported to the mass spectrometer via a jet separator which acts as an additional enrichment device. The performance and response characteristics of non-porous silicone and microporous polytetrafluoroethylene (PTFE) membranes are studied. The microporous membrane allows sufficient water to pass for it to be used as a reagent gas for chemical ionization. Both types of membranes provide detection limits in the parts per trillion (pptr) to parts per billion (ppb) range with a linear dynamic range of 3 orders of magnitude for some volatile organic compounds. Results show that there is no detectable matrix effect on response in the selected cases examined. The use of microporous membranes to analyze more polar compounds, such as 5-hydroxymethyl furfuraldehyde and lactic acid, is also demonstrated. The effects of other experimental parameters, such as membrane temperature and length, on sensitivity are also investigated.     

Hydrogen transport through Pd-Ni alloy electrodeposited on Pd substrate

Hydrogen transport through a Pd-Ni alloy electrodeposited on a Pd substrate (Pd-Ni/Pd bilayer symmetric electrode) has been investigated using cyclic voltammetry and a.c. impedance spectroscopy combined with the electrochemical hydrogen permeation method. The permeation build-up current transients and the measured impedance spectra were analyzed using the time-lag method for the bilayer electrode and a complex non-linear least squares data-fitting method based upon the derived Faradaic admittance for the hydrogen absorption into and diffusion through the bilayer electrode under the permeable boundary condition, respectively. The value of the hydrogen diffusivity in the Pd-Ni layer was lower than that in the Pd layer. Furthermore, the values of the charge transfer resistance and equilibrium absorption constant for the Pd-Ni/Pd bilayer electrode were higher than those for the Pd single layer electrode. From the experimental results, the role of the thin Ni(OH)₂ film formed on the Pd-Ni layer surface in the hydrogen transport through the Pd-Ni/Pd bilayer electrode is discussed in terms of its passivating effect and extremely large hydrogen solubility. Received: 22 January 1997 / Accepted: 15 April 1997     

β—环糊精对D／L—酪氨酸对映体的手性识别及超分子包合物的合成

利用圆二色谱研究了β－环糊精（β－ＣＤ）对Ｄ／Ｌ酪氨酸的手性识别行为，制备出了β－ＣＤ与Ｌ－酪氨酸（Ｌ－Ｔｙｒ）的固体超分子化合物，并用元素分析、薄层分析、Ｘ射线粉末衍射及热分析对包合物进行了表征，用荧光光谱法测定了包合物的形成常数．实验结果表明，β－ＣＤ具有选择包结Ｌ－酪氨酸的特性；主客体形成１１的包合物，其组成为Ｌ－Ｔｙｒ／β－ＣＤ·１２Ｈ２Ｏ；稳定常数为５．１３×１０３Ｌ／ｍｏｌ；包合物的热稳定性比主客体皆有改善     

Fast simultaneous determination of 23 veterinary drug residues in fish,poultry, and red meat by liquid chromatography/tandem mass spectrometry

The misuses of veterinary drugs can result in the accumulation of residues in food of animal origin that can make its way to the final consumer. Herein we describe a simple method for the accurate determination of beta-lactams, quinolones, sulphonamides, and tetracyclines in fish, poultry, and red meat. No extraction cartridges were used; instead, the extraction process consisted of the addition of an organic solvents, shaking, centrifugation, and dilution. An extensive validation process demonstrated an excellent linearity (R² ≥ 0.99) for 23-drug residues. The recovery of drugs in different matrices at two concentration levels (n = 6) was in the range of 82–119%. The method was proved to be repeatable and reproducible with intra/inter-day measurements (RSDs lower than 20%). The quantification limits of drug residues were in the range of 0.8 to 45.3 ug/kg, which is well below the maximum residue limits set by most regulatory authorities. This method was successfully applied to the routine analysis of 20 fish, poultry, and red meat samples (n = 60).