原位漫反射红外光谱研究氮氧化物在Ag-ZSM-5催化剂上的吸附态及选择性催化还原反应机理

利用原位分析方法对催化剂表面吸附态进行动态表征，对了解催化反应机理具有重要的意义。漫反射红外光谱是一种理想的原位方法，应用该方法在298－773K范围原位考察了以丙烯为还原剂，NO在Ag-ZSM-5催化剂上的吸附态及选择性催化还原过程。认为NO的选择性催化还原符合直接作用机理，还原的关键是形成有机－氮氧化物（R－NO2或R－ONO）中间体。O2的作用是使C3H6充分活化，并是有效产生有机－氮氧化物不可缺少的条件。     

Studies on synthesis and infrared and fluorescence spectra of new europium and terbium complexes with an amide-based open-chain crown ether

An amide-based open-chain crown ether ligand and its complexes with europium and terbium were synthesized. The complexes were characterized by elemental analysis, infrared spectra and conductivity. The europium and terbium ions were found to coordinate to the C=O oxygen atoms and pyridine nitrogen atoms. The fluorescence properties of these complexes in DMF and CH3OH/CHCl3 were studied. Under the excitation of UV light, these complexes exhibit characteristic fluorescence of europium and terbium ions. The solvent factors influencing the fluorescent intensity are discussed.     

Determination of inosine 5′-monophosphate and guanosine 5′-monophosphate in pig feed by capillary zone electrophoresis

A capillary zone clectrophoresis method was developed for the determination of IMP and GIMP, commonly used as flavor enhancers in poultry feed, in a real sample of complex composition. A baseline separation of inosine 5′-monophosphate and guanosine 5′-monophosphate was achieved within 10 min and the other components in the sample did not interfere with the separation. Quantitative results obtained from pig feed samples are presented. The separation conditions and experimental reproducibility are also discussed.     

4-(N-甲酰基-N′-邻氯苯基硫脲)-N-邻氯苯基苯氧乙酰胺的核磁共振研究

在超声波辐射下,以PEG-400为固-液相转移催化剂,用邻氯苯胺与双酰基异硫氰酸酯反应,合成出了一种新的化合物——4-(N-甲酰基-N′-邻氯苯基硫脲)-N-邻氯苯基苯氧乙酰胺。实验中观察到了取代和加成反应的竞争。利用元素分析,1H、13C、APT及二维核磁共振技术确定了所合成的新化合物的结构。给出了该化合物的化学位移数据。所得的结果对这类化合物的结构解析很有价值。     

Rhodium(I)‐Catalyzed [4 + 2] Cycloaddition Reactions of 2‐Alkylenecyclo‐butanols with Alkynes and (E)‐2‐Nitroethenylbenzene through C(sp2)—C(sp3) Bond Cleavage

An intermolecular [4 + 2] cycloaddition was realized through C—C bond cleavage in the presence of Rh(I) catalyst. The selective ring opening of 2‐alkylenecyclobutanols enables the generation of active alkenylrhodium species, which underwent smooth cross addition over alkynes and (E)‐2‐nitroethenylbenzene, leading to highly substituted all‐carbon six‐membered rings in a single step and in a complete atom economy.     

离子色谱-质谱联用技术测定污泥样品中的痕量高氯酸盐

建立了离子色谱-质谱联用技术测定活性污泥样品中高氯酸盐的分析方法。以高容量、强亲水性的IonPacAS20(2mm)阴离子交换柱为分析柱,EGC在线产生等浓度KOH为淋洗液,淋洗液经抑制成水后将样品带入质谱检测。ESI-MS-MS以多元反应监测模式监控100.8/84.9、98.8/66.9、100.8/68.9和98.8/82.9离子对,以98.8/82.9离子对的峰面积进行定量。该方法对高氯酸盐的检出限(S/N=3)为0.01μg/L,高氯酸盐在0.05~100μg/L浓度范围内具有良好的线性,线性相关系数r=0.9988。0.2μg/L的标准溶液重复进样9次,高氯酸盐峰面积的相对标准偏差(RSD)为2.3%。运用该方法测定采自不同地区的活性污泥样品中的高氯酸盐,并对样品加标回收,得回收率在88.5%~102.2%之间。     

稀土对MoSi2力学性能和抗氧化性能的影响

采用自蔓延和真空烧结方法制备了掺杂0．9％La2O3的MoSi2基复合材料，利用热重分析法，SEM和X射线考察了La2O3颗粒对MoSi2力学性能、抗氧化特性以及循环氧化后力学性能的影响。结果表明，与纯MoSi2相比，RE／MoSi2材料的弯曲强度和断裂韧性分别提高了46％和78％；稀土对MoSi2材料的强韧化机制主要是细晶强化、弥散强化和细晶韧化。RE／MoSi2的氧化增重是纯MoSi2的2．5倍，稀土使MoSiz材料的抗氧化性能降低。由于纯MoSi2材料氧化后的晶粒长大，其抗弯强度比氧化前降低了17％。稀土对MoSi2氧化时的晶粒长大倾向有抑制作用，使得RE／MoSi2材料的抗弯强度基本不变。     

不对称氢化反应

本文总结了各种手性膦配体以及它们的铑络合物在不对称氢化中的应用,并讨论了不对称氢化的机理和影响不对称诱导的各种因素。     

Theoretical and experimental study of the biamperometry for irreversible redox couple in flow system

The biamperometry for the direct determination of irreversible redox analytes in flow system has been proposed based on coupling two independent and irreversible couples to form the biamperometric detection scheme. In this work, the method is studied both theoretically and experimentally. Equations describing the current–voltage characteristics and the current–concentration relationship are presented. The influence of the applied potential difference (ΔE) and the half-wave potential difference (ΔE_1/2) between two irreversible couples on the method are discussed. It shows that small ΔE_1/2 is favorable to construct the biamperometric detection system and to achieve high sensitivity and selectivity. Increasing ΔE leads to an increase in sensitivity. This is, however, accompanied by a decrease in selectivity and signal-to-noise ratio. To construct the biamperometric scheme for the irreversible systems with large ΔE_1/2, two approaches, adjusting acidity of supporting electroyte or adding new irreversible couple, are proposed by taking uric acid/platinum oxide and phenol/permanganate systems as examples. Uric acid and phenol are, respectively, detected in a flow injection system with a biamperometric detector.