苯和乙烯一步法合成苯乙烯反应研究

首次采用苯和乙烯在无氧存在下, 于多种固体酸和金属负载HZSM-5分子筛催化剂上反应直接得到苯乙烯与其它固体酸相比, HZSM-5分子筛催化剂表现出最高的反应活性和较高的对苯乙烯的选择性。HZSM-5分子筛负载不同金属后, 苯乙烯的选择性均有明显提高, 其中以Co/HZSM-5、Fe/HZSM-5和Pd/HZSM-5催化剂显示出较高的反应活性和苯乙烯选择性。反应温度、苯烯比、金属负载量、液空速、催化剂的焙烧及还原温度均会不同程度地影响反应转化率和产物分布。     

β-环糊精-氧化石墨烯超分子杂化体的构筑及应用进展

β-环糊精是由7个D-吡喃葡萄糖单元通过α-1,4-糖苷键键连成环的超分子主体分子，“内疏水、外亲水”的独特结构赋予了其优异的分子识别能力；氧化石墨烯类材料凭借其优良特性成为近几年的研究热点。由β-环糊精和氧化石墨烯构筑的超分子杂化体在兼具二者特有性能的基础上又有新功能的引入。本文综述了β-环糊精-氧化石墨烯超分子杂化体的构筑方式，按二者间的连接方式，分别为共价键和非共价键两种连接方式，其中通过共价键连接是目前最主要的构筑方式；此外对β-环糊精-氧化石墨烯超分子杂化体的特征和表征进行了简述。同时对β-环糊精-氧化石墨烯超分子杂化体在水污染处理、电化学检测、药物控释和催化等领域的应用进展进行了综述。最后对该超分子杂化体在构筑和应用上的发展趋势进行了展望。     

Interactions between Cytochrome c and DNA Strands Self-Assembled at Gold Electrode

In this work, we reported the investigation on the interaction between DNA strands self-assembled at gold electrodes and an electron transfer protein, cytochrome c. We observed that cytochrome c exhibited well-defined electrochemistry in both double-stranded and single-stranded DNA films. This suggested that the electron transfer reaction of cytochrome c arose possibly due to the electron hopping along DNA strands rather than wiring along the double helix. We also compared the heterogeneous electron transfer rate of cytochrome c with that of a ruthenium complex, which further confirmed this mechanism.     

竹红菌甲素衍生物13－SO_3Na－DDHA电化学及光诱导还原的研究

本工作研究了化合物１３－ＳＯ＿３Ｎａ－ＤＤＨＡ在不同ｐＨ的缓冲溶液中的电化学氧化还原行为．实验证明：化合物中羰基的还原电位与ｐＨ之间存在线性关系，其直线的斜率为６０ｍＶ／ｐＨ．并证明了此过程为一步两电子、两质子还原过程：Ｑ＋２Ｈ￣＋＋２ｅ＝ＱＨ＿２．ＤＭＦ作为非质子溶剂，具有很好的稳定自由基的作用．向缓冲溶液中加入ＤＭＦ后，化合物１３－ＳＯ＿３Ｎａ－ＤＤＨＡ为两步单电子还原过程，相应溶液中的光诱导电子转移吸收光谱证实了以上电化学的结果．     

直接凝固注模成型Si_3N_4及SiC陶瓷──基本原理及工艺过程

直接凝固注模成型（ｄｉｒｅｃｔｃｏａｇｕｌａｔｉｏｎｃａｓｔｉｎｇ，ＤＣＣ）是一种崭新的（准）净尺寸陶瓷成型方法。本文报道了采用此法成型Ｓｉ_３Ｎ_４及ＳｉＣ陶瓷的基本原理和工艺过程。ＤＣＣ成型工艺过程为把高固相含量低粘度的陶瓷浆料浇注到无孔模具中，事先加入到浆料中的生物酶及化学物质通过改变浆料的ｐＨ或电解质浓度来改变浆料的胶体化学行为，从而使浆料原位凝固，得到有足够脱模强度的陶瓷坯体。ＤＣＣ成型的特点为坯体密度高（理论密度的５５％～７０％），坯体均匀，不用或只需少量的有机添加剂（少于１％），可成型大尺寸、复杂形状、高可靠性的陶瓷部件。     

Electrochemical copolymerization of carbazole and 3‐methylthiophene

The copolymerization of carbazole (CZ) and 3‐methylthiophene (3MeT) was successfully performed electrochemically in freshly distilled boron trifluoride diethyl etherate by direct anodic oxidation of the monomer mixtures, although the oxidation potentials of CZ and 3MeT were quite different. The electrochemical properties of the copolymers were studied with cyclic voltammetry. The influence of the applied polymerization potential on the synthesis of the copolymers was investigated. The higher potential favored the incorporation of 3MeT units into the copolymers. The insertion of 3MeT units into polycarbazole (PCZ) was helpful in improving the conductivity of PCZ. The novel copolymers had the advantages of both PCZ and poly(3‐methylthiophene), that is, good redox activity, good thermal stability, and high conductivity. The structure and morphology of the copolymers were investigated with ultraviolet–visible, infrared spectroscopy, thermal analysis, and scanning electron microscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1877–1885, 2006     

Prediction of Experimental Methanol Decomposition Rates on Platinum from First Principles

A microkinetic model for methanol decomposition on platinum is presented. The model incorporates competitive decomposition pathways, beginning with both O–H and C–H bond scission in methanol, and uses results from density functional theory (DFT) calculations [Greeley and Mavrikakis, J. Am. Chem. Soc. 124 (2002) 7193, Greeley and Mavrikakis, J. Am. Chem. Soc. 126 (2004) 3910]. Results from reaction kinetics experiments show that the rate of H₂ production increases with increasing temperature and methanol concentration in the feed and is only nominally affected by the presence of CO or H₂ with methanol. The model, based on the values of binding energies, pre-exponential factors and activation energy barriers derived from first principles calculations, accurately predicts experimental reaction rates and orders. The model also gives insight into the most favorable reaction pathway, the rate-limiting step, the apparent activation energy, coverages, and the effects of pressure. It is found that the pathway beginning with the C–H bond scission (CH₃OH→H₂COH→HCOH→CO) is dominant compared with the path beginning with O–H bond scission. The cleavage of the first C–H bond in methanol is the rate-controlling step. The surface is highly poisoned by CO, whereas COH appears to be a spectator species.     

对二甲苯直接电解氧化反应的研究

研究了在有机溶剂、支持电解质和碳棒存在下，对二甲苯的直接电解氧化反应，使用GC－MS方法分析鉴定了主要电解氧化产物，讨论了电解氧化产物成分随电解时间的变化规律，提出了对二甲苯的直接电解氧化反应过程。     

Analysis of the polyethylene glycol glucosides and FA esters thereof by atmospheric-pressure ionization MS

Polyethylene glycol (PEG) glucosides (PEGG) and the PEGG esters of lauric acid were analyzed by atmospheric-pressure ionization MS (API-MS) with electrospray ionization. Straightforward mass characterization of the complex mixtures could be achieved without prior chromatographic separation. The constituents were identified on the basis of quasi-molecular ions. Individual components could be observed as protonated molecular ions [M+H]⁺ and/or as their NH₄ ⁺, Na⁺, or K⁺ adducts in positive ion mode. The mass spectrometric investigation showed that mixtures of PEGG consisted of monoglucoside, diglucoside, polyglucoside, and free PEG. The esterification product is a mixture of two types of nonionic surfactants: PEG-laurates and PEGG-laurates. The reasons for distortion of the quasi-molecular ion intensities and the stabilization of adduct ions were discussed. The rapid and highly sensitive API-MS analysis technique proposed here is well suited for direct characterization of complex mixtures and suitable for development as a routine analytical method.     

新型螺旋式浓硝酸漂白塔及其应用

针对传统的帽罩式浓硝酸漂白塔存在的缺点和不足，找出原因并予以改进，开发研制出螺旋式浓硝酸漂白塔，改进了工艺状况，减少了维修工作量，达到了节能降耗的目的，确保了直接法浓硝酸装置的长周期运行。