锂/铌镁催化剂中碳酸锂的熔点与甲烷氧化偶联反应的活化和失活的关系

研究了铌掺杂的Li/MgO甲烷氧化偶联催化剂的反应性质及铌的助剂作用。铌的引入使得该催化剂上甲烷氧化偶联反应的活化温度降低50℃以上, 使此温度降到了催化剂中碳酸锂的熔点附近。试验观察到部分催化剂上甲烷氧化偶联反应的活性曲线在碳酸锂的熔点附近有一转折, 这一转折现象的出现与否及程度取决于制备条件。在碳酸锂的熔点附近, 含有铌的催化剂得到活化, 观察到无稀释气体时的反应引燃现象, 即温度增加几度活性便达到最大值。当在比碳酸锂熔点稍高的温度下且不稀释时反应, 含铌催化剂活性很高但很快失活, 在稍低于此熔点下则不失活, 但活性较低。这些试验结果表明, 含铌催化剂的活化与失活均与催化剂中的碳酸锂的相变化有关。试验还观察到了在稍高于碳酸锂的熔点下做寿命试验时, 甲烷氧化偶联反应的振荡现象。     

铁丝在氧气中燃烧的实验改进

“铁丝在氧气中燃烧”是初中化学教材中证明氧气化学性质的一个演示实验,该实验证明了氧气比较活泼,在一定条件下可以和金属发生剧烈反应。但是与木炭在氧气中燃烧、硫在氧气中燃烧、蜡烛在氧气中燃烧的演示实验相比,铁丝在氧气中燃烧的实验存在着一些不足的地方,针对这些不足,对铁丝在氧气中燃烧的实验进行了改进。1实验存在的问题按照教材要求,铁丝在氧气中燃烧的实验,须将铁丝绕成螺旋状,并在铁丝的末端绑上一根火柴杆,实验时先将火柴杆点燃,待火柴杆将燃尽时,迅速伸入盛满氧气的集气瓶中。这样的操作存在2个问题:第一,火柴燃烧的程度不…     

提高纤维素酶水解效率和降低水解成本

在我国可大量转化乙醇的是纤维质材料.纤维质材料转化乙醇的关键问题是纤维质转化为糖的过程,提高纤维素酶转化效率的方法有:(1)对纤维质材料进行预处理;(2)研究纤维素酶的最适作用条件;(3)纤维素酶的重复利用;(4)合理的发酵工艺等.本文分析了纤维素的结构以及纤维素酶的作用方式,总结了目前研究较多的几种纤维质材料预处理方法,及其对纤维素酶水解率的影响,并对研究纤维素酶的最适作用条件、纤维素酶的重复利用以及合理的发酵工艺进行了综述和分析.     

银镜的实验室制备

在高中化学“烃的衍生物”,“糖类、油脂、蛋白质”2章的教学中,安排了有关银镜反应的演示实验,其目的是通过实验证明含有醛基的有机物具有还原性。按照教材的方法进行实验操作,往往由于水浴的温度掌握不好,制得银镜的效果不理想。为了快速明显地观察到银镜的产生,采用平板玻璃     

2011年国际化学年《高分子通报》征稿启示

2011年是联合国确定的国际化学年,为纪念化学学科所取得的成就以及对人类文明的贡献,2011年化学年的主题是我们的生活,我们的未来。     

CO催化氧化用纳米材料及其最新研究成果

当前,环境问题和能源危机已经威胁到人类的健康和生存。用于环境治理和化学能源合成新概念的纳米催化材料越来越受到人们的关注。催化作为一个特殊的纳米现象,是纳米材料应用领域的一个重要方向,在环境净化、能量转化和新化学品的生产等方面具有广泛的应用前景。早期的一氧化碳(CO)催化氧化研究主要集中在催化剂的制备方法以及制备条件对催化反应的影响等方面。本文针对CO催化氧化这一基础课题,以影响CO催化氧化的关键因素(如金属颗粒的大小,金属与载体之间的相互作用以及载体本身的作用等)为主线,简要概述了近年来CO催化氧化的催化机理及相关催化剂的最新研究进展。同时,结合我们课题组的一些最新研究结果,进一步指出了纳米材料在CO催化氧化方面还存在的一些值得关注的问题,并对未来CO氧化催化剂的研究做出展望,提出一些可行的研究方向。     

漫话饮用水消毒剂

饮用水消毒剂的种类很多,国内大规模工业化生产主要还是用氯气来消毒。饮用水消毒的目的是杀灭水中可能引起霍乱、伤寒、痢疾等疾病的病菌与病毒。随着科学技术的发展和人们生活水平的提高,饮用水消毒剂也在不断发展,安全、高效、经济的消毒剂将成为主流。下面就目前使用或已开     

序言——《高分子通报》创刊20周年回顾

《高分子通报》是1988年10月创刊的。回顾20年来的发展历程,《高分子通报》是在各级领导的关怀下不断成长的,是在我国高分子科学领域的专家、学者的大力支持下发展的,也是在历届编委、编辑艰苦奋斗,辛勤耕耘下不断提高和前进的。早在1981年冬,昆明功能高分子学术会议中就正式提     

羟基甘氨酸溶液性质研究

采用核磁共振等仪器分析与官能团鉴定相配合的方法，对乙醛酸与铵盐反应形 成的羟基甘氨酸进行了研究。确认了羟基甘氨酸的结构，探讨了羟基甘氨酸的水溶 液中的主要存在形式，得出了与普遍接受的羟基甘氨酸在水溶液中不稳定的观点相 悖的结论。并对羟基甘氨酸的溶液稳定性，氨解，水解进行了研究。本结果为乙醛 酸以及羟基甘氨酸在有机合成上的应用提供了依据。     

在血卟啉衍生物光敏体系中DMPO捕集自由基的ESR研究

光照血卟啉衍生物(HPD)用于肿瘤的诊断和治疗已取得很大的成效,对此药理过程的分子机理的探索也开始引起生物和化学工作者的重视.我们的实验表明,在HPD光敏体系中自由基起着重要作用,特别是羟基自由基可能是HPD光致杀伤肿瘤细胞的主要原因.HPD光敏过程所产生的自由基的寿命极短,用化学方法或用一般ESR直接检测非常困难,但可被     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

酞菁染料的金属化和溴化与光物理影响的研究

以α位(2,4-二特戊基)苯氧基邻苯二腈作为环合前体,制备了多种金属酞菁,产物经元素分析、紫外、红外、核磁氢谱等分析手段进行表征.并选择了部分酞菁进行溴化,其中着重研究了不同中心金属以及溴化对染料Q带吸收的影响.结果表明,酞菁染料的金属化对于其Q带吸收影响很大,多数染料金属化后会出现蓝移,而选择合适的条件进行溴化,可以使得金属酞菁的Q带吸收出现一定程度的红移,其中部分溴化金属酞菁的吸收波长与光信息产业中使用的近红外激光器很接近,具有潜在的实用价值.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

OPTIMIZATION OF THE SYNTHESIS OF ACRYLAMIDE HYDROGEL BY γ-RAY IRRADIATION

Hydrogels have been synthesized from 10%, 20%, 30%, 40%, 50% and 60% aqueous solutions of acrylamide monomer by gamma radiation employing doses in the range of 0.2-30 kGy from a Co-60 source. The effect of solution concentration, γ-ray dose, pH and time was studied in order to observe the optimizing conditions in the characterization of hydrogels. Gel fraction increases with dose for all concentrations indicating hundred-percentage conversion of gel at doses ≥5 kGy for homogenous solutions in the range of 20%-50% concentration. On the other hand, 10% solution provides conversion less than 86% even at 30 kGy, whereas 60% monomer makes an inhomogeneous solution which stile gives about 100% gel fraction. Swelling of hydrogels under water with respect to time varies with both the doses and concentrations due to the change of crosslinking density in the gels. The maximum volume change of hydrogels during swelling and water desorption mainly occurs within 24 h. Swelling is also enhanced with the rise of pH due to change of ionic content of the solvent. Considering the amount of gel fraction and the properties of hydrogel, the samples prepared from 20% solution at 5kGy show better results. Moreover, the effect of bacteria on hydrogel was found to be nil, suggesting a prohibition of growth of microorganism in it.     

ELECTROCHEMICAL POLYMERIZATION OF ANILINE IN PHOSPHORIC ACID AND THE PROPERTIES OF POLYANILINE

The behavior of the electrochemical polymerization of aniline in a weak acid, phosphoric acid, is very similar to that in strong acids, i.e. its polymerization rate increases quickly with the electrolysis time. The FTIR spectra of polyaniline samples synthesized in phosphoric acid indicate that the counter ion H2PO4^- is present in both the oxidized form and the reduced form of polyaniline. The counter ion plays an important role in adjusting the pH value at the electrode surface of polyaniline during the oxidation and reduction processes. As a result, a pair of redox peaks still appear in cyclic voltammograms of polyaniline in a solution of sodium sulfate of pH 5.5 and in a solution of NaH2PO4 of pH 7.0,respectively, at low potential scan rate; and the color of polyaniline film also changes with applied potential at pH 7.0. Thus,the pH region for the electrochemical activity and the electrochromism of polyaniline is extended to pH 5.5 for a solution of sodium sulfate and to pH 7.0 for a solution of NaH2PO4. The conductivity of polyaniline is 3.3 S cm^-1, depending on the concentration of phosphoric acid used in the stage of polymerization of aniline. The result of elemental analysis of polyaniline is presented here.     

Contributions to the Chemistry of the Binary Compounds of the Transition Elements

Phase and structural relationships of the sulfur, selenium, and tellurium compounds of the 4d and 5d transition elements of groups IV to VII of the periodic system are discussed. Homologous elements behave very similarly with respect to the chalcogens, and this is particularly the case for niobium and tantalum, and for molybdenum and tungsten. However, zirconium, niobium, and molybdenum have a greater tendency towards formation of chalcogen-poor phases than their homologues hafnium, tantalum, and tungsten. Subchalcogenides are known only for zirconium and niobium. The number of phases and the tendency towards formation of solid solutions are considerably smaller among the tellurides than among the sulfides and selenides. The crystal structures of the telluride phases also differ from those of the sulfide and selenide phases of analogous composition. In addition, a review of the phase and structural relationships of the arsenic and antimony compounds of the 4d and 5d transition elements of groups V to VII is given.     

液晶聚合物/柔性链聚合物共混体系相分离形态

利用元胞动力学方法在二维情况下对浓度、取向序参量的含时Ginzberg-Landau方程进行数值求解,研究了液晶聚合物/柔性链聚合物共混体系的相分离动力学,考察了浓度、取向有序过程的耦合对相分离形态的影响.结果表明,此耦合作用对相分离的时间进程以及相分离图样的空间排布都有影响.液晶聚合物的取向有序相当于增加了两组分间的不相容性而促进两相分离;两个序参量在热力学方面的耦合使液晶聚合物趋向于沿着界面方向取向,而动力学方面的耦合使液晶聚合物分子沿着其取向方向扩散,相分离图样的空间排布由这两种效应共同决定通过极化率张量的定义用数值方法模拟得到了相分离体系的小角光散射图样,结果表明,散射强度分布具有方位角依赖性,它是由浓度、取向序参量的空间变化共同决定的.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

LOW DENSITY POLYETHYLENE/CLAY NANOCOMPOSITES MODIFIED BY ETHYLENE COPOLYMERS： EFFECTS OF FUNCTIONALIZED SEGMENTS ON MORPHOLOGY

Melt extrusion was used to prepare binary nanocomposites of ethylene copolymers and organoclay and trinary nanocomposites of low-density polyethylene （LDPE）, ethylene copolymer and organoclay. X-ray diffraction （XRD） and transmission electron microscopy （TEM） were used to analyze the structure of the clay phase and the morphology of the nanocomposites. Influences of the comonomer in the copolymer and the content of the copolymer on the morphology of the resulting nanocomposites were discussed. The binary and the trinary composites may form intercalated or exfoliated structures depending on the interaction between the copolymer and the clay layers and the content of the copolymer.