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     

A confirmatory method for the simultaneous extraction,separation, identification and quantification of Tetracycline,Sulphonamide, Trimethoprim and Dapsone residues in muscle by ultra-high-performance liquid chromatography–tandem mass spectrometry according to Commission Decision 2002/657/EC

A rapid confirmatory multi-residue method for the analysis of tetracyclines, sulphonamides, trimethoprim and dapsone by UPLC-MS/MS is described. The method is able to quantify and confirm the following 19 compounds, oxytetracycline, tetracycline, chlortetracycline, doxycycline, sulfadiazine, sulfathiazole, sulfapyridine, trimethoprim, sulfamerazine, sulfamethizole, sulfamethazine, sulfamethoxypyridazine, sulfamonomethoxine, sulfachlorpyridazine, dapsone, sulfamethoxazole, sulfisoxazole, sulfaquinoxaline and sulfadimethoxine. Samples are extracted with 0.1 M EDTA and acetonitrile, which is then evaporated under a stream of nitrogen and reconstituted in water. Following centrifugation and filtering, an aliquot is analysed by UPLC-MS/MS using positive electrospray ionisation and multiple reaction monitoring. The method is deemed rapid as all analytes are extracted by a single extraction technique, with no solid-phase extraction clean up required. Validation is according to Commission Decision 2002/657/EC and was carried out for bovine, porcine, ovine and poultry species. Specificity, recovery, repeatability, reproducibility, CCα and CCβ data is presented.     

Simultaneous analysis of pesticides from different chemical classes by using a derivatisation step and gas chromatography-mass spectrometry

This work presents a new method to analyse simultaneously by GC–MS 31 pesticides from different chemical classes (2,4 D, 2,4 MCPA, alphacypermethrin, bifenthrin, bromoxynil, buprofezin, carbaryl, carbofuran, clopyralid, cyprodinil, deltamethrin dicamba, dichlobenil, dichlorprop, diflufenican, diuron, fenoxaprop, flazasulfuron, fluroxypyr, ioxynil, isoxaben, mecoprop-P, myclobutanil, oryzalin, oxadiazon, picloram, tau-fluvalinate tebuconazole, triclopyr, trifluralin and trinexapac-p-ethyl). This GC–MS method will be applied to the analysis of passive samplers (Tenax^® tubes and SPME fiber) used for the evaluation of the indoor and outdoor atmospheric contamination by non-agricultural pesticides. The method involves a derivatisation step for thermo-labile or polar pesticides. Different agents were tested and MtBSTFA (N-(t-butyldimethylsilyl)-N-methyltrifluoroacetamide), a sylilation agent producing very specific fragments [M−57], was retained. However, diuron could not be derivatised and the isocyanate product was used for identification and quantification. Pesticides which did not need a derivatisation step were not affected by the presence of the derivatisation agent and they could easily be analysed in mixture with derivatised pesticides. The method can be coupled to a thermal-desorption unit or to SPME extraction for a multiresidue analysis of various pesticides in atmospheric samples.     

MORPHOLOGY EVOLUTION IN PTFE AS A FUNCTION OF MELT TIME AND TEMPERATURE Ⅱ. LOW MOLECULAR WEIGHT FOLDED CHAIN SINGLE CRYSTALS AND BAND STRUCTURES

The effect of sintering dispersed and bulk, low molecular weight (Mn = 50,000 Da), nano-emulsion polytetrafluoroethylene (PTFE) particles near their melting point is described. With the nascent particles consisting of ca.75 nm diameter, hexagonal, single crystals, sintering at, e.g., 350℃, results, initially, in merger of neighboring particles,followed by individual molecular motion on the substrate and the formation of folded chain, lamellar single crystals and spherulites, and on-edge ribbons. It is suggested these structures develop, with time, in the mesomorphic "melt". Sintering of the bulk resin yields extended chain, band structures, as well as folded chain lamellae; end-surface to end-surface merger,possibly by end-to-end polymerization, occurs with increasing time.     

Alkaloids of Nitraria schoberi. N-Methylnitrarine

Nitrarine, isonitrarine, schoberidine, isoschoberidine, nitramidine, nitraroxine, nitraraine, schoberine, dehydroschoberine, tetramethylenetetrahydro--carboline, dl-vasicinone, deoxypeganine, deoxyvasicinone, dihydronitraraine, nitraramine, nitraramine N-oxide, tetramethylenetetrahydro--carboline N-oxide, tryptamine, and a new alkaloid N-methylnitrarine were isolated from the aerial part ofNitraria schoberiL. Spectral data and chemical transformations were used to establish the structure of the last, which was found in nature for the first time.     

367名幼儿智力发育与血中五种元素相关性分析

为探讨血铜、锌、钙、镁、铁5种元素对儿童智力的影响及其相关性,采用首都儿科研究所编制的0—6岁儿童神经心理发育量表,对367名2—4岁儿童进行现场智力测试并对抚养人进行问卷调查;采集其指尖末梢血,运用原子吸收光谱仪检测了儿童血铜、锌、钙、镁、铁5种元素含量。结果表明,调查对象血铜、锌、钙、镁、铁5种元素低下,检出率分别为25．1％、76．6％、5．7％、1．4％、37．1％,城乡儿童全血铜、锌、钙存在明显差异（P〈0．05）;儿童智力低下检出率为2．4％,儿童智能发育与其年龄、母亲文化水平、是否接受学前教育、血锌、铁呈正相关,与血钙、铜呈负相关。提示该地区2—4岁儿童血铜、锌、铁低下检出率较高,智能发育总体较为合理,但受血铜、锌、铁等多种因素影响,提高父母文化素质,加强儿童早期教育及营养有助于促进儿童智能发育。     

Multi-Elemental Analysis as a Tool to Ascertain the Safety and the Origin of Beehive Products: Development,Validation, and Application of an ICP-MS Method on Four Unifloral Honeys Produced in Sardinia,Italy

Despite unifloral honeys from Sardinia, Italy, being appreciated worldwide for their peculiar organoleptic features, their elemental signature has only partly been investigated. Hence, the principal aim of this study was to measure the concentration of trace and toxic elements (i.e., Ag, As, Ba, Be, Bi, Cd, Co, Cr, Cu, Fe, Hg, Li, Mn, Mo, Ni, Pb, Sb, Sn, Sr, Te, Tl, V, and Zn) in four unifloral honeys produced in Sardinia. For this purpose, an original ICP-MS method was developed, fully validated, and applied on unifloral honeys from asphodel, eucalyptus, strawberry tree, and thistle. Particular attention was paid to the method’s development: factorial design was applied for the optimization of the acid microwave digestion, whereas the instrumental parameters were tuned to minimize the polyatomic interferences. Most of the analytes’ concentration ranged between the relevant LoDs and few mg kg⁻¹, while toxic elements were present in negligible amounts. The elemental signatures of asphodel and thistle honeys were measured for the first time, whereas those of eucalyptus and strawberry tree honeys suggested a geographical differentiation if compared with the literature. Chemometric analysis allowed for the botanical discrimination of honeys through their elemental signature, whereas linear discriminant analysis provided an accuracy level of 87.1%.     

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%.     

电感耦合等离子体原子发射光谱测定混合稀土铜合金中稀土和非稀土元素

本文提出了用电感耦合等离子体原子发射光谱(ICP—AES)法直接测定混合稀土铜合金中13个非稀土和稀土元素。选用了合适的分析线对及ICP光源的工作参数。探讨了观察高度、功率、酸度、载气和基体量的变化对被测元素谱线强度的影响。不用化学分离,可一次同时测定La、Ce、pr、Nd、Sm、Sn、Zn、Fe、Al、Ni、Pb,Mg和Mn。测定范围(％):La_2O_3:0.096～6.4;CeO_2:0.24～16;Pr_6O_(11):0.0384～2.56;Nd_2O_3:0.096～6.4;Sn:0.096～3.2;Mg、Mn、Fe,Sm_2O_3:0.024～1.6;Zn:0.396～6.7;Pb:0.092～6.4;Ni:0.096～3.2;Al:0.0384～1.28。相对标准偏差±3.0～9.1％;回收率85～116％满足冶炼上的要求,得到了满意的结果。     

Unusual metals as electrode materials for electrochemical sensors

Although noble metals are still widely used in electroanalysis, a plethora of different nonconventional metals is now enriching the panorama of materials acting as the electrochemical transducer in sensing systems. In particular, Ti, Cu, Co, Fe, Mo, Ta, W, Rh, Bi, Sb, Te and Pb are discussed here in view of their peculiar physicochemical properties and of the interesting electrocatalytic activities ascribable to these elements and to the relevant metal oxide ultrathin films that spontaneously form at the electrode–solution interface. This behaviour, exploitable in electroanalysis for the detection of a number on analytes, is often accompanied by low price and high resistance to corrosion and to abrasion characterising these materials. These peculiarities encourage the possible use of the cited metals in a wide number of analytical frames, ranging from process control to bioimplantable sensing systems.     

Self-Assembling Drug Formulations with Tunable Permeability and Biodegradability

This review focuses on key topics in the field of drug delivery related to the design of nanocarriers answering the biomedicine criteria, including biocompatibility, biodegradability, low toxicity, and the ability to overcome biological barriers. For these reasons, much attention is paid to the amphiphile-based carriers composed of natural building blocks, lipids, and their structural analogues and synthetic surfactants that are capable of self-assembly with the formation of a variety of supramolecular aggregates. The latter are dynamic structures that can be used as nanocontainers for hydrophobic drugs to increase their solubility and bioavailability. In this section, biodegradable cationic surfactants bearing cleavable fragments are discussed, with ester- and carbamate-containing analogs, as well as amino acid derivatives received special attention. Drug delivery through the biological barriers is a challenging task, which is highlighted by the example of transdermal method of drug administration. In this paper, nonionic surfactants are primarily discussed, including their application for the fabrication of nanocarriers, their surfactant-skin interactions, the mechanisms of modulating their permeability, and the factors controlling drug encapsulation, release, and targeted delivery. Different types of nanocarriers are covered, including niosomes, transfersomes, invasomes and chitosomes, with their morphological specificity, beneficial characteristics and limitations discussed.