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     

Comparative chronic toxicity,including tumorigenicity,of gallium arsenide and arsenic trioxide intratracheally instilled into hamsters

Chronic toxicity, including tumorigenicity, of gallium arsenide (GaAs) and arsenic trioxide (As₂O₃) were studied using Syrian golden hamsters given intermittent intratracheal instillations. GaAs particles (0.25 mg × 15 times/animal) were likely to produce relatively severe lung damage and the survival of the animals was shortened significantly compared with a control group. The tumor incidence of each group examined was GaAs (3.3%), As₂O₃ (3.3%) respectively, at a dose of 3.75 mg total metal given during 15 weeks. In this experiment, both arsenic trioxide and gallium arsenide had no apparent carcinogenicity or tumorigenicity.     

Interference of arsenic trioxide on magnesium dependent polymerization of microtubule proteins

Prevention of microtubule polymerization is considered as one of the promising approaches towards inhibition of cell proliferation, especially in treatment of malignancies. Arsenic trioxide, As₂O₃, is being successfully used in the treatment of human lymphoma, while the mechanism of its therapeutic function is still under investigation. Experiments were designed to determine if indeed As₂O₃ interferes with polymerization of nanotube microtubule. Microtubules were extracted from sheep brain and their interaction with arsenic trioxide was examined by spectrometery. Electrical conductometry of 2 mM MgSO₄ solution containing various concentrations of As₂O₃ was studied in order to determine their possible interaction. Transmission electron microscopy was used to show microtubule structure in the presence of arsenic trioxide. Fluorometric characteristics of tubulin dimer were examined in presence of varying concentrations of arsenic trioxide. It is concluded that arsenic trioxide interacts with Mg²⁺ ion around GTPase site of β-tubulin, resulting enhancement of depolymerization of the microtubule polymer.     

Analytical artefacts in the speciation of arsenic in clinical samples

Urine and blood samples of cancer patients, treated with high doses of arsenic trioxide were analysed for arsenic species using HPLC-HGAFS and, in some cases, HPLC-ICPMS. Total arsenic was determined with either flow injection-HGAFS in urine or radiochemical neutron activation analysis in blood fractions (in serum/plasma, blood cells). The total arsenic concentrations (during prolonged, daily/weekly arsenic trioxide therapy) were in the μg mL⁻¹ range for urine and in the ng g⁻¹ range for blood fractions. The main arsenic species found in urine were As(III), MA and DMA and in blood As(V), MA and DMA.With proper sample preparation and storage of urine (no preservation agents/storage in liquid nitrogen) no analytical artefacts were observed and absence of significant amounts of alleged trivalent metabolites was proven. On the contrary, in blood samples a certain amount of arsenic can get lost in the speciation procedure what was especially noticeable for the blood cells although also plasma/serum gave rise to some disappearance of arsenic. The latter losses may be attributed to precipitation of As(III)-containing proteins/peptides during the methanol/water extraction procedure whereas the former losses were due to loss of specific As(III)-complexing proteins/peptides (e.g. cysteine, metallothionein, reduced GSH, ferritin) on the column (Hamilton PRP-X100) during the separation procedure. Contemporary analytical protocols are not able to completely avoid artefacts due to losses from the sampling to the detection stage so that it is recommended to be careful with the explanation of results, particularly regarding metabolic and pharmacokinetic interpretations, and always aim to compare the sum of species with the total arsenic concentration determined independently.     

Thermodynamic and kinetic studies of As2O3 toxicological effects on human insulin in generation diabetes mellitus

The interaction of arsenic trioxide with human insulin was investigated by circular dichroism (CD), cyclic voltammetry and electrophoresis techniques. The interfacial behavior of insulin in presence of As₂O₃ onto the Ag electrode surface was studied at 310 K in phosphate buffer solution (PBS). According to Far-UV CD spectroscopy results, As₂O₃ caused to decrease in structural compactness and variety of alpha helix into beta structures. Near-UV CD indicated that As₂O₃ dissociates disulfide linkage in insulin structure. The kinetic parameters, including charge-transfer coefficient and apparent heterogeneous electron transfer rate constant were also determined. The thermodynamic parameters of insulin denaturation in presence of arsenic trioxide were calculated and reported. The obtained results indicated strong adsorption of insulin in presence of arsenic trioxide onto the Ag surface via chemisorptions.

     

Arsenic speciation in saliva of acute promyelocytic leukemia patients undergoing arsenic trioxide treatment

Arsenic trioxide has been successfully used as a therapeutic in the treatment of acute promyelocytic leukemia (APL). Detailed monitoring of the therapeutic arsenic and its metabolites in various accessible specimens of APL patients can contribute to improving treatment efficacy and minimizing arsenic-induced side effects. This article focuses on the determination of arsenic species in saliva samples from APL patients undergoing arsenic treatment. Saliva samples were collected from nine APL patients over three consecutive days. The patients received 10 mg arsenic trioxide each day via intravenous infusion. The saliva samples were analyzed using high-performance liquid chromatography coupled with inductively coupled plasma mass spectrometry. Monomethylarsonous acid and monomethylmonothioarsonic acid were identified along with arsenite, dimethylarsinic acid, monomethylarsonic acid, and arsenate. Arsenite was the predominant arsenic species, accounting for 71.8 % of total arsenic in the saliva. Following the arsenic infusion each day, the percentage of methylated arsenicals significantly decreased, possibly suggesting that the arsenic methylation process was saturated by the high doses immediately after the arsenic infusion. The temporal profiles of arsenic species in saliva following each arsenic infusion over 3 days have provided information on arsenic exposure, metabolism, and excretion. These results suggest that saliva can be used as an appropriate clinical biomarker for monitoring arsenic species in APL patients.

Methyl transfer from a hydrophobic vitamin B12 derivative to arsenic trioxide

The methylation reaction of arsenic trioxide conducted at 37 °C and pH 7.0 for 24 h using hydrophobic methylated vitamin B₁₂, (methyl) (aquo) heptamethylcobyrinate perchlorate, CH₃B₁₂ ester, as a methyl donor in the presence of reduced glutathione (GSH) yielded monomethylarsonous acid (MMA), dimethylarsinic acid (DMA), and trimethylarsine oxide (TMAO) as products with a methylation rate over 95%. In contrast, when methylcobalamin (CH₃B₁₂) was used as the methyl donor, only MMA and DMA were produced and the methylation rate dropped to around 20%. Reductive demethylation of a methyl-corrinoid coordination complex mediated by GSH is suggested as a mechanism of methyl transfer to arsenic trioxide. The differences observed for different corrinoid coordination complexes with respect to the reactivity of methyl transfer to arsenic is ascribable to differences inherent in the base-on (CH₃B₁₂) and base-off (CH₃B₁₂ ester) natures of the compounds.     

砒霜——亦敌亦友,千年情仇

It's believed that everyone is familiar with arsenic trioxide. It has been one of the most famous poisons since ancient time. Because of this, it is largely unfairly described. In this article, we combine research results with clear chemical knowledge and terms, in order to prove that arsenic trioxide can also be useful in human life and production.     

A highly accurate and precise method for the assay of chromium metal and chromium(III) oxide

A method capable of a precision of 3 to 5 parts in ten thousand has been developed for the routine assay of high purity chromium metal and chromium trioxide. Use has been made of the favourable gravimetric factor of ferrous ammonium sulfate and of an amperometric end-point. Comparison with the arsenic trioxide method was made.     

Industries using arsenic and arsenic compounds

This paper reviews industries using arsenic and arsenic compounds such as wood preservatives and agricultural chemicals, the use of arsenic trioxide in glass manufacture, and the applications of metallic arsenic in non-ferrous alloys and of high-purity arsenic in the electronics industry.     

Arsenic compounds in marine and terrestrial organisms: Analytical,chemical and biochemical aspects

Arsenic has a reputation as a poison, because arsenic trioxide was used during medieval times as an agent for murder. Lingering memories of these events make any arsenic-containing material suspect. Toxicity is a property of a specific compound and varies with the composition and structure of compounds. Developments in analytical methodology made it possible not only to determine total arsenic in a variety of matrices but also arsenic compounds. Knowledge about the arsenic cycle in marine systems has expanded considerably during the past decade. The marine arsenic cycle appears to be more complex than the cycle in the terrestrial environment. More attention must be given to the minor arsenic-containing compounds detected in organisms and experiments should be undertaken that provide information about the biochemical pathways used for the transformation of arsenic compounds.