Epimerization and racemization of some chiral drugs in the presence of cyclodextrin and liposomes

The effects of alpha-, beta-, gamma- and dimethyl-beta-cyclodextrins (alpha-, beta-, gamma- and DM-beta-CyDs) and liposomes on epimerization or racemization of etoposide, ethiazide and carbenicillin were examined kinetically. alpha- and beta-CyDs accelerated both epimerization and hydrolysis of carbenicillin. They had no effect on epimerization of etoposide, and did not affect racemization and hydrolysis of ethiazide. DM-beta-CyD retarded epimerization of etoposide, hydrolysis of picroetoposide (which is an epimer of etoposide), and racemization and hydrolysis of ethiazide, but had no effect on epimerization and hydrolysis of carbenicillin. gamma-CyD retarded epimerization of etoposide and hydrolysis of picroetoposide. On the other hand, gamma-CyD accelerated epimerization of carbenicillin. It is suggested that the formation of inclusion complexes between CyDs and etoposide, picroetoposide and ethiazide inhibited the attack of bases such as OH- and buffer components, thereby retarding epimerization, racemization and hydrolysis. On the other hand, alpha-, beta- and gamma-CyDs increased the reactivity of carbenicillin through the OH group, accelerating its epimerization and hydrolysis. Liposomes retarded epimerization of etoposide, hydrolysis of picroetoposide and racemization of ethiazide. Liposomes did not affect epimerization and hydrolysis of carbenicillin. These differences in the effect of liposomes on reactivity may be interpreted in terms of the solubility of the drugs.     

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.     

Application of radioisotope XRF for the determination of noble metals in aqueous solutions

Radiometric methods of determination of platium and palladium (0.1 to 5% of Pt and 0.1 to 2% of Pd), gold and indium (0.01 to 1% of Au and 1 to 4 g In/l) and of platinum and rhodium (0.1 to 9% of Pt and 0.05 to 1% of Rh) in aqueous solution has been worked out. A suitable measuring device has been designed and constructed. The methods are based on the measurement of characteristic radiation of the L_α line for gold and platinum and of the K-series for indium, palladium and rhodium, as well as on the measurement of scattered radiation from a²³⁸Pu source. The r.m.s. error of the determination varies from 0.01 to 0.10% of Pt, 0.002 to 0.01% of Au and 0.01 to 0.15% of Pd depending on the concentration. In the case of Rh and In the errors are 0.008% and 0.04 g In/l, respectively.     

Latest achievements in the analytical chemistry of actinides

New methods for separation and determination of actinides, widely used in analysis of actinides in technological and environmental samples are reviewed. Special attention is paid to obtaining and stabilizing transplutonium elements. (TPE) in extreme oxidation states. Their use in analytical practice resulted in expanding possibilities of methods for separation and determination of TPE. Solvent extraction, sorption and extraction chromatography are the basic methods for separation of TPE. Solvent extraction, sorption and extraction chromatography are the basic methods for separation of TPE. Methods of separation in gas phase and some other methods such as precipitation and coprecipitation are applied, however, to a lesser degree. Trends of development of these methods including those of various types of membrane extraction that succeeded in separation of TPE in both trivalent and other valence states have been shown. Attention is paid mainly to consideration of modern methods for determination of actinides, special distinction of such methods being low limits of determination, high precision and selectivity. Alpha- and beta-spectrometric methods with semiconductor detectors are the most advanced among various methods based on registration of nuclear radiation. Tremendous success has been achieved in development of emission-spectrometric methods for determination of trace amounts of actinides and various impure elements occurring in samples of actinides. Sensitive mass-spectrometric methods are widely used for determination of both isotope composition and content of elements in various samples including those which are highly radioactive. More simple and precise titrimetric methods based on using oxidizing-reducing or complexing agents are developed successfully. A large number of coulometric methods for determination of americium and berkelium, characterizing high precision and selectivity as well as luminescence methods have been developed.     

Phenolic potential of Tannat, Cabernet-Sauvignon and Merlot grapes and their correspondence with wine composition

The phenolic potential of Tannat, Cabernet-Sauvignon and Merlot grapes was evaluated in 2001 and 2002 and its correspondence with the colour and composition of the respective wines was established. Three vineyards of each variety, situated in the south of Uruguay were considered. Two samples of each vineyard were taken at the moment of the harvest. Phenolic richness, extractable anthocyanins contents and total potential in anthocyanins of the grapes were estimated. Two fermentations on skins were carried out for each vineyard using 50 kg of grape in each one. The anthocyanic and total polyphenols contents of the musts were analysed every 24 h, and skins extractions were carried out in parallel in the laboratory. The duration of the maceration for each variety was decided in function of the analytical results in the grapes, musts and skins extractions. Wines were analysed 2 months after the alcoholic fermentation, determining its phenolic composition and colour. Tannat grapes presented anthocyanic and total polyphenols contents significantly higher in both years. Therefore, wines from this variety presented colour intensity and phenolic contents statistically higher than Cabernet-Sauvignon and Merlot. The correlations between the phenolic contents of the grapes, skins, musts and wines were very significant. Colour intensity and phenolic contents of the wines were highly correlated with the total polyphenols of the grapes and with anthocyanins of the grapes, skins, musts and wines. The estimate of the phenolic potential of the grapes and the extractability of the pigments allows to manage more adequately the fermentation on skins and is an interesting tool to predict the colour and the composition of the wines.     

岩相及煤阶对煤的燃烧特性的影响

为了确定手选富显微组分煤及焦的燃烧特性，从显微组分和煤阶的角度用热天平的燃烧曲线研究反应性，并给出焦的活化能。煤和焦的比表面积由液氮等温吸附求得，并用扫描电镜观察了焦的表面形态。用灰色关联法分析各显微组分和煤阶对反应性和表面形态的影响。结果表明，镜质组对煤和焦反应性和表面形态均有重大影响，煤的反应性受显微组分的影响比煤焦更显著，若不考虑矿物质的影响，则各因素对煤及焦反应性影响次序为Ｖ＞Ｒ＞Ｉ＞Ｅ。     

Determination of complex mixtures of volatile organic compounds in ambient air: an overview

This article reviews developments in the sampling and analysis of volatile organic compounds (VOCs) in ambient air since the 1970s, particularly in the field of environmental monitoring. Global monitoring of biogenic and anthropogenic VOC emissions is briefly described. Approaches used for environmental monitoring of VOCs and industrial hygiene VOC exposure assessments are compared. The historical development of the sampling and analytical methods used is discussed, and the relative advantages and disadvantages of sorbent and canister methods are identified. Overall, there is considerable variability in the reliability of VOC estimates and inventories. In general, canister methods provide superior precision and accuracy and are particulary useful for the analysis of complex mixtures of VOCs. Details of canister methods are reviewed in a companion paper. C. C. Austin is an Invited Scientist of the National Research Council of Canada.     

A sampling and analytical methodology for dental trace element analysis

The role of trace elements in human health and environmental pollution has developed into an extensive field of research. This study describes a sampling and analytical strategy to determine the trace element content of primary (deciduous) teeth and to assess their use in environmental health and nutrition studies. Exfoliated and extracted primary teeth were collected from 21 Ugandan and 27 UK children. The crown and root of the teeth were separated and the former digested and analysed for several elements by inductively coupled plasma mass spectrometry. The influence of country, tooth type, age and gender were statistically investigated in addition to within-person variation. A principal components analysis (PCA) was used to treat the data in a multivariate fashion and facilitated the moderation of outliers. The results demonstrated that country of origin has an important influence on the elemental composition of teeth and that tooth type should be controlled in these types of studies. Given such a restriction, the age and gender of the donor should have no effect and do not need to be controlled. In addition, where country of domicile, age and gender were controlled, the concentrations of most elements within a single tooth type were representative of an individual and therefore may be indicative of health status.     

纳米粒子的精准组装

纳米材料由于其独特的光、电、磁、力学等性质,成为了构建功能材料与器件的理想基元。实现纳米粒子的精确组装,是探究粒子之间的耦合聚集性质和制备宏观功能器件的基础。但是由于纳米粒子的小尺寸以及在溶液中运动的随机性与复杂性,精准控制纳米粒子组装体的形貌以及在空间中的相对位置仍存在巨大挑战。为了将纳米粒子组装成理想的有序结构,许多控制粒子组装的策略与方法得到发展。本文首先概述了纳米粒子自组装的控制方法与典型形貌,着重分析了影响粒子精准排布的因素与控制方法,并对纳米粒子及其组装体的光学性质与器件应用的最新研究进展进行了讨论,最后对目前纳米粒子精准组装所面临的挑战以及未来发展的方向进行了展望。     

稻杆的热溶剂提质及多级分离

采用1-甲基萘(1-MN)为溶剂,在不同温度下(250、300、350 ℃)对稻秆进行热溶剂提质及多级分离,获得3种主要固体产物:低分子量萃取物(soluble)、高分子量萃取物(deposit)和萃取残渣(residue),以及少量气体产物和液体产物。对各组分的元素组成、化学结构、物理化学特性等进行了详细分析,并采用ICP-MS测定了其碱金属和碱土金属(AAEM)含量。结果发现,低分子量萃取物收率随着温度的升高而增大,350 ℃时碳基收率达到33.48%。3种固体产物的碳含量和氧含量随着温度的升高而分别升高和降低,350 ℃时soluble、deposit的碳含量分别高达82.36%、80.59%,氧含量分别低至9.50%、12.03%,稻杆原样中高达86.99%的氧以H₂O或CO₂的形式释放。soluble几乎无灰,deposit的灰含量也低于1.50%。3种固体产物的高位发热量显著高于稻杆原样。FT-IR结果表明,稻杆热溶剂处理过程中除发生了脱水反应、脱羧基反应外,还有明显的芳香化反应。soluble和deposit的Na、Mg和K含量极低,而且随温度的升高其含量逐渐降低。总之,热溶剂提质及多级分离法实现了温和条件下的生物质脱水脱氧提质,并获得低灰低氧含量、高碳含量和发热量的多种产物,此方法有较好的应用前景。     

DABTZ as a new reagent for solid phase extraction and spectrophotometric determination of trace amount of Hg(II) in water sample

A novel sensitive and simple method for rapid and selective extraction, preconcentration and determination of mercury as its 2,2' diamino-4,4' bithiazole (DABTZ) complex by using octadecylsilica cartridges and spectrophotometry is presented. Extraction efficiency and the influence of flow rates of sample solution and eluent, pH, amount of DABTZ, type and least amount of eluent for elution of mercury complex from cartridges, break through volume and limit of detection were evaluated. Also the effects of various cationic and anionic interferences on percent recovery of mercury were studied. Average extraction efficiency > 90% was obtained by elution of the cartridge with minimal amount of solvent in the presence of interferences. A preconcentration factor of 152 and a detection limit of 10.92 ng mL(-1) were obtained. The method was applied to the recovery and determination of mercury in different water samples.     

剌梨利康饮对汞中毒大鼠汞铜锌含量的影响

用高汞水喂养大鼠８周,复制出慢性汞中毒模型,再分别自由饮用利康饮饮料和腹腔注射二巯基丙磺酸钠３周,探讨剌梨利康饮和二巯基丙磺酸钠对慢性汞中毒大鼠体内汞、铜、锌含量的影响。结果显示：慢性汞中毒引起血清、肝、脑和肾中汞含量升高的同时,引起血清、脑和肾中铜、锌含量及肝中锌含量降低;利康饮可降低血清和肾中汞含量,并可提高血清、脑和肾中铜、锌含量及肝含量;二巯基丙磺酸钠虽可降低血清、肝和肾中汞含量,升高血清     

顺序注射氢化物发生-原子荧光光谱法同时测定中草药中As和Bi

建立了一种顺序注射氢化物发生-原子荧光光谱法同时测定中草药中的As和Bi含量的方法,考察了光电倍增管负高压、As和Bi灯电流、原子化器高度、载气流量、屏蔽气流量等因素对测定结果的影响。结果表明,载流HCl的浓度为0.3 mol/L,KBH4质量浓度为10 g/L时,同时测定As和Bi的效果最佳;在最佳实验条件下,As和Bi的检出限分别为0.058μg/L和0.006μg/L,加标回收率为94.6%~103.2%,相对标准偏差小于3.0%,中草药试样中共存的离子对As和Bi的测定没有干扰。该法操作方便、快速,用于中草药中As和Bi的同时测定,具有很好的可行性和实用性。     

燃烧过程中碱/碱土金属对重金属迁移转化影响的研究进展

碱/碱土金属广泛存在于各种固体燃料中，在燃烧过程中碱/碱土金属与燃料中重金属及其他矿物发生复杂的物理化学反应，从而影响重金属的迁移和转化。本研究主要介绍了碱/碱土金属对As、Se、Pb和Cr四种重金属迁移转化的影响规律，包括碱金属和碱土金属对重金属迁移转化的影响，颗粒物团聚与黏结对重金属排放的影响三个方面。碱/碱土金属能够抑制重金属的挥发：碱金属与Cl元素的结合，降低了PbCl₂的生成；碱金属的存在有利于提升高岭土对Pb的吸附效率；碱/碱土金属可以与As和Se形成稳定的化合物。但同时需要注意碱/碱土金属与Cr的部分结合产物中，Cr以六价态存在，具有较高的毒性。碱/碱土金属对于团聚现象发生，分别起到了促进和抑制作用，适当含量的碱金属有利于减少重金属的释放。通过总结碱/碱土金属对重金属迁移转化的影响规律，以期为降低重金属的危害提供思路。     

Synthesis and Properties of Cerium and Titanium Oxide Thin Coatings for Corrosion Protection of 304 Stainless Steel

Powders and thin coatings of ceria and titania were synthesized from aqueous and solvent-based precursors. Thin coatings were deposited on polished 304 stainless steel coupons by dipping them in the appropriate sol-gel oxide precursors. The coatings were subsequently densified and crystallized at several hundreds of degrees. It was possible to obtain dense titania coatings by applying thin coatings of cerium dioxide prior to titania on stainless steel substrates. Underlayer ceria coatings proved to be pivotal in obtaining dense titania coatings and preserving the integrity of the stainless steel while going through the high temperature treatments. The effect of processing parameters such as the atmosphere of heat-treatment, and temperature on the microstructure and crystal structure of the films and powders of ceria and titania was investigated. X-ray diffraction was used to identify the crystal structure of films and powders upon heat-treatment. Electrochemical measurements in NaCl, and analytical techniques such as SEM and EDX were used to evaluate the corrosion performance and pitting morphology of coated samples. A composite coating of ceria and titania was able to prevent crevice corrosion and increase the pitting resistance of the 304 stainless steel relative to the uncoated substrate.     

智能响应材料在磷酸化肽和糖肽富集中的应用

蛋白质的磷酸化和糖基化作为研究最广泛的两种翻译后修饰(PTMs),在疾病的早期无创诊断、预后和治疗评估中表现出越来越大的潜力。蛋白质的异常磷酸化和糖基化经常被用于临床蛋白质组学研究和疾病相关生物标志物的发现。目前已有多种材料被开发用于磷酸化肽和糖肽的富集研究,其中,智能响应材料由于具有独特的响应特性,已被陆续报道用于磷酸化肽和糖肽的富集。智能响应材料可对外界刺激做出响应,发生结构和性质上的变化,将光、电、热、机械等信号转化为生物化学信号。响应分子是决定智能响应材料响应特性的先决条件,它们在不同刺激条件下(如温度、pH、光、机械应力、电磁场等)的可逆异构化将导致材料的宏观物理和化学性质的动态变化。与传统材料相比,智能响应材料可以可逆地“打开”和“关闭”,具有更好的可调控性。由于引起智能材料响应的刺激信号对其性能具有重要的影响,综述根据施加的刺激种类对智能响应材料进行分类,具体分为外源性响应材料和内源性响应材料,且分别总结了外源性响应材料、内源性响应材料以及内外源共同响应材料在磷酸化肽和糖肽富集方面的工作。此外,综述对智能响应材料在磷酸化肽和糖肽富集方面的发展前景进行了展望,并且提出了智能响应材料在其他蛋白质翻译后修饰方面的应用中存在的挑战。     

Esophageal carcinoma-associated proteins detected by two-dimensional polyacrylamide gel electrophoresis

Patterns of proteins of five surgically resected esophageal carcinomas were studied by two-dimensional polyacrylamide gel electrophoresis with silver staining. The samples of normal esophageal mucosa and esophageal carcinoma from the same patient were compared. Each gel had ca. 300 protein spots and had a similar pattern of proteins. Four spots were observed in all of the esophageal carcinomas that were not present in any of the normal mucosae. The molecular weights and isoelectric points were 46,000 and 5.3, 46,000 and 5.2, 36,000 and 4.7 and 33,000 and 5.1, respectively. One spot was observed in all of the normal mucosae but not in any of the esophageal carcinomas. Its molecular weight and isoelectric point were 27,000 and 5.3, respectively.     

Some pharmaceutical properties of 3-hydroxypropyl- and 2,3-dihydroxypropyl-beta-cyclodextrins and their solubilizing and stabilizing abilities

3-Hydroxypropyl- and 2,3-dihydroxypropyl-beta-cyclodextrins (3-HP- and DHP-beta-CyDs) with different degrees of substitution (D.S.) were prepared and their pharmaceutical properties were investigated. The aqueous solubility of 3-HP- and DHP-beta-CyDs was much higher than that of the parent beta-CyD and the dissolution of DHP-beta-CyD in water was endothermic. The acid- and alpha-amylase-catalyzed hydrolysis rates of 3-HP- and DHP-beta-CyDs were slower than those of the parent beta-CyD. The hemolytic activity (human erythrocytes) and local irritancy (rabbit muscle) of DHP-beta-CyD were considerably less than those of natural, methylated or other hydroxyalkylated beta-CyDs, and decreased with increasing D.S. The ability of the hydroxyalkylated beta-CyDs to remove cholesterol and proteins from human erythrocytes decreased with increasing D.S., and correlated well with their hemolytic activity. 3-HP-beta-CyD was a more effective solubilizer for poorly water-soluble drugs than the parent beta-CyD, and its stabilizing effect on chemically instable drugs was higher than that of the parent beta-CyD. The above data suggest a considerable pharmaceutical potential of 3-HP- and DHP-beta-CyDs as parenteral carriers.     

Analysis of anti-inflammatory dehydrodiisoeugenol and metabolites excreted in rat feces and urine using HPLC-UV

Dehydrodiisoeugenol (DDIE) is a lignan in the fruit of Myristica fragrans. It can be converted into several metabolites in in vitro and in vivo metabolism. In this study, the excretion of DDIE in urine and feces was investigated after intravenous (i.v.) and intragastric (i.g.) administration to rats. DDIE and its metabolites (M-1 and M-2) were measured using HPLC. The amount of DDIE and its metabolites excreted was higher in feces than in urine, suggesting that DDIE and its metabolites are eliminated primarily in the feces. Significant differences in the excretion levels of DDIE and its metabolites were seen between i.v. and i.g. administration. Greater amounts of DDIE and its metabolites were excreted following i.v. administration, suggesting that DDIE can exert a longer period of anti-inflammatory activity following i.g. administration. The accuracy, precision, recovery and stability of the analytical method in this study were satisfactory for the measurement of DDIE and its metabolites in rat urine and feces. Observations made in this study will contribute to understanding of the absorption, distribution, metabolism and excretion pathway of DDIE and will aid decision-making regarding the best mode of DDIE administration during treatment to maximize its anti-inflammatory effects.     

浙江省宁波、海宁部分地区幼儿头发和全血中的微量元素相关性研究

测定了浙江省宁波、海宁部分地区223例3-4岁健康幼儿同一个体头发和全血铅和锌含量,并研究两类样本两种微量元素的相关性。发现除血锌男女性别间含量差异不明显外,发中的锌、铅,全血中的铅均有显著的性别差异;无论是头发或是全血,男性或女性铅和锌均呈负相关且大多数有显著性;发铅和血铅男性和女性均呈显著正相关,而发锌与血锌女性也呈显著相关。本文还求出发铅与血铅、发锌与血锌含量间的一元线性回归方程。