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.     

亚麻的化学组成和微观结构对染色性能的影响

本文通过X衍射法、纤维化学成分分析法测试了亚麻纤维的微观结构、化学成分，通过对亚麻进行液氨整理改变其结晶度和取向度，从而测得亚麻的结晶度和取向度对染色性能的影响，利用碱煮、H2O2和NaOCl漂白处理降低了亚麻中木质素和半纤维素的含量，从而测量得木质素和半纤维素含量对亚麻上染率的影响。结果表明亚麻的上染率随着结晶度的降低呈线性上升，随着取向度的降低而上升；随着木质素和半纤维素含量的降低而呈上升趋势。     

Impact of the physical and topographical characteristics of adsorbent solid-phases upon the fluidised bed recovery of plasmid DNA from Escherichia coli lysates

A comparison is made of the performance of two types of adsorbent solid phases (commercially sourced Streamline composites and custom-assembled Zirblast pelliculates), derivatised with similar anion exchange chemistries and applied to the recovery of plasmid DNA from Escherichia coli extracts prepared by chemical lysis and coarse filtration. Streamline and Zirblast adsorbents were characterised by average particle diameters of 200 and 95 microm, densities of 1.16 and 3.85 g/m2, and small ion capacities of 170 and 8 micromol/ml settled adsorbent, respectively. Detailed analysis of products and impurities in a full operational cycle of adsorption, washing, pre-elution, elution and regeneration processes was enabled by the harnessing of a battery of analyses for nucleic acid and organic solute content of feedstocks and bed effluents exploiting ultra-violet spectrophotometry, agarose gel electrophoresis and specific reactions with the fluorescent probe PicoGreen. In comparative tests operated under near identical conditions, Streamline and Zirblast adsorbents exhibited plasmid recoveries of 76 and 90% of bound product characterised by purity ratios (relative PicoGreen and A254 estimates of mass) of 9 and 32, respectively. Conclusions are drawn regarding the specific impact of the physical and topographical characteristics of solid-phase geometry upon product throughput, achievable product purity, process time-scales and operational economics for the manufacture of plasmid DNA.     

视网膜脱离后PVR的形成与氧自由基和锌、铜关系的研究

为探讨氧自由基和锌、铜在视网膜脱离后增殖性玻璃体视网膜病变 (PVR)中的作用 ,收集了 48例视网膜脱离患者视网膜下液 (SRF) ,利用紫外分光光度计测定了SRF中LPO的含量和SOD的活性 ,用原子吸收光谱法测定了Zn、Cu的含量。结果表明 ,随着PVR程度及玻璃体浑浊的加重、病程的延长 ,LPO含量增加 ,SOD活性明显下降 ,P <0 0 5 ,差异有统计学意义。提示SRF中LPO、Zn、Cu含量及SOD活性的改变与视网膜脱离后PVR的发生、发展有密切关系。     

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.     

Advancing the Drug Discovery and Development Process

The current state of affairs in the drug discovery and development process is briefly summarized and then ways to take advantage of the ever‐increasing fundamental knowledge and technical knowhow in chemistry and biology and related disciplines are discussed. The primary motivation of this Essay is to celebrate the great achievements of chemistry, biology, and medicine and to inform and inspire students and academics to enter the field of drug discovery and development while, at the same time, continue to advance the fundamentals of their disciplines. It is also meant to encourage and catalyze multidisciplinary partnerships between academia and industry as scientists attempt to merge their often complementary interests and expertise to achieve new improvements and breakthroughs in their respective fields, and the common goal of applying them to the discovery and invention of new and better medicines, especially in areas of unmet needs.     

色质联用仪生物标志物数据库的建立与扩展

随着我国石油工业的发展和色质联用仪广泛应用，生物标志化合物的鉴定与研究越来越重要。由于目前缺少完整的和系统的生物标志物数据资料．研究人员往往要花费大量的时间寻查文献，许多化合物无法鉴定，本谱库针对有机地球化学家们鉴定生物标志物的迫切需要以及弥补现有商业质谱数据库的不足，作者长期积累和广泛收集各类生物标志物的质谱数据文献，建立了有机地球化学研究工作中各类生物标志物的质谱库。该库提供化合物名称、分子式、分子峰、基峰、质谱强度等。     

Studies of surface properties of pure and modified by Mn<Superscript>2+</Superscript> and Ni<Superscript>2+</Superscript> ions of aluminium oxide samples using complex methods

Complex studies of physicochemical properties of pure and modified of aluminia oxides samples are presented. The presence of Mn²⁺ and Ni²⁺ modifiers on the aluminium oxide surface causes increase in water adsorption capacity and decrease in benzene and n-octane adsorption. This is due to decrease of specific surface area, volume and radius of pores as a result of surface impregnation and microcrystal formation during modification with manganese and nickel chlorides. Microcrystal formation on the surface and porosity decrease as confirmed by AFM, EDX and powder diffraction studies using automated diffractometer by step scanning. From the Q-TG and Q-DTG data, the energies of liquid desorption from the surface of the samples and the functions of desorption, energy distribution were calculated. High degree of nonlinearity of the functions resulting from great heterogeneity of the studied surface was found. Adsorption of cations creates more homogeneous surface in aluminium oxide, and it is responsible for the change in adsorbate molecule interaction energy and changes mechanism of adsorption and desorption as well as thickness and structure of the adsorbed film. From the experimental data some parameters characterizing adsorption properties and porosity of the studied samples were determined using the complex measuring methods (thermal analysis, sorptometry, porosimetry, AFM and EDX).     

聚合物光老化、光稳定机理与光稳定剂(下)

大多数聚合物材料,包括塑料、橡胶、纤维、涂料等,在户外使用时会发生光老化而使使用寿命缩短。为有效防止聚合物材料的光劣化,人们已对聚合物的光老化和光稳定机理进行了广泛的研究并先后研发出了几个类型的光稳定剂。但由于户外应用范围不断扩大和环境不断恶化正使聚合物的光老化变得越来越复杂而光防护难度也日益加大,因此国内外有关聚合物光老化、光稳定机理的研究和光稳定剂的研发一直十分活跃。本文下篇阐述光稳定剂的作用机理并综述光稳定剂的研发进展。     

能量色散X射线荧光光谱法分析金元时代的钧窑瓷器

应用能量色散X射线荧光光谱法测定了16个金元时期钧窑瓷器胎、釉样品的化学组成。由结果可知:金元钧瓷胎具有低硅高铝的北方瓷器特点,釉则多为钙碱釉。金元时期样品与北宋时期钧窑瓷器胎釉化学组成比较,金元时期钧窑样品的化学组成变化较大,从因子分析散点图可见,北宋钧官窑样品化学组成变化不大;金元钧窑与北宋钧民窑样品制作工艺上存在继承和发展的关系,但金元时期对原料选择和配方的控制已不如北宋时期严格,反映出金元时期的钧窑已处于衰落阶段。     

Relevance of analytical pyrolysis studies to biomass conversion

The principles and methods of soft ionization mass spectrometry in combination with pyrolysis of macromolecules are outlined. Essential features of the newly developed techniques are the extension of the recorded mass range and the almost exclusive formation of molecular ions of the pyrolyzates. Using field ionization and field desorption mass spectrometry at low and high mass resolution, with electrical and photographic detection, pyrolysis products of biomass were analyzed for the first time. The results of flash pyrolysis by Curie-point heating and thermally programmed degradation of biopolymers are compared.The main topic is the evaluation of the methodology for time- and temperature-resolved pyrolysis. The thermograms and pyrolysis mass spectra obtained enable the study of pyrolysis reactions and the chemical fingerprinting of complex biological matter. The kinetics for the devolatilization of individual chemical species or classes of compounds can be monitored. Curie-point pyrolysis of biopolymers such as kappa-carrageenan and time-programmed degradation of cellulose and lignin are reported. Furthermore, preliminary investigations of pine wood and coal illustrate the potential of the introduced methods.     

Electrical processes upon the evaporation and condensation of water and ice

A mathematical model of electrical processes that take place upon the evaporation of water and sublimation of ice, as well as the condensation growth of water and ice phases from vapor, is proposed. The transfer of the main charge carriers, such as (i) protons and hydroxide ions (in ice, water, and vapor and (ii) orientational defects (in ice and water) is taken into account. Upon the evaporation of water and the sublimation of ice, the first carriers are accumulated before the phase front and cause positive charges in the surface of the water and ice, while the second carriers are depleted (their concentration becomes lower than the thermodynamic value) and impart a negative charge to water and ice. The contribution of protons and hydroxide ions dominates at a low rate of evaporation. In the condensation of vapor and relevant growth of water and ice phases, the polarity of surface charge is opposite to that observed upon evaporation. The values of interfacial current and signs of phase charges upon sublimation, evaporation, and condensation that are predicted in the model comply with experimental data.     

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.     

Herkunft und Authentizität von Lebensmitteln: Stabilisotopenanalytik

The correlations between isotope ratios in water, organic mass, and trace elements of food and beverages, and the circumstances and sites of their origin and production are outlined, and the methods of mass spectrometric isotope ratio determination and the positional ²H analysis by quantitative NMR measurement are explained. In context with the application of these methods for origin and authenticity investigations of food, examples are given for the proof of watering or sugar addition to wine and fruit juices and methods for the identification of nondeclared additions of L‐malic and Lascorbic acids are described. The possibilities of multielement isotope ratio analysis for the identification of origin of animal products (eggs, milk products, meat) and methods for the discriminations between natural and nature identical aroma compounds are outlined. Finally, the possibilities of isotope ratio measurements for the discrimination between plant and animal food from conventional and organic production are discussed.     

Effective Ionic Radii and Hydration Volumes for Evaluation of Solution Properties and Ionic Adsorption

Evaluation of effective ionic radii and corresponding individual hydrated-ion volumes provides data required for interpretation of various ion-specific solution properties and for understanding of specificity of ion adsorption at electrode and colloid interfaces. Principles involved in assignment of intrinsic ionic radii and hydrated-ion volumes are comparatively reviewed and examined as a basis for discussion of electrostriction volume changes. Three examples are given of applications of procedures for evaluation of individual hydrated-ion radii and volumes: (a) partial molal volumes and isentropic compressibilities of a series of oxyanions of various structures; (b) steric effects in hydration of alkylammonium and pyridinium cations; and (c) role of ion-hydration effects in specificity of chemisorption of electron donative anions at electrode surfaces.     

Measurement of protein-DNA interaction parameters by electrophoresis mobility shift assay

Native gel electrophoresis (mobility shift) assays may be used to obtain quantitative information about the site distribution, equilibria and kinetics of protein-DNA interactions. These applications depend on the ability of the electrophoretic system to resolve the reaction components, and on their stabilities during the separation process. Factors which affect the lifetimes and mobilities of protein-DNA complexes during electrophoresis include reaction and electrophoresis buffer composition, pH, and ionic strength; the presence of low molecular weight effectors and enzymatic substrates; the nature and concentration of the gel matrix; the temperature; the molecular weights of protein and DNA; the stoichiometric ratios of their complexes; and the possibility of conformational and configurational isomerization of reaction components. We discuss how these factors influence the acquisition of quantitative data from electrophoretic patterns and band intensities, and present formulas for the estimation of equilibrium constants and rate constants for prototypical DNA-protein interactions.     

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     

Effect of reaction medium on the radical polymerization and copolymerization of potassium and sodium p-styrenesulphonate

The kinetics of the homogeneous free radical polymerization of potassium p-styrenesulphonate and sodium p-styrenesulphonate (SSS) in water-salt, water-dioxane, water-dimethyl sulphoxide (DMSO), DMSO—dioxane mixtures and copolymerization of SSS with acrylamide in water-salt and water-DMSO mixtures have been investigated. The overall rate of the process, the kinetic orders with respect to monomer and initiator, overall activation energy and also the properties of the resulting polymers (molecular weight, copolymer composition and compositional inhomogeneity) depend on the nature of the reaction medium. It is mainly connected with the influence of ionic strength (due to varying ionogenic monomer concentration, addition of salts and also the change of the conversion degree) and with the influence of the polarity of solvent on the rate constants for propagation and termination. The chemical and physical characteristic of the reaction mainly influence parameters of the electrostatic interactions in the system “macroradical-counterions-anions of monomer”. This leads to conformational variation of polymer chains and influences the reactivities of growing macroradicals and ionogenic monomers in polymerization and copolymerization. Data on conductivity and viscometric measurements confirmed the dependence of the conformation of polymer and copolymer macromolecules upon the composition of the medium.     

质谱实验室大型仪器设备开放共享的实践与探索

介绍了大型仪器公共平台质谱室大型仪器设备的开放共享,包括各项制度的建立,开放使用运行模式的探索与实践,以及有偿共享的经验与成果.最后总结了开放共享的成效和存在的问题.