Application of water as a solvent in microwave-assisted extraction for analysis of PCBs and CBzs in fly ash

Polychlorinated biphenyls (PCBs) and chlorobenzenes (CBzs) are two classes of dioxin precursors formed in municipal solid waste incinerators (MSWIs); they produce negative health effects similar to those of dioxins. Reducing the analytical time required for determining the concentrations of these compounds in MSWIs is important for quickly evaluating their importance and assessing associated health risks. In the present study, water is used as a safe and environmentally friendly solvent in microwave-assisted extraction (MAE) for PCB and CBz analyses. MAE is compared with traditional Soxhlet extraction (SE) to determine the extraction efficiencies. The evaluation of extraction efficiencies shows that MAE has a high extraction efficiency compared with that of SE when water content is lower than 60%. Furthermore, the extraction time and organic solvent consumption are reduced with MAE compared with SE.     

Propylene polymerization in liquid monomer with a Ziegler-Natta catalyst in bench scale reactors. Kinetics and model to predict reaction yields

The study of new catalytic systems is critical in order to develop improved and cost effective polymerization processes. One of the methods to evaluate the performance of a catalytic system is by means of bench scale reactors. Despite its difference in size with large scale industrial plants, bench scale reactors have proved to be a valuable tool to understand the behavior of the catalytic system during the polymerization. In this work, a method to estimate the kinetic parameters of propylene polymerization over a conventional Ziegler Natta catalyst is evaluated. Thus, it was possible to set up a semi-empirical model to correlate the reaction yield with the polymerization time, the hydrogen content in the reactor and the reaction temperature. This model proves to be useful to evaluate the performance of a catalytic system within the range of normal operating conditions. A brief study on the particle size distribution of the products is also carried out.     

近年国内固相萃取-色谱分析的进展

对近两年国内各个领域的学者在使用固相萃取做样品前处理的色谱分析方面的研究和应用作了综述, 这一综述包括10个部分: 1. 国内近两年有关固相萃取的综述报告;2. 固相萃取-色谱分析在水质分析中的应用;3. 固相萃取-色谱分析在奶制品和肉类食品分析中的应用;4. 固相萃取-色谱用于蔬菜和水果中有害物质分析的应用;5. 固相萃取-色谱用于粮食和其他食品中有害物质分析的应用;6. 固相萃取-色谱在血药浓度、体液及组织中有害物质分析中的应用;7. 固相萃取-色谱在药物分析中的应用;8. 固相萃取-色谱在其他使用色谱分析中的应用;9. 基质固相分散在色谱分析中的应用;10. 分子印迹SPE在样品前处理中的应用.     

Narrow-bore liquid chromatography with multichannel detection in paediatric biochemistry: Analysis of phenylalanine and tyrosine in phenylketonuria

Summary In paediatric biochemistry, the analysis of drugs and endogenous compounds in preterm or low-birth weight neonates presents particular analytical problems. Sensitive techniques with small sample capacity are essential and in this context, narrow-bore (1–2mm) LC columns, coupled with appropriate low-volume detector cells and connections to reduce band dispersion, have been shown to offer significant advantages. By comparison with conventional columns an increase in sensitivity by a factor ofca. 2 can be achieved. The combination of narrow-bore columns and rapid-scanning UV detectors in reversed-phase LC enables the spectral information to be used for both peak recognition and homogeneity validation. Furthermore, “diode bunching” in the wavelength domain leads to a further two-fold increase in sensitivity. This combination of column and detector technology has been utilised in the design of a sensitive serum micro-assay of the essential aromatic amino acids in paediatric samples, capable of being used with 500nl sample, sensitive to 13pg phenylalanine and 9pg tyrosine and linear over the requisite therapeutic range.     

铜在3%NaCl溶液中腐蚀行为的光电化学研究

Cu以其优异的导电性、导热性和易加工性广泛用于工农业生产中．自然Cu的腐蚀和防腐成为人们很关注的问题．人们已经注意到，Cl-对Cu的腐蚀有影响，并进行过一些研究．但目前使用光电化学方法研究这一问题的文章尚不多见，特别是利用测量开路光电压及其瞬态波形这一现场的、无损的、灵敏的监测方法研究户对Cu电极腐蚀全过程的文章尚未见到．本文正是利用如上方法及XPS，AES方法，研究了Cl-对Cu电极腐蚀的全过程，取得了一些有意义的结果．1实验方法Cu电极用99．99％（质量分数）的Cu制成，面积约为39mm2；电极底部由Cu导线焊接引出，…     

Influence of the Oxide Content in the Catalytic Power of Raney Nickel in Hydrogen Generation

The influence of oxides in the hydrogen evolution on Raney nickel electrocatalysts was characterized by electrochemical impedance measurements. In addition, these materials show competitive overpotentials for hydrogen evolution with a modified Watts bath as a binder for the Raney nickel. The optimum result was ?190?mV of overpotential at 100?mA?cm^?2. Oxygen in the Raney Ni catalyst affects its electroactivity toward hydrogen evolution. The source of oxygen is related to the presence of chloride ions in the modified Watts bath. A Watts bath binds Raney Ni particles to the surface of the catalysts and chloride regulates the oxygen content in the nickel binder during electrodeposition. High oxygen content increases the hydrogen evolution overpotential of the electrode. The electroactivity of the synthesized porous coatings was evaluated by polarization curves and impedance plots. In addition, surface characterization by X-ray diffraction, field emission–scanning electron microscopy equipped with energy-dispersive analysis, and X-ray photoelectron spectroscopy is reported.     

环境水样及食品中亚硝酸根的分析进展

评述了自1997年至2002年国内外环境水样及食品中亚硝酸根(NO2^-)的分析进展。包括分子光谱法、电化学分析法和色谱分析法，引用文献96篇。     

Applications of homemade kit in mutation detection of genes

With the accomplishment of Human Genome Project (HGP), single nucleotide polymorphism (SNP) and mutation detection in human genome are becom-ing a new researching focus. These researches can help us to understand the phenotype diversity of indi-vidual, disease susceptibility and drug resistance of different colonies. Traditional method used for muta-tion detection is slab gel electrophoresis, which re-mains labor-intensive and time-consuming because of the requirement of radioactivity or te…     

Measurement of in situ Monomer Sorption in Poly(propylene)

Summary: An experimental method has been developed to compare the amount of monomer absorbed in freshly produced poly(propylene) with the amount of monomer absorbed in the same material after degassing. It has been found that propylene sorption in freshly produced poly(propylene) is significantly higher than the sorption in the same but degassed polymer. The difference depends on the degree of drying and is time‐dependent. This fact can be an explanation for reduced activity often observed in the transition from liquid‐ to gas‐phase polymerization.

Pressure profile during the pressure‐swing part of the experiment.     

聚多巴胺表面修饰毛细管电色谱的研究进展

毛细管电泳（CE）具有分离时间短、分离效率高、样品消耗量低等优点,在分离分析领域有着重要应用。原始的未修饰熔融石英毛细管只能提供阴极流向的电渗流和单一的电泳分离机制,分离性能有限,重复性较差,不能满足各类复杂样品体系尤其是中性和手性样品的分离需求。因此,有必要在CE中引入各类毛细管修饰策略,以拓展其实际应用潜力。贻贝仿生聚多巴胺（PDA）及其衍生材料因其简便易行的制备过程、优异的表面黏附性、良好的生物相容性、较强的二次反应活性和化学稳定性等优点,在催化、传感、水处理、样品前处理、生物医药以及CE分离等领域得到了广泛应用。PDA涂层的制备过程与物理吸附涂层一样简便,而表面黏附涂层的稳定性又可与共价键合涂层相媲美,因此非常适用于石英毛细管柱的修饰。更重要的是,PDA涂层较强的二次反应活性使其可作为反应平台进行灵活多样的二次表面修饰,便于构建多功能PDA涂层毛细管电色谱（CEC）固定相。基于这些突出优点,PDA涂层材料在CEC中的巨大应用价值逐渐得到了研究者们的广泛关注。该文首先对近3年有关PDA形成机理及PDA快速沉积表面化学的最新研究进展进行了总结,在此基础上综述了近10年PDA涂层材料在开管毛细管电色谱（OT-CEC）和毛细管电色谱整体柱中的最新应用。此外,还对PDA涂层材料在CEC中的发展方向进行了展望。     

聚乙烯吡咯烷酮存在时反相微乳液中水的状态

运用傅立叶变换红外光谱（FTIR）研究不同分子量的聚乙烯吡咯烷酮（PVP）存在时,十二烷基甜菜碱(C12BE)/正庚烷 /正戊醇 /水（Ⅰ）及二（2 乙基）己基磺化琥珀酸钠（AOT）/正庚烷 /水（Ⅱ） 反相微乳液中水的存在状态.采用计算机分峰技术将微乳液中水分子的O－H伸缩振动进行曲线拟合, （Ⅰ）得到三个子峰,分别位于(3560±20)cm－1,(3430±10)cm－1,(3280±10)cm－1附近; （Ⅱ）得到四个子峰,分别位于3618 cm－1, 3550 cm－1, 3446 cm－1和3292 cm－1处.尽管PVP均增溶于W/O型微乳液中表面活性剂分子的极性基团附近,却没有引起长链间自由水的变化.但由于两体系的差异,PVP的存在,导致微乳液（Ⅰ）的本体水减少,结合水增多,却使体系（Ⅱ）的结合水减少,本体水增多.由于W/O型微乳液中水与生物膜中水相似,这些研究有助于理解生物膜界面上的生物化学和生物物理现象.     

Electrochemistry of copper in aqueous acetonitrile

The electrochemical characteristics of the Cu (II)/Cu (I) and the Cu (I)/Cu (0) couples at platinum, carbon, mercury and copper have been studied in acetonitrile-water (AN-H₂O) mixtures. All the electrode processes are moderately fast with mercury the fastest but slower on platinum and carbon paste in that order. A slow chemical step precedes oxidation of Cu (I) to Cu (II) on allectrodes in solutions of high AN content. The slow step may be partial removal of AN from the solvated Cu (I) ion prior to electron transfer. Electrode processes are faster in chloride ions than in sulfate ion solutions. Reduction of Cu (I) in AN–H₂O is quite slow on glassy carbon. Adsorption of AN on platinum and carbon influences the processes. Diffusion coefficients in sulfate solutions are in the order, Cu (I) (AN–H₂O)>Cu (II)(AN–H₂O)>Fe (III)(H₂O) and 2-hydroxy-cyanoethane (2-HCE) strongly decreases the mobility of Cu (I) when added to H₂O. The relevance of the measurements to hydrometallurgical processes is considered. CuSO₄ in 30% v/v AN–H₂O is a faster oxidant than the common oxidant Fe₂(SO₄)₃ in H₂O because of the greater mobility and faster electron acceptance from a corroding surface of Cu (II). Only in solutions of very high nitrile content is the reduction potential of CuSO₄ as high as that of Fe₂(SO₄)₃ in H₂O.     

生物样品中神经递质的定量测定及其应用研究进展

神经递质（NTs）是神经传递的内源性化学信使，在大脑功能中发挥重要作用。中枢神经系统中神经递质浓度的变化与许多精神和生理疾病有关。神经递质的测定已成为疾病诊断和监测以及治疗干预的重要手段，有效的神经递质体内监测对于疾病诊疗乃至新药研发都至关重要。该文就近年来神经递质的检测方法，包括仪器检测法、电化学检测法以及一些新型检测方法等进行综述，并总结了目前神经递质检测在一些疾病研究中的应用进展。     

Nuclear magnetic relaxation in polyolefin resins

Nuclear magnetic resonance (NMR) spin–lattice relaxation times (T₁) in various polyethylene and polypropylene resins were measured at 20 MHz and at temperatures of 130–490 K. At each temperature and for all resins, only a single value of T₁ was found, which was consistent with the occurrence of rapid spin diffusion throughout the protons attached to the polymer chains. The data were analyzed for the estimation of activation energies corresponding to molecular motion causing spin–lattice relaxation. Two well‐defined minima were found for log_e(T₁) plotted as a function of temperature for all of the polypropylene resins. Single very broad minima were found for all of the polyethylene samples. In contrast, the free induction decay signals from all of the resins following single radio‐frequency pulses were observed to contain a rapidly decaying component followed by a much more slowly decaying signal. These components were used to estimate the amount of rigid component present in the solid resins at room temperature. Samples of one high‐density polyethylene and one low‐density polyethylene were irradiated with γ radiation up to a 500‐kGy dose to examine the effects of crosslinking on the NMR relaxation. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 572–584, 2002; DOI 10.1002/polb.10116     

Gels from a semifluorinated n-alkane in fluorinated solvents as a probe for intermolecular interactions

Diblock semifluorinated n-alkanes can form aggregates and gels in fluorinated solvents. We have investigated the thermal behavior of binary mixtures comprising F(CF₂)₈(CH₂)₁₆H and fluorinated solvents. The solvents were perfluorohexane, perfluoroheptane, perfluorooctane, perfluorooctyl bromide, perfluorodecalin, and perfluorotributylamine. The phase diagrams were used to calculate the activity coefficients of the two components and the main excess thermodynamic functions. The solubility and self-assembly behavior of F₈H₁₆ in the fluorinated solvents are related to the different solute–solvent dispersion interactions that depend on the polarizabilities and ionization potentials of the interacting species, and on the structural properties of the solvent.     

不同垃圾焚烧炉排放的PM10 中多环芳烃的研究

对大气可吸入颗粒物采样器进行改装，建立了垃圾焚烧炉烟气中PM10采样系统，并采集了三家垃圾发电厂焚烧炉排放烟气中的可吸入颗粒物。利用GC-MS对可吸入颗粒物中的16种多环芳烃进行定量研究，获得了多环芳烃的质量分数和浓度，并对不同环数的芳烃进行了比较，分析了不同样品中的多环芳烃的毒性参数。结果表明，颗粒物中的多环芳烃主要集中在4环、5环和6环，3环和2环所占比例较少；与燃煤电厂相比，垃圾焚烧发电厂排放的烟气中多环芳烃的浓度和毒性参数更高。     

Energy relationship and the polarization of C_(60) cage in the endohedral complexes (X@C_(60))

In this paper, we carry out the calculation on the system (X@C60)(X=Li, Na, K, Kb, Cs; F, Cl, Br, I), where the position of X changes along 5 typical symmetry directions. For the calculation of quantum chemistry we use EHMO/ASED method, for the calculation of molecular mechanics we use Buckingham potential (exp-6-1) function, and for the calculation of thermo-chemical cycle we use individually isolating the processes such as the structure variation, charge transfer and charge distribution, and their interactions etc. The calculation results show that (1) In the region of radius r≈0.2 nm of the Ceo cage, the potential field is nearly spherical; (2) Except for Li and Na, the systems are the most stable with minimum energies at the center of C60 cage. For Li and Na, the systems are the most stable with minimum energies at r≈0.16 nm and r≈0.13 nm, respectively. In view of the interactive region of chemical bonds, the interactions between X and the C60 cage do not belong to the classical chemical bonds; (     

Gel Chromatography of Metal Acetylacetonates in Organic Solvents

Abstract

Tris (acetylacetonato)cobalt(III) and tris(acetylacetonato)-chromium(III) have been eluted by gel chromatography through styrene-divinylbenzene copolymer gel using an organic solvent as an eluent. Elution counts of these chelates in these solvents reflect some mutual interactions between metal chelate, gel and solvent. When benzene or chloroform was used as an eluent, sieving effect seems to be dominant for the separation of these chelates. Discussions were done in relation to solubility parameters of the solvent, the complex and the gel.     

三维同步偏振荧光光谱研究蛋白质溶液变性时氨基酸残基的发光行为

将偏振技术、同步技术与三维技术结合起来的三维同步偏振荧光光谱(TDSPS)能分辨蛋白质溶液中的色氨酸(Trp)和酪氨酸(Tyr)残基,具有同步光谱分辨率高、三维技术信息丰富的优点．本文用TDSPS表征牛血清白蛋白(BSA)、人血清白蛋白(HSA)受各种因素影响(酸效应、碱效应、盐效应、猝灭剂等)时Trp,Tyr残基荧光光谱的变化,用于区分HSA和BSA．