Synthesis, X-ray structure and properties of a new nitrite-bound copper(II) complex with 2-(3,5- dimethylpyrazol-1-ylmethyl)pyridine in a CuN4(O) coordination

Synthesis and characterization of a nitrite-bound copper(II) compound [CuL⁴)₂(ONO)]ClO₄ have been achieved (L⁴ = 2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine]. The bidentate ligand L⁴ provides a pyridine and a pyrazole donor site; however, they are separated by a methylene spacer. The complex has been structurally characterized and it belongs to only a handful of complexes having nitrito-bound mononuclear copper(II) centre. The metal atom has a distorted square pyramidal geometry with the copper atom displaced from the equatorial plane by 0.25 Å. In MeCN solution the green complex exhibits a broad ligand-field transition at 655 nm with a shoulder at 675 nm and in dichloromethane-toluene glass (80 K) it exhibits an EPR spectral feature characteristic of the unpaired electron in the d_x²−y² orbital. Variable-temperature (80–300 K) magnetic susceptibility measurements in the solid state as well as room temperature measurement in MeCN solution reveal mononuclear magnetically dilute copper(II) centre. When examined by cyclic voltammetry (MeCN solution) it displays electrochemically irreversible Cu^II---Cu^I response [cathodic peak potential, E_pc (V vs saturated calomel electrode (SCE)): −0.32]. An oxidative response is observed at 1.14 V, probably due to bound-nitrite oxidation and is partially removed to generate a solvated complex at the electrode surface. The latter species gives rise to reversible Cu^II---Cu^I redox response [ ].     

Emission characteristics of high-powered microwave induced plasma optical emission spectrometry by using nitrogen–oxygen mixture gas

A high-powered, microwave-induced nitrogen–oxygen plasma (N₂–O₂–MIP) generated by using an Okamoto cavity at atmospheric pressure was investigated when the observation height, the flow rate of carrier gas, and the oxygen content were varied as the experimental parameters. The emission characteristics of the plasma were evaluated with regard to the excitation temperature and the intensity ratio of atomic line to ionic line. The excitation temperature of the N₂–O₂–MIP was in the range of 5100–5700 K when the oxygen content was varied from 0 to 30% at the observation height of 7 mm and the carrier gas flow rate of 0.6 l/min. The intensity ratio of atomic line to ionic line was elevated with an increase in the oxygen content.     

Sequential injection analysis for benzophenone-4 and phenylbenzimidazole sulphonic acid in sunscreen sprays by solid-phase extraction coupled with ultraviolet spectrometry

A sequential injection UV method was developed to determine benzophenone-4 (BZ4) and phenylbenzimidazole sulphonic acid (PBS) simultaneously, these being the most commonly used UV-filters in aqueous formulations used as sunscreen sprays. The selective elution of both was performed by on-line solid-phase extraction, by retention on a SAX microcolumn and separation by varying the pH of elution. The sensitivity obtained was 0.042±0.001 ml μg⁻¹ for PBS and 0.0159±0.0003 ml μg⁻¹ for BZ4. The limit of detection was 1.6 μg ml⁻¹ for PBS and 0.6 μg ml⁻¹ for BZ4. The R.S.D. of the results was 1-6% for PBS and 1-12% for BZ4. The method was validated using commercial sunscreen formulations with concentrations determined by a liquid chromatographic procedure. The two procedures gave comparable results. Automation of the method means the amount of reagents used and residues generated are decreased. The system allows the required analysis sequence to be programmed using suitable software.     

Thermal behavior of bismaleimide resin

The cure of a bismaleimide (BMI) neat resin modified with an aromatic diamine and a siloxane elastomer, has been studied by ¹³C solid state nuclear magnetic resonance. Two chemical reactions occur during the cure cycle; at a low temperature, Michael's reaction predominates, while at a high temperature the polymerization of the double bond maleimide creates the network. The degradation of this BMI material was characterized with isothermal and dynamic thermogravimetric analyses in air and in nitrogen. The BMI thermal stability is lower in nitrogen than in air. This behavior is an indication of oxygen participating in reactions at high temperatures. The activation energy (E_a) of thermal degradation was determined from isothermal data using an Arrhenius equation (In V vs. 1/T). The global E_a for the weight loss in air was found to be 91 kJ/mol. The nature and the evolution of the thermal degradation products were the combined analyzed by techniques of pyrolysis, gas chromatography and mass spectrometry. The major thermal decomposition products obtained in the temperature range of 300–700°C are identified as benzene, methyl formamide, aniline, toluene and isocyanate-derived products.     

Azocalixarenes: Synthesis, Characterization, Complexation, Extraction, Absorption Properties and Thermal Behaviours

Azocalixarenes, which have a conjugated chromophore azo (–N=N–) group in p-positions, are synthesized in “one-pot” procedures in satisfactory yields. Their structures in the solid and solution are elucidated by UV–vis, FT-IR, ¹H and ¹³C NMR spectroscopic methods as well as elemental analysis techniques. Some of them are complexed with metal ions (alkali, alkaline-earth and transition metal ions) under neutral conditions. A wide variety of applications is expected by the functionalization of the side arms. The selective liquid–liquid extraction of various alkali, alkaline-earth and transition metal cations from the aqueous phase to the organic phase is carried out by using azocalixarenes. Furthermore, the synthesized azocalixarenes are utilized for selective extraction of Fe³⁺ cations from the aqueous phase to the organic phase. The effects of varying pH and solvent upon the absorption ability of azocalixarenes substituted with electron-donating and electron-withdrawing groups at their o-, m-, p-positions are examined. The thermal behaviours of azocalixarenes containing upper rim functionalized groups are investigated by means of thermogravimetry (TG), differential thermal analysis (DTA) and differential thermogravimetry (DTG).     

Comparative characterisation by atomic force microscopy and ellipsometry of soft and solid thin films

Ellipsometry and atomic force microscopy (AFM) were used to study the film thickness and the surface roughness of both ‘soft’ and solid thin films. ‘Soft’ polymer thin films of polystyrene and poly(styrene–ethylene/butylene–styrene) block copolymer were prepared by spin‐coating onto planar silicon wafers. Ellipsometric parameters were fitted by the Cauchy approach using a two‐layer model with planar boundaries between the layers. The smooth surfaces of the prepared polymer films were confirmed by AFM. There is good agreement between AFM and ellipsometry in the 80–130 nm thickness range. Semiconductor surfaces (Si) obtained by anisotropic chemical etching were investigated as an example of a randomly rough surface. To define roughness parameters by ellipsometry, the top rough layers were treated as thin films according to the Bruggeman effective medium approximation (BEMA). Surface roughness values measured by AFM and ellipsometry show the same tendency of increasing roughness with increased etching time, although AFM results depend on the used window size. The combined use of both methods appears to offer the most comprehensive route to quantitative surface roughness characterisation of solid films. Copyright © 2007 John Wiley & Sons, Ltd.     

Rapid liquid chromatographic-mass spectrometric analysis of withanolides in crude plant extracts by use of a monolithic column

Summary A rapid analytical method has been developed for the mutual resolution of three steroidal compounds, withaferin A, iochromolide, and withacnistin. Liquid chromatography was performed on a Chromolith analytical column (4.6 mm i.d.×50 mm), made from a cylindrical silica rod, operated at a flow rate of 4 mL min⁻¹ with a simple linear gradient prepared from 0.1% aqueous formic acid and 0.1% formic acid in acetonitrile. Under optimum conditions simultaneous separation of the compounds was achieved in less than 7 min, one eighth the time required for conventional LC separation. The overall analysis time was reduced without sacrificing chromatographic performance—essential for the resolution of positional isomers such as iochromolide and withacnistin. The column was coupled to a single-quadrupole mass spectrometer and the method was characterized by good performance in terms of repeatability, selectivity, linearity, and sensitivity. Detection limits in the single-ion-monitoring mode were 0.15 μg mL⁻¹ or below. Finally, the developed method was successfully applied to the determination of withanolides in extracts fromlochroma gesnerioides obtained by three different processes—traditional Soxhlet extraction and two faster methods, microwave-assisted extraction and pressurized solvent extraction.     

能量选择中子成像技术及其应用

能量选择中子成像技术是利用特定范围波长(能量)的中子进行成像。在热/冷中子范围内(<25meV),能量选择中子成像技术主要基于布拉格边效应和衍射机制,相比常规中子成像技术不但可以显著提高图像对比度,而且能分析应变、应力、织构。在超热中子范围内(>1eV),能量选择中子成像技术主要基于中子共振吸收,中子截面随能量变化是同位素特有的,存在明显的共振吸收峰,因此可以进行同位素的“指纹”识别。能量选择中子成像技术在工程、材料、化学、物理、生物、考古等众多科研领域中有着非常广阔的应用前景。     

原子荧光光谱法测定砷过程中还原反应条件的优化

自然界中砷和砷的化合物一般可通过水、大气和食物等途径进入人体,危害人体健康,原子荧光光谱法测定砷含量被广泛应用。为准确测定样品中砷的含量,以原子荧光光谱法(AFS)测定土壤中总砷含量为例,重点研究高价态砷(Ⅴ)还原为低价态砷(Ⅲ)的实验条件,采用正交实验进行条件优化,建立适合的实验方法。通过设计L9(34)正交实验,高价态砷的还原反应与四个因素有关,即与反应温度、反应时间、盐酸加入量和硫脲的用量呈一定的正相关,结果表明,四个因素中硫脲用量的影响最为显著,其次是盐酸加入量、反应时间和反应温度。通过对四个因素的多水平检验,优化后的实验条件为：硫脲用量2.0 mL、盐酸加入量10%、反应时间20 min、温度20～35 ℃(即普通室温)。采用土壤标准物质验证优化后条件的可行性,得出砷的测定值在标准值范围内,RSD在2.2%～4.2%,精密度和准确性均满足质控要求。优化后的实验条件使得操作简便易行,提高了工作效率。     

基于化学计量学结合ICP-MS的党参道地性的研究及安全评价

微量元素与中药的功效和安全性密切相关,也是药材道地性研究的一部分,为探讨党参中重金属元素的安全性、风险性及道地性的相关性。本文采用电感耦合等离子体质谱法（ICP-MS）及原子荧光光谱法(AFS)测定来源于甘肃、山西、湖北、四川等产区的39批党参药材中的20种元素的含量,结果结合化学计量学分析对党参产区进行差异判别。通过单因子污染指数法和内梅罗综合污染指数法对其进行安全性评价,通过健康风险基于暴露量、危害指数法和暴露限值法对其进行风险评估。结果表明,重金属在各自范围内线性关系良好,加样回收率,仪器精密度和重复性良好,其中 Ba、Sr、Mn的含量最高。主成分分析显示39批药材分为三类,同一产区的党参能较好的聚在一起,元素含量差异与产区分布有一定规律,其中Cs、Ga、As、Co、Li、Pb、Hg、Se、V、Mn为关键的差异标志物,为产地元素特征分析鉴别提供依据。安全评价结果为39批党参药材污染等级为安全,但风险评估后DS-31、DS-32、DS-34、DS-36及 DS-37在人体长期蓄积中具有健康风险。结论：本研究方法高效、准确、简便,结合化学计量学可以对党参进行有效的产地判别,评价党参中元素的安全性及风险性,为党参道地性及健康评价提供了科学依据。