Critical evaluation of the determination of pharmaceuticals, personal care products, phenolic endocrine disrupters and faecal steroids by GC/MS and PTV-GC/MS in environmental waters

An analytical method is described for the determination of a broad range of emerging and priority pollutants, together with sewage molecular markers in environmental waters. The step-by-step study of the GC/MS analyses focuses on the effects of experimental variables using a large volume injection (LVI) technique [a programmed temperature-vaporising (PTV) inlet], the evaluation of a clean-up step using classical and newer sorbents (i.e. Al-N, Fl, NH₂, PSA, Si, CN and DIOL), and the revision of how organic matter [i.e. humic acids (HA) content] affects method performance. Reproducibility and recoveries from spiked coastal water samples at different analyte concentrations (100, 250 and 500 ng L⁻¹) as well as with different levels of spiked humic acids (2, 10 and 20 mg L⁻¹) are reported indicating a good performance of the extraction procedure with low levels of HA (<10 mg L⁻¹). The presence of HA is a critical parameter during the solid-phase extraction (SPE) procedures. Of the clean-up sorbents tested, CN and DIOL proved most efficient in cleaning-up the extracts with recoveries in the range of 66-77% and 100-114%, respectively for the selected analytes. Both GC/MS and PTV-GC/MS instrumental configurations were tested using final sewage effluents, riverine, estuarine and coastal water samples. However, limited applicability of the PTV inlet is reported for environmental applications, affording only a modest improvement in chromatographic signal-to-noise ratios.     

Au nanoparticles as a novel coating for solid-phase microextraction

A novel solid-phase microextraction fiber based on a stainless steel wire coated with Au nanoparticles was prepared and has been applied, coupled with gas chromatography, to the extraction of aromatic hydrophobic organic chemical pollutants in rainwater and soil extract. The solid-phase microextraction fiber exhibited excellent extraction efficiency and selectivity. Effects of extraction time, extraction temperature, ionic strength, stirring rate and desorption conditions were investigated and optimized. Single fiber repeatability and fiber-to-fiber reproducibility were less than 7.90% and 26.40%, respectively. The calibration curves were linear in a wide range for all analytes. Correlation coefficients ranged from 0.9941 to 0.9993. The as-established SPME-GC method was used successfully to two real natural samples. Recovery of analytes spiked at 10 μg L(-1) and 100 μg L(-1) ranged from 78.4% to 119.9% and the relative standard deviations were less than 11.3%.     

Synthesis of SET–LRP‐induced galactoglucomannan‐diblock copolymers

Polysaccharides are biorenewable and biodegradable starting materials for the development of functional materials. The synthesis of a monofunctional macroinitiator for single electron transfer‐living radical polymerization was successfully developed from a wood polysaccharide‐O‐acetyl galactoglucomannan (GGM) using a beforehand synthesized amino‐functional α‐bromoisobutyryl derivative applying reductive amination. The GGM macroinitiator was employed to initiate a controlled radical polymerization of [2‐(methacryloyloxy)ethyl]trimethylammonium chloride (MeDMA), methyl methacrylate (MMA), and N‐isopropylacrylamide (NIPAM) using Cu⁰/Me₆‐Tren as a catalyst. The either charged or amphiphilic GGM‐b‐copolymers with different chain lengths of the synthetic block were successfully synthesized without prior hydrophobization of the GGM chain and dimethyl sulfoxide (DMSO) or DMSO/water mixtures were used as solvents. This novel synthetic approach may find untapped potentials particularly for the development of polysaccharide‐based amphiphilic additives for cosmetics or paints and for the design of novel temperature or pH responsive polymers with such potential applications as in drug delivery systems or in biocomposites. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5100–5110     

有机化学品的生物降解性及构效关系

介绍了描述生物降解性的主要测定参数，测定过程的影响因素及常用的结构描述符，并结合实例综述了目前应用比较广泛的定量结构－生物降解性关系（QSBR）技术，最后，分析了QSBR工作存在的主要问题及研究前景。     

An electrochemical DNA-sensor developed with the use of methylene blue as a redox indicator for the detection of DNA damage induced by endocrine-disrupting compounds

An electrochemical biosensor capable of indirect detection of DNA damage induced by any one of the three endocrine-disrupting compounds (EDCs) – bisphenol A (BPA), 4-nonylphenol (NP) and 4-t-octylphenol (OP), has been researched and developed. The methylene blue (MB) dye was used as the redox indicator. The glassy carbon electrode (GCE) was modified by the assembled dsDNA/graphene oxide-chitosan/gold nano-particles to produce a dsDNA/GO-CS/AuNPs/GCE sensor. It was characterized with the use of electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and scanning electron microscopy (SEM) techniques. The loading/release of the MB dye by the dsDNA/GO-CS/AuNPs film was investigated, and the results showed that the process was reversible. Based on this, the sensor was used to measure the difference between the loading capabilities of intact and damaged dsDNA in the films. The sensor was then successfully applied to detect DNA damage electrochemically. The differential pulse voltammetry (DPV) peak current ratio for MB, observed before and after DNA damage, increased linearly in the presence the BPA, NP or OP compounds; the treatment range was 10–60 min, and the respective damage rates were 0.0069, 0.0044 and 0.0031 min⁻¹, respectively. These results were confirmed by the binding constants: 2.09 × 10⁶ M⁻¹ (BPA-DNA), 1.28 × 10⁶ M⁻¹ (NP-DNA) and 9.33 × 10⁵ M⁻¹ (OP-DNA), all of which were obtained with the use of differential pulse stripping voltammetry (DPSV).     

High resolution mass spectrometry based profiling of diet-related deoxyribonucleic acid adducts

Exposure of DNA to endo- and exogenous DNA binding chemicals can result in the formation of DNA adducts and is believed to be the first step in chemically induced carcinogenesis. DNA adductomics is a relatively new field of research which studies the formation of known and unknown DNA adducts in DNA due to exposure to genotoxic chemicals. In this study, a new UHPLC-HRMS(/MS)-based DNA adduct detection method was developed and validated. Four targeted DNA adducts, which all have been linked to dietary genotoxicity, were included in the described method; O⁶-methylguanine (O⁶-MeG), O⁶-carboxymethylguanine (O⁶-CMG), pyrimidopurinone (M1G) and methylhydroxypropanoguanine (CroG). As a supplementary tool for DNA adductomics, a DNA adduct database, which currently contains 123 different diet-related DNA adducts, was constructed. By means of the newly developed method and database, all 4 targeted DNA adducts and 32 untargeted DNA adducts could be detected in different DNA samples. The obtained results clearly demonstrate the merit of the described method for both targeted and untargeted DNA adduct detection in vitro and in vivo, whilst the diet-related DNA adduct database can distinctly facilitate data interpretation.     

Selective pressurized liquid extraction of estrogenic compounds in soil and analysis by gas chromatography-mass spectrometry

A selective pressurized liquid extraction (SPLE) method, followed by gas chromatography–mass spectrometry (GC–MS), for the simultaneous extraction and clean-up of estrone (E1), 17β-estradiol (E2), 17α-ethynylestradiol (EE2), estriol (E3) and bisphenol A (BPA) from soil samples is described. The on-line clean-up of soil by SPLE was achieved using different organic matter retainers, including silica, alumina and Florisil, the most effective being silica. Thus, different amounts of silica, in conjunction with different extraction solvents (acetone, ethyl acetate, isohexane and dichloromethane), either alone or in combination, were used to extract the target chemicals from spiked soil samples. It was shown that 3 g silica resulted in satisfactory rates of recovery of target compounds and acetone:dichloromethane (1:3, v/v) was efficient in extracting and eluting estrogenic compounds for SPLE. Variables affecting the SPLE efficiency, including temperature and pressure were studied; the optimum parameters were 60 °C and 1500 psi, respectively. The limits of detection (LODs) of the proposed method were 0.02–0.37 ng g⁻¹ for the different estrogenic chemicals studied. The outputs using the proposed method were linear over the range from 0.1 to 120 ng g⁻¹ for E1, E2, EE2, 0.2–120 ng g⁻¹ for E3, and 0.5–120 ng g⁻¹ for BPA. The optimized method was further verified by performing spiking experiments in natural soil matrices; good rates of recovery and reproducibility were achieved for all selected compounds and the method was successfully applied to soil samples from Northeast Scotland, for the determination of the target compounds.     

基于拉曼光谱的危险液体快速识别研究

快速准确识别不明危险液体在公共安全领域需求明显。拉曼光谱技术因具有快速、灵敏、可非接触式检测等优点,成为近年来此领域的研究热点。以沙林、梭曼、塔崩、维埃克斯、芥子气等化学毒剂,磷酸三甲酯、磷酸三乙酯、磷酸三丁酯、甲基膦酸二甲酯、甲基膦酸二异丙酯等化学毒剂模拟剂,亚磷酸二甲酯、亚磷酸三甲酯、亚磷酸三乙酯、甲基膦酰氯乙酯、甲基膦酰二氯、甲基膦酰二氟、氯沙林、二乙胺基磷酰氯、2-二乙胺基乙硫醇、硫二甘醇、异丙醇、频呐基醇、甲基膦酸、甲基膦酸异丙酯、甲基膦酸频呐基酯等化学毒剂前体、中间产物、水解产物以及有毒工业化学品如邻二甲苯、间二甲苯、苯甲醚、氯代苯、乙酸乙酯、乙酸乙烯酯、乙酸苄酯、甲醇、乙醇、乙腈、丙酮、1,1,1-三氯乙烷、正己烷、正丁醇、四氯化碳等和汽油、水等42种危险液体和常见溶剂为研究对象,使用配备785 nm激光器的便携式拉曼光谱仪,针对上述化合物建立了拉曼光谱检测方法,获得了高信噪比的散射光谱数据,对谱图特征进行了分析。采用线性判别分析（LDA）、二次判别分析（QDA）、k近邻（kNN）、朴素贝叶斯（NB）模型、分类决策树（CT）、支持向量机（SVM）6种模式识别算法对上述拉曼光谱数据进行识别归类。研究结果表明,支持向量机、线性判别分析模型具有100%的识别准确率,考虑到实际使用过程中非标准谱图、仪器条件以及外界环境改变等因素会对支持向量机识别结果产生影响,将线性判别分析模型确定为危险液体的快速识别方法。全部测试过程在1~2 min内即可完成且不损耗样品,成功实现水和危险品汽油与其他有毒液体的区分。该研究揭示了具有指纹谱特征的拉曼光谱结合模式识别算法可用于化合物的快速筛查,为及时发现通关夹带,保证物流安全以及化学恐怖事件应急处置等提供了技术支撑。     

危险化学品家族

The dangerous chemicals are special chemicals. They are very important to human being though they are dangerous generally. In this paper, we will vividly introduce the family of dangerous chemicals and classification so that readers can better understand them.