三甲基杯[6]芳烃固相微萃取-气相色谱法测定土壤中的多环芳烃

采用溶胶-凝胶方法制备了三甲基杯[6]芳烃/羟基硅油(C[6]/OH-TSO)固相微萃取(SPME)探头,通过与气相色谱-氢火焰(GC-FID)联用测定了土壤中的多环芳烃(PAHs)。考察了影响萃取效率的因素如时间、温度和盐浓度等,比较了杯[6]芳烃探头和杯[4]芳烃探头以及商用PDMS探头对PAHs的萃取效果。结果表明:杯[6]芳烃SPME探头具有耐高温(380℃)、使用寿命长(7200次)等特点,对样品中PAHs的萃取效果明显优于其它探头。本方法检出限低(0.008~0.440mg/L),重现性好(RSD<7%),线性范围宽(3个数量级)。回收率在70.20%~105.1%之间。     

杯[4]芳烃顶空固相微萃取-气相色谱法快速分析环境样品中的多氯联苯

本文以多氯联苯(PCBs)模拟水样为实验样品,优化了杯[4]芳烃探头顶空固相微萃取(HS-SPME)的分析条件,并将杯[4]芳烃探头和商用PDMs探头对PCBs的萃取效果进行了比较。利用杯[4]芳烃-HS-SPME法与USEPA608法同时测定了模拟水样和典型污染地区环境样品中的多氯联苯。研究结果表明：杯[4]芳烃SPME探头对样品中高氯代PCBs的萃取效果优于商用PDMs探头;杯[4]芳烃-HS-SPME和USE-PA608法对同一样品的检测结果一致;该法对水样中PCBs的检出限达1～6ng／L,比USEPA608法的灵敏度提高近3个数量级。     

胺桥杯［4］芳烃固相微萃取探头的特性及其应用

采用溶胶-凝胶方法制备了25,27-二羟基-26,28-(1′,10′-二氧代-4′,7′-二氮杂-3′,8′-二氧代亚辛基)-对-特丁基-杯［4］芳烃/羟基硅油(胺桥杯［4］/OH-TSO)固相微萃取(SPME)探头,通过对脂肪胺和芳胺的分析研究了它的特性。该探头具有耐高温、抗溶剂冲洗、使用寿命长、重现性好等特点。杯环上极性胺桥的引入增强了涂层的极性,因而在不需衍生的情况下对脂肪胺和芳胺都具有很好的萃取能力,表现出对胺类化合物的特殊选择性。脂肪胺的检出限为0.19～39.51 μg/L,线性范围达3个数     

SPME-GC-ECD法测定含硫蔬菜中的有机氯农药

建立了顶空固相微萃取(HS-SPME)与气相色谱-电子捕获检测器(GC-ECD)联用测定含硫蔬菜中有机氯农药(OCPs)的方法。该方法采用的是自制的三苄基杯[6]芳烃/羟基硅油(Benzyl-C[6]/OH-TSO)探头,该探头具有耐高温、使用寿命长等特点。采用10%磷酸处理含硫蔬菜,使其中的酶失去活性,避免产生干扰的硫化物影响有机氯农药的测定。为了得到最佳的萃取效果,对影响涂层萃取效率的条件进行了优化。该方法的检测限为0. 10~1. 8 ng·L~(-1),重现性好(RSD12. 3%),线性范围宽(2~3个数量级),准确度高,回收率在83. 2%~107%之间。实验结果表明该方法适合于含硫蔬菜中痕量OCPs的分析检测。     

基于杯［6］芳烃萃取头的固相微萃取-气相色谱法测定啤酒中痕量的酞酸酯类化合物

选用自制杯［6］芳烃溶胶-凝胶固相微萃取(SPME)萃取头,建立了顶空SPME与气相色谱联用检测啤酒中8种酞酸酯(PAEs)的方法。采用L25(56)正交设计对萃取条件进行了优化,所得方法检出限为0.003～3.429 μg/L,相对标准偏差不超过13.5%,加标回收率为86.3%～109.3%。采用标准加入法对3种瓶装啤酒中PAEs进行了检测,结果表明邻苯二甲酸二(2-乙基己)酯(DEHP)是啤酒中最主要的酞酸酯类污染物,含量最高达5.24 μg/L。迁移试验表明,瓶装啤酒所用塑料垫圈中高含量的DEHP可能成为酒体中PAEs的一种来源,且延长贮存时间、提高贮存温度和振荡都能加快垫圈中DEHP的迁移。     

新型杯[4]芳烃衍生物的合成及其氨基酸萃取性能

杯[4]-1,3-二乙酸乙酯衍生物(1)与水合肼反应生成杯[4]芳烃酰肼衍生物(2),化合物(2)与异硫氰酸苯酯反应得到含酰胺和硫脲单元的新型杯[4]芳烃衍生物(3).总产率达70%.系列氨基酸萃取实验表明化合物(3)对异亮氨酸有较好的选择性萃取能力.     

杯芳烃的配位化学研究 Ⅰ.对叔丁基杯芳烃对铜的萃取

新一代大环化合物杯芳烃(calixarcne)的研究已引起广泛的兴趣,它是由酚环和亚甲基组成的环多聚体,其结构呈杯状.杯底OH及杯盖R基可被各种基团取代,在其环形结构中具有适当体积的洞穴,在此空穴中能容纳客体而形成主客体配合物,可模拟酶催化的初始过程,在催化及分析分离等方面也有广泛的应用.但杯芳烃的配位化学研究很少,本文首先合成了对叔丁基杯[4]芳烃、对叔丁基杯[6]芳烃及对叔了基杯[8]芳烃(分别简称杯[4]、杯[6]及杯[8]),研究它们对铜的萃取,并探讨了萃取机理.     

硫代杯[6]芳烃衍生物从汽车尾气净化催化剂残渣中选择性识别贵金属离子的研究

以对叔丁基硫代杯[6]芳烃(p-tert-butyl-thiacalix[6]arene, TC6A)为底物, 对其上缘进行脱叔丁基、氯甲基化反应后, 在无水N,N-二甲基甲酰胺(DMF)溶液中将氯甲基化的硫代杯[6]芳烃与硫代乙酸钾进行反应合成了一种新的TC6A衍生物--乙酰硫甲基硫代杯[6]芳烃(TC6A-CH₂SCOCH₃). 对含有铂族金属离子的车用尾气净化催化剂残渣溶液进行萃取研究表明, 在pH为1.5的萃取液中TC6A-CH₂SCOCH₃对其中的钯离子具有最高的选择性萃取能力, 萃取率可达86.2%,在pH为4.0的萃取液中对锆离子具有第二高的选择性萃取能力, 萃取率可达57.3%.     

硫(硒)杂多杯[4]芳烃合成及其络合性能研究

合成了下缘硫、硒杂杯[4]芳烃, 然后与杯芳烃片段2,6-二(溴甲基)-4-甲氧基-甲苯在NaH存在条件下缩合得到硫、硒杂多杯[4]芳烃5a和5b. 离子萃取实验表明硫、硒杂多杯[4]芳烃显著增加了对Ag＋和Hg2＋重金属离子的萃取效果.     

杯芳烃的配位化学研究 Ⅰ.对叔丁基杯芳烃对铜的萃取

新一代大环化合物杯芳烃(calixarcne)的研究已引起广泛的兴趣,它是由酚环和亚甲基组成的环多聚体,其结构呈杯状.杯底OH及杯盖R基可被各种基团取代,在其环形结构中具有适当体积的洞穴,在此空穴中能容纳客体而形成主客体配合物,可模拟酶催化的初始过程,在催化及分析分离等方面也有广泛的应用.但杯芳烃的配位化学研究很少,本文首先合成了对叔丁基杯[4]芳烃、对叔丁基杯[6]芳烃及对叔了基杯[8]芳烃(分别简称杯[4]、杯[6]及杯[8]),研究它们对铜的萃取,并探讨了萃取机理.     

Preparation and characteristics of sol-gel-coated calix[4]arene fiber for solid-phase microextraction

5,11,17,23-Tetra-tert-butyl-25,27-diethoxy-26,28-dihydroxycalix[4]arene/hydroxy-terminated silicone oil coated fiber was first prepared and applied for solid-phase microextraction (SPME) with sol-gel technology. The possible sol-gel mechanism was discussed and confirmed by IR spectra. It showed wonderful selectivity and sensitivity to polar (aromatic amines), nonpolar (benzene derivatives, polycyclic aromatic hydrocarbons) and high boiling point compounds (phthalates) and the extraction equilibria were reached quite fast. The coating has high thermal stability (380 degrees C) and solvent stability (organic and inorganic), thus its lifetime is longer than conventional fibers. In addition, it has surprising fiber-to-fiber and batch-to-batch reproducibility. The detection limits were quite low and the linear ranges were pretty broad for all analytes.     

Solid-phase Microextraction with Benzoxy-calix[6]arene Fiber Coupled to Gas Chromatography for the Analysis of Polycyclic Aromatic Hydrocarbons in Water

Headspace solid-phase microextraction(HS-SPME) with sol-gel calix[6]arene-containing fiber followed by gas chromatography with a flame ionization detector was used to examine the composition and distribution of seven polycyclic aromatic hydrocarbons(PAHs) in water. The novel SPME fiber exhibited higher extraction efficiency to PAHs compared with poly(dimethylsiloxane) and other calixarene-containing fibers. Extraction/retention mechanism based on the interactions between calixarenes and PAHs was discussed. ...     

Solid-phase microextraction combined with gas chromatography/triple quadrupole tandem mass spectrometry for determination of nitrated polycyclic aromatic hydrocarbons in sediments

Nitro-polycyclic aromatic hydrocarbons have been detected in various environmental media. However, determination in sediment matrix is challenging due to the lack of a suitable method. In this study, a reliable method for determining 15 nitro-polycyclic aromatic hydrocarbons in sediments was developed based on accelerated solvent extraction and solid-phase microextraction coupled with gas chromatography–tandem mass spectrometry. The accelerated solvent extraction and solid-phase microextraction are sample pre-treatment techniques that have advantages, such as rapid operation and minimal sample volume. Initially, the solid-phase microextraction was optimized using five commercial fibers and from that 65 μm polydimethylsiloxane/divinylbenzene fiber was selected as the best fiber. Further, the accelerated solvent extraction conditions were optimized by Taguchi experimental design, such as extraction temperature (120℃), extraction solvent (dichloromethane), number of cycles (two), static extraction period (4 min), and rinse volume (90%). The method parameters, such as limits of quantitation, and intraday and interday accuracy and precision, were in the range of 0.067–1.57 ng/g, 75.2–115.2%, 69.9–115.4%, and 1.0–16.5%, respectively. Upon meeting all the quality criteria, the method was applied successfully to analyze real sediment samples. Therefore, our study creates a new prospect for the future application of direct immersion solid-phase microextraction in sediment analysis.     

Recent developments in headspace microextraction techniques for the analysis of environmental contaminants in different matrices

Headspace microextraction procedures such as solid-phase microextraction (SPME) and single drop microextraction (SDME) or liquid-phase microextraction (LPME) are increasingly used for the extraction of environmental organic pollutants from a variety of aqueous, viscous, semisolid and solid environmental and biological matrices. In this article, recent analytical applications of these methodologies when used as an isolation and trace enrichment step prior to the analysis of organic pollutants (pesticides, polycyclic aromatic hydrocarbons, polychlorinated compounds, organotin compounds, phenolic derivatives, aromatic amines, phthalates, etc.) by gas and liquid chromatography are reviewed. The applicability and inherent limitations of headspace microextraction are also discussed. The future direction of research in this field and general trends toward commercial applications are considered.     

Rapid validated method for the analysis of benzo[a]pyrene in vegetable oils by using solid-phase microextraction-gas chromatography-mass spectrometry

A solid-phase microextraction method coupled with comprehensive gas chromatography and time-of-flight mass spectrometry for the determination of polycyclic aromatic hydrocarbons in vegetable oils has recently been reported. The present paper tested the possibility to use the solid-phase microextraction method coupled with one-dimensional gas chromatography-mass spectrometry of the only benzo[a]pyrene. Furthermore, an in-house validation for benzo[a]pyrene, used as a marker, as requested by the European regulation no. 208/2005, was carried out. Statistical tests were performed to elaborate the data. Linearity was satisfactory (r(2)=0.999), between about 0.5 and 15 microg/kg. Detection limit and quantification limit were 0.17 and 0.46 microg/kg, respectively. In-day and inter-day repeatability were less than 6% in both cases.     

C18-MCM-41复合介孔材料的合成及其在固相微萃取中的应用

以十八烷基三氯硅烷为偶联剂,采用分步合成法合成了烷基官能化的介孔分子筛C18-MCM-41,用元素分析、傅立叶红外光谱(FT-IR)、X射线衍射(XRD)对合成的复合材料进行表征,结果表明,有机官能化后材料仍保持介孔材料的结构特性。以该材料为固相微萃取涂层材料对水中的多环芳烃(萘、蒽、菲)进行了分析,方法的线性范围分别为5.0~250、0.4~300、0.5~400μg/L,检出限分别为5.0、0.10、0.25μg/L,加标回收率在94.3%~104.4%之间,分析结果令人满意,说明C18-MCM-41介孔材料可作为涂层材料用于固相微萃取。     

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%.     

Supported nanohydroxyapatite on anodized titanium wire for solid-phase microextraction

In this paper, a simple and versatile route was introduced to prepare solid-phase microextraction coatings on the chemically inert titanium wire. Titania nanotube array film can be created on metallic substrates by electrochemical anodization in fluoride-containing electrolytes and subsequently support various secondary reactions to prepare functional surfaces. In the present work, titania nanotube array-coated titanium wire was successfully modified by nanostructured hydroxyapatite by a simple solution-based in situ chemical deposition method. This coating has a high surface-to-volume ratio with a thickness of about 10 μm. Extraction performance of the fiber was assessed on several polycyclic aromatic hydrocarbons in water solutions. The nanohydroxyapatite-coated fiber showed good precision (<7.4 %), low detection limits (1.79–4.89 ng/L), and wide linearity (0.1–200 μg/L) under the selected conditions. The repeatability of fiber to fiber was 1.9–18.2 %. The new solid-phase microextraction fiber has a lifetime of over 150 extractions due to the hydroxyapatite nanoslices uniformly and strongly deposited on the wire surface. The environmental water sample was used to test the reliability of the solid-phase microextraction–gas chromatography method; some analytes were detected and quantified.

新型固相微萃取涂层材料的制备及其在迷迭香挥发性成分检测分析中的应用

利用溶胶-凝胶法制备了含全羟基取代五元瓜环(Q[5])的新型固相微萃取涂层。以全羟基取代五元瓜环(Q[5](OH)_(10))和端羟基聚二甲基硅氧烷(OH-PDMS)为起始原料,γ-缩水甘油醚氧丙基三甲氧基硅烷(KH-560)为偶联试剂,通过水解和缩合反应制备了PDMS/Q[5](OH)_(10)新型涂层。采用扫描电镜、傅立叶红外光谱、差示扫描量热分析和热重分析分别对涂层组织形貌、结构特点以及热稳定性进行了检测。结果表明该涂层具有较大的表面积,良好的热稳定性(360℃)和较长的使用寿命。将该涂层制备成固相微萃取纤维,联用气相色谱-质谱技术对迷迭香的挥发性成分进行了分析,并用面积归一法测定其相对含量。优化的萃取条件为:萃取温度80℃,萃取时间45 min,样品质量0.200 0 g。在此条件下,鉴定出迷迭香中的25种挥发性成分,含量较高的成分为1,8-桉叶素、樟脑和α-蒎烯。将自制纤维与商用纤维(PDMS/DVB/CAR)的萃取效果进行了对比,从萃取成分的数量和含量来看,自制纤维的萃取效果和商用纤维相当,说明自制的固相微萃取纤维可用于植物中挥发性成分的快速检测分析。