固相微萃取-高效液相色谱法测定水中的酞酸二(2-乙基己基)酯

分别采用PDMS、PDMS／DVB、CWX／DVB三种萃取头,应用固相微萃取与高效液相色谱联用技术(SPME-HPLC)分析了水溶液中的痕量酞酸二(2-乙基已基)酯(DE-HP)。实验发现,PDMS／DVB萃取头的萃取效果较其他两种萃取头理想;对SPME的萃取条件进行了优化,建立了水中痕量DEHP的SPME-HPLC分析方法,并对实际水样进行了分析。该方法的线性范围为0．62～15．60mg／L,相关系数为0．9991,检出限为0．06mg／L(3σ,n=11),相对标准偏差(RSD)为3．3％,回收率为89．9％～101．3％。     

固相微萃取-高效液相联用分析环境水样中的痕量■

 应用固相微萃取与高效液相联用技术 (SPME HPLC)分析了环境水样中的痕量 艹屈 。对SPME的条件如萃取时间、萃取温度、离子强度、解吸方式、解吸溶剂、解吸时间和HPLC条件进行了优化 ,建立了SPME HPLC分析环境水样中痕量 艹屈 的方法 ,并将其用于分析自来水、雨水、矿泉水和江水等实际水样。方法的线性范围为 0 0 13μg/L～ 3 0 μg/L ,检出限为 2 7ng/L ,相对标准偏差 (RSD ,n =6 )为 5 6 % ,回收率为 10 3 2 %～ 119 3%。该方法适合于环境水样中痕量 艹屈 的分析 ,体现了SPME在样品前处理中快速、灵敏、简单、无溶剂的特点。     

Determination of diethylhexyl phtalate in water by solid phase microextraction coupled to high performance liquid chromatography

Difficulties detected in the determination of the diethylhexylphthalate (DEHP) at trace levels by gas chromatography–mass spectrometry (GC–MS) using SPME, due to its ubiquitous distribution in the environment has been overcome and a new method for the determination of DEHP in drinking water has been proposed. The method is based on solid phase microextraction (SPME) coupled to high-performance liquid chromatography (HPLC). Detection was carried out spectrophotometrically. Calibration graph was linear in the range 10–110 μg/L with a regression coefficient of r² = 0.998 and a detection limit of 0.6 μg/L. The relative standard deviation was 5 and 2% (n = 4) for chromatographic areas and retention times, respectively. The usefulness of the SPME–HPLC technique was confirmed.     

固相微萃取/高效液相色谱联用分析食品中痕量苯并咪唑

建立了整体柱固相微萃取/高效液相色谱-紫外联用方法用于食品中6种痕量苯并咪唑的分析。在三元溶剂(N,N-二甲基甲酰胺、对二甲苯和异辛烷)体系下,以4-乙烯基苯硼酸与乙二醇二甲基丙烯酸酯原位聚合法制备了4-乙烯基苯硼酸-乙二醇二甲基丙烯酸酯固相微萃取整体柱,并采用热重分析仪、红外光谱、电镜进行表征。分别研究了萃取溶剂、萃取流速、净化体积、解吸溶剂、解吸流速和解吸体积对富集量的影响。在优化条件下,该方法对苯并咪唑的富集倍数高达1 607~3 015倍,方法的线性范围为0.100~100μg/L,检出限为21~33 ng/L,相对标准偏差(RSD)不大于7.4%。采用该方法分析鱼肉、鸭肉、鸭血和鸭肝样品中的苯并咪唑,加标回收率为75.0%~118%,RSD为1.6%~8.7%。该方法灵敏、准确,能满足食品中痕量苯并咪唑的分析要求。     

Solid‐phase microextraction based on polyaniline doped with perfluorooctanesulfonic acid coupled to HPLC for the quantitative determination of chlorophenols in water samples

A porous and highly efficient polyaniline‐based solid‐phase microextraction (SPME) coating was successfully prepared by the electrochemical deposition method. A method based on headspace SPME followed by HPLC was established to rapidly determine trace chlorophenols in water samples. Influential parameters for the SPME, including extraction mode, extraction temperature and time, pH and ionic strength procedures, were investigated intensively. Under the optimized conditions, the proposed method was linear in the range of 0.5–200 μg/L for 4‐chlorophenol and 2,4,6‐trichlorophenol, 0.2–200 μg/L for 2,4‐dichlorophenol and 2–200 μg/L for 2,3,4,6‐tetrachlorophenol and pentachlorophenol, with satisfactory correlation coefficients (>0.99). RSDs were <15% (n = 5) and LODs were relatively low (0.10–0.50 μg/L). Compared to commercial 85 μm polyacrylate and 60 μm polydimethylsiloxane/divinylbenzene fibers, the homemade polyaniline fiber showed a higher extraction efficiency. The proposed method has been successfully applied to the determination of chlorophenols in water samples with satisfactory recoveries.     

Determination of chlorophenols in landfill leachate using headspace sampling with ionic liquid-coated solid-phase microextraction fibers combined with gas chromatography–mass spectrometry

A new microextraction technique based on ionic liquid solid-phase microextraction (IL-SPME) was developed for determination of trace chlorophenols (CPs) in landfill leachate. The synthesized ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([C₄MIM][PF₆]), was coated onto the spent fiber of SPME for extraction of trace CPs. After extraction, the absorbed analytes were desorbed and quantified using gas chromatography–mass spectrometry (GC/MS). The term of the proposed method is as ionic liquid-coated of solid-phase microextraction combined with gas chromatography–mass spectrometry (IL-SPME-GC/MS). No carryover effect was found, and every laboratory-made ionic liquids-coated-fiber could be used for extraction at least eighty times without degradation of efficiency. The chlorophenols studied were 2,4-dichlorophenol (2,4-DP), 2,4,6-trichlorophenol (2,4,6-TCP), 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP), and pentachlorophenol (PCP). The best results of chlorophenols analysis were obtained with landfill leachate at pH 2, headspace extraction for 4 min, and thermal desorption with the gas chromatograph injector at 240 °C for 4 min. Linearity was observed from 0.1 to 1000 μg L⁻¹ with relative standard deviations (RSD) less than 7% and recoveries were over 87%. The limit of detection (LOD) for pentachlorophenol was 0.008 μg L⁻¹. The proposed method was tested by analyzing landfill leachate from a sewage farm. The concentrations of chlorophenols were detected to range from 1.1 to 1.4 μg L⁻¹. The results demonstrate that the IL-SPME-GC/MS method is highly effective in analyzing trace chlorophenols in landfill leachate.     

Preparation and evaluation of solid-phase microextraction fiber based on molecularly imprinted polymers for trace analysis of tetracyclines in complicated samples

Molecularly imprinted polymer (MIP) is widely used in many fields because of its characteristics of high selectivity, chemical stability and easy preparation. To enhance the selectivity and applicability of solid-phase microextraction (SPME), a novel MIP-coated SPME fiber was firstly prepared by multiple co-polymerization method with tetracycline as template. It could be coupled directly to high-performance liquid chromatography (HPLC) and used for trace analysis of tetracyclines (TCs) in complicated samples. The characteristics and application of the fibers were investigated. The electron microscope provided a crosslinked and porous surface, and the average thickness of the MIP coating was 19.5 microm. Compared with the non-imprinted polymer (NIP) coated fibers, the special selectivity to tetracycline and structure-similar oxytetracycline, doxycycline, chlortetracycline were discovered with the MIP-coated fibers. The adsorption and desorption of TCs with the MIP-coated fiber could be achieved quickly. A method for the fluorimetric determination of four TCs by the MIP-coated SPME coupled with HPLC was developed. The optimized extraction conditions such as extraction solvent, desorption solvent, and stirring speed were studied. Linear ranges for the four TCs were 5.00-200 microg/L and detection limits were within the range of 1.0-2.3 microg/L. The method was applied to simultaneous multi-residue analysis of four TCs in the spiked chicken feed, chicken muscle, and milk samples with the satisfactory recoveries.     

一次性固相微萃取-高效液相色谱法测定环境水样中的3种多环芳烃

以涂有聚二甲基硅氧烷(PDMS)的石英光导纤维作为固相微萃取纤维,建立了一次性固相微萃取与高效液相色谱联用测定环境水样中的菲、荧蒽和屈3种多环芳烃(PAHs)的方法。实验考察了解吸时间、萃取时间、搅拌速度、盐效应以及样品溶液pH值对萃取效率的影响,优化得到的萃取和解吸条件为: 于60 mL样品溶液中放入两段萃取纤维(1.5 cm)和1.2 g氯化钠,在1200 r/min搅拌速度下萃取60 min,取出萃取纤维并转入120 μL甲醇中密封静置解吸24 h后,取20 μL解吸液进行液相色谱测定。该方法对于菲、荧蒽和屈的检出限分别为0.17、0.17和0.08 μg/L;精密度(以测定0.5 μg/L PAHs标准溶液6次的相对标准偏差计)小于8%;实际样品中3种PAHs的加标回收率为80.0%～107%。该方法快速简便,纤维一次性使用,克服了污染物在纤维上残留的问题。     

基于低共熔溶剂的整体式萃取头的制备及其对湖水中3种多环芳烃的固相微萃取（英文）

采用氯化胆碱-乙二醇低共熔溶剂(DES)作致孔剂,制备了聚(甲基丙烯酸丁酯-乙二醇二甲基丙烯酸酯)[poly(BMA-EDMA)]固相微萃取头,并与超高效液相色谱法(UPLC)结合测定了湖水中的3种多环芳烃(PAHs)。实验与不使用DES致孔剂的固相微萃取头和商品化聚二甲硅氧烷(PDMS)萃取头进行比较,含DES的poly(BMA-EDMA)固相微萃取头的富集效果最好。系统考察了萃取条件(萃取时间、萃取溶剂、解吸时间、解吸溶剂及离子强度)对水样中多环芳烃萃取效率的影响。在最优的实验条件下,3种多环芳烃类化合物(萘、联苯、菲)的线性范围为0.1~6.0 mg/L(r≥0.990 3),检出限为2.1~4.9μg/L,回收率为86.4%~111.3%,相对标准偏差(RSD,n=6)为11.2%~15.1%。该法操作简便,稳定性好,成本低,适用于实际环境水样中多环芳烃类化合物的测定。     

Coupling of solid‐phase microextraction with micellar desorption and high performance liquid chromatography for the determination of pharmaceutical residues in environmental liquid samples

A residue analytical method combining solid‐phase microextraction (SPME) with external micellar desorption (MD) and high‐performance liquid chromatography with diode array detector (HPLC‐DAD) has been developed and validated for the simultaneous determination of six pharmaceutical compounds, belonging to various therapeutic categories in water samples. Target compounds include antiinflamatory drugs (ibuprofen, ketoprofen and naproxen), an analgesic (phenazone), a lipid regulator (bezafibrate) and an antiepileptic (carbamazepine). A detailed study of the experimental conditions of extraction and desorption with different surfactants was performed in order to obtain the best results during instrumental analysis. Of the different fibers and surfactants investigated, 65 µm polydimethysiloxane‐divinilbenzene (PDMS‐DVB) fiber and polyoxyethylene 10 lauryl ether (POLE) and polyoxyethylene 6 lauryl ether (C₁₂E₆) as desorbing agents produced the optimal response to pharmaceutical residues. Recoveries obtained were generally higher than 80% and the variability of the method was below 16% for all compounds in both surfactants. Method detection limits were 0.05–12 ng mL^?1 for POLE and 0.1–5 ng mL^?1 for C₁₂E₆. The developed method was compared using external desorption with organic solvent and it was successfully applied to the determination of these pharmaceutical compounds in water samples from different origin. Solid‐phase microextraction with micellar desorption (SPME‐MD) represents a new approach for the extraction of different pharmaceutical compounds in natural waters because it combines shorter handling time, better efficiency, safety and more environmentally friendly process than the traditional methods. Copyright © 2009 John Wiley & Sons, Ltd.     

Determination of pyrethroid residues in tobacco by means of solid phase microextraction and GC/MS with the aid of ultrasonic assisted extraction using water as extracting solvent.

A rapid and simple sampling approach using solid phase microextraction (SPME) for pyrethroid residues analysis in flue-cured tobacco was studied. The fibers coated with poly-dimethylsiloxane (PDMS) at 100 microm thickness were chosen. Extraction time of 180 s, desorption time of 120 s and desorption temperature of 280 degrees C were selected. The whole sampling process, only including an ultrasonic assisted extraction step and a solid phase microextraction step, can be completed within 15 min. The associated SPME and ultrasonic assisted extraction using water as extracting solvent shows good results for tobacco pyrethroid residues determination. Results indicated that four pyrethroids can be determined simultaneously, and the limits of detection are below 35 ng g(-1) using GC/MS in selected ion monitoring (SIM) mode. The reproducibility of the technique is found to be better than 11.8% RSD.     

Fabrication of the Monolithic Fiber for the Solid Phase Micro‐extraction of Malachite Green

A monolithic fiber of molecularly imprinted polymer (MIP) was prepared by in situ polymerization within the capillary with an inner diameter of 530 µm. It was carried out in 8 min by microwave irradiation using malachite green (MG) as a template molecule, α‐methacrylic acid (MAA) as a functional monomer, acetonitrile (ACN) as a porogenic solvent, ethylene dimethacrylate (EDMA) as a crosslinker, azodiiso‐butyronitrile (AIBN) as a thermal initiator. The resulted MIP fibers were pushed out from the capillary, eluted and inserted in the capillary again, which successfully used for the solid phase microextraction (SPME) procedure. The factors affecting the extraction of MG, such as the molar ratio of template/monomer (MG/MAA), concentration of NaCl, extraction and desorption time, and extraction and desorption solvents were investigated in detail. The selectivity of the MIP fibers was compared using MG analogues crystal violet (CV) and non‐analogue Sudan II. It was also employed for the pretreatment of trace MG in the fish feed followed by high‐performance liquid chromatography (HPLC) detection. Under the optimal conditions, the linear range of MG was 10‐600 μg/L, the detection limit (LOD) was 1.23 μg/L and the recovery of spiked fish feed sample was 88.7～113.9%.     

Determination of bisphenol A in water by isotope dilution headspace solid-phase microextraction and gas chromatography/mass spectrometry without derivatization

The original solid-phase microextraction (SPME) fibers use an epoxy resin adhesive that releases bisphenol A (BPA) during thermal desorption of the fiber. This adversely affects the method detection limit and accuracy when these products are used for the determination of BPA. In this work, 5 new metal alloy SPME fibers that do not use epoxy resins were compared for the extraction of BPA in water. The performance of the optimum SPME fiber with 60 microm carbowax-polyethylene glycol coating for the headspace SPME of BPA in water was investigated systematically under different extraction conditions. Salt was found to increase the partitioning of BPA from water into the headspace until saturation was reached. Partitioning of BPA from water into the headspace also increased at higher extraction temperatures, as did longer extraction times. However, extraction of BPA from water onto the SPME fiber was not improved for solutions adjusted to pH 2 compared to the unadjusted neutral solutions. The new BPA method showed good linearity over the concentration range of 2.5 to 40 microg/L [correlation coefficient (r2) = 0.995] .The method detection limit for BPA was 0.5 microg/L, while the instrument detection limit was as low as 0.05 microg/L. Good repeatability was observed for BPA at levels of 5 and 20 microg/L with relative standard deviation values < 10%. The automated headspace SPME method developed in this work was used to investigate migration of BPA from polycarbonate bottles into water, and levels of BPA in water ranged from 1.7 to 4.1 microg/L.     

Determination of organophosphorus insecticides in natural waters using SPE-disks and SPME followed by GC/FTD and GC/MS

Two methods for the analysis of ten organophosphorus insecticides in natural waters using solid phase extraction disks containing C18 and SDB and solid phase microextraction fibers containing polyacrylate (PA) are developed. Bromophos ethyl, bromophos methyl, dichlofenthion, ethion, fenamiphos, fenitrothion, fenthion, malathion, parathion ethyl and parathion methyl were determined by GC/MS and GC/FTD. The SPE-disks require only 1000 mL of sample and provide a method limit of detection in the range of 0.01-0.07 microgram/L and recovery rates from 60.7 to 104.1%. The solid phase microextraction (SPME) technique requires 2-5 mL of water sample and provides a method limit of detection in the range of 0.01 to 0.05 microgram/L for all detectors and the recoveries compared to distilled water ranged from 86.2 to 119.7%. The proposed methods were applied to the trace level screening determination of insecticides in river water samples originating from different Greek regions.     

Determination of organophosphorus insecticides in natural waters using SPE-disks and SPME followed by GC/FTD and GC/MS

Two methods for the analysis of ten organophosphorus insecticides in natural waters using solid phase extraction disks containing C₁₈ and SDB and solid phase microextraction fibers containing polyacrylate (PA) are developed. Bromophos ethyl, bromophos methyl, dichlofenthion, ethion, fenamiphos, fenitrothion, fenthion, malathion, parathion ethyl and parathion methyl were determined by GC/MS and GC/FTD. The SPE-disks require only 1000 mL of sample and provide a method limit of detection in the range of 0.01–0.07 μg/L and recovery rates from 60.7 to 104.1%. The solid phase microextraction (SPME) technique requires 2–5 mL of water sample and provides a method limit of detection in the range of 0.01 to 0.05 μg/L for all detectors and the recoveries compared to distilled water ranged from 86.2 to 119.7%. The proposed methods were applied to the trace level screening determination of insecticides in river water samples originating from different Greek regions.     

固相微萃取中高分子涂层的研究

聚甲基乙烯基硅氧烷首次被用作固相微萃取（ＳＰＭＥ）装置的固相涂层,通过顶空固相微萃取气相色谱分析（ＨＳ－ＳＰＭＥ－ＧＣ）对使用聚甲基乙烯基硅氧烷固相涂层的ＳＰＭＥ装置进行了评价。对其使用厚度、温度及选择性进行了较深入的研究,找到了它的最佳使用条件和适用范围,并与商品化的ＳＰＭＥ涂层作了比较。对ＨＳ－ＳＰＭＥ－ＧＣ和ＨＳ－ＧＣ两种方法也作了比较,指出两者的适用范围不同。     

微孔有机聚合物固相微萃取纤维的制备及在有机氯农药检测中的应用

利用1,3,6,8-四(4-醛基)芘和三聚氰胺为单体合成微孔有机聚合物(MOP),并将其固定在不锈钢丝上,制备成固相微萃取纤维涂层。将其用于顶空固相微萃取(HS-SPME),结合气相色谱-电子捕获检测手段,建立了对大米中有机氯农药的在线检测方法。实验考察了4种实验参数对富集能力的影响,得到了最优的实验条件:萃取温度80℃、萃取时间25 min、NaCl质量浓度200 g/L、解吸时间6 min。在此实验条件下,对有机氯农药的富集倍数达到115~318倍。方法在0.05~50μg/kg范围内具有良好的线性关系,检出限为2.4~11.3 ng/kg。同一纤维及不同纤维富集后测定结果的相对标准偏差范围分别为1.3%~13.1%和2.3%~13.6%。该方法简单、快速,可以实现对实际样品中有机氯农药的痕量分析。     

Determination of free formaldehyde in vaccines and biological samples using solid‐phase microextraction coupled to GC–MS

A headspace solid‐phase microextraction method coupled to GC–MS was successfully developed for the trace determination of formaldehyde in veterinary bacterial and human vaccines, and diphtheria–tetanus antigen. The formaldehyde was derivatized by means of the Hantzsch reaction prior to extraction and subsequent determination. Three different types of solid‐phase microextraction fibers, polar, and nonpolar poly(dimethylsiloxane) and polyethylene glycol were prepared by using a sol–gel technique. The effects of different parameters such as type of fiber coating, extraction time and temperature, desorption conditions, agitation rate, and salt effect were investigated. Under the optimized conditions, the detection limit of the method was 979 ng/L using the selected ion‐monitoring mode. The interday and intraday precisions of the developed method under the optimized conditions were below 13%, and the method shows linearity in the range of 1.75–800 μg/L with a correlation coefficient of 0.9963. The optimized method was applied to the determination of formaldehyde from some biological products. The results were satisfactory compared to the standard method.     

C18-MCM-41新型涂层在固相微萃取中的应用

固相微萃取（SPME）是集采样、萃取和富集于一体的样品前处理技术,该技术于1990年由Pawliszyn提出。由于其不使用有机溶剂,且简便、快速、样品用量少,因而,倍受分析工作者的青睐。     

On-line solid-phase microextraction of triclosan, bisphenol A, chlorophenols, and selected pharmaceuticals in environmental water samples by high-performance liquid chromatography–ultraviolet detection

A method using on-line solid-phase microextraction (SPME) on a carbowax-templated fiber followed by liquid chromatography (LC) with ultraviolet (UV) detection was developed for the determination of triclosan in environmental water samples. Along with triclosan, other selected phenolic compounds, bisphenol A, and acidic pharmaceuticals were studied. Previous SPME/LC or stir-bar sorptive extraction/LC-UV for polar analytes showed lack of sensitivity. In this study, the calculated octanol–water distribution coefficient (log D) values of the target analytes at different pH values were used to estimate polarity of the analytes. The lack of sensitivity observed in earlier studies is identified as a lack of desorption by strong polar–polar interactions between analyte and solid-phase. Calculated log D values were useful to understand or predict the interaction between analyte and solid phase. Under the optimized conditions, the method detection limit of selected analytes by using on-line SPME-LC-UV method ranged from 5 to 33 ng?L^?1, except for very polar 3-chlorophenol and 2,4-dichlorophenol which was obscured in wastewater samples by an interfering substance. This level of detection represented a remarkable improvement over the conventional existing methods. The on-line SPME-LC-UV method, which did not require derivatization of analytes, was applied to the determination of TCS including phenolic compounds and acidic pharmaceuticals in tap water and river water and municipal wastewater samples.