自制丙烯酸酯类共聚物固相微萃取/气相色谱对水中农药残留的分析

合成了一种丙烯酸酯类共聚物并将其作为固相微萃取涂层,使用微量进样器自制了固相微萃取装置,并用该装置萃取分析了水体中4种农药（异稻瘟净、乙草胺、赤死蜱、除草醚）,对影响分析灵敏度的各种实验因素进行了优化。在优化条件下4种农药标准样品质量浓度在1～1000μg/L内与色谱峰面积呈良好的线性关系（r=0．992～0．997）,检出限为7．62～13．96ng／L。结果表明,自制的固相微萃取头对水样中4种农药残留具有良好的分离富集效果。     

聚醚砜酮涂层纤维顶空固相微萃取-气相色谱法分析水中痕量的酚类化合物

应用自制的聚醚砜酮(PPESK,30 μm)涂层纤维,采用顶空固相微萃取-气相色谱法测定水中痕量的酚类化合物。优化了固相微萃取温度、萃取时间、pH值和离子强度。方法的检出限为0.003～0.041 μg/L,相对标准偏差低于16%(n=5)。将PPESK涂层纤维与商品化的聚丙烯酸酯涂层纤维对比,结果表明PPESK萃取酚类化合物有较高的萃取富集倍数。用所制备的PPESK萃取头分析自来水、海水等实际水样,20 μg/L添加水平下的回收率分别为100.5%～111.8%和94.8%～117.3%。     

石墨烯/聚二甲基硅氧烷涂层顶空固相微萃取与气相色谱联用测定环境水和果汁中菊酯农药残留

建立了石墨烯/聚二甲基硅氧烷涂层顶空固相微萃取与气相色谱在线联用测定环境水和果汁样品中6种菊酯类农药的检测方法。该涂层的萃取性能优于商用聚二甲基硅氧烷(PDMS,Polydimethylsilane)及聚丙烯(PA,Polypropylene)涂层。对影响萃取性能的因素(如萃取温度、离子强度、萃取时间及解吸时间)依次进行了优化。在最优条件下,丙烯菊酯与联苯菊酯的线性范围为0.02~5μg/L,甲氰菊酯、氯氰菊酯、氰戊菊酯的线性范围为0.1~20μg/L,溴氰菊酯的线性范围为0.2~20μg/L,其相关系数均高于0.99,检出限为6.8~58.2 ng/L,定量下限为18.2~154.9 ng/L。同一涂层的相对标准偏差(RSD,n=5)不高于9.2%,3根涂层之间的RSD为6.7%~10.8%。将该方法用于河水、鱼塘水、苹果汁和橙汁中6种菊酯残留的分析,加标回收率分别为81.6%~92.9%,82.3%~96.1%,78.2%~92.8%和79.9%~91.7%。方法简便、灵敏,能够满足环境水样及浓缩果汁样品中痕量农药残留的分析要求。     

分散液相微萃取-气相色谱联用分析水样中菊酯类农药残留

将分散液-液微萃取(DLLME)与气相色谱-电子俘获检测(GC-ECD)技术相结合,建立了高灵敏度测定水样中7种菊酯类农药残留的新方法。对影响萃取富集效率的因素进行优化,萃取条件选定为:在5.0mL样品溶液中加入10.0μL氯苯和1.0mL丙酮,分散混匀后,以5000r/min离心5min,吸出萃取溶剂氯苯直接进样分析。在优化条件下7种菊酯类农药的富集倍数高达708～1087倍。以α-六六六为内标,7种菊酯类农药在0.8～600μg/L范围内具有良好的线性关系,线性相关系数在0.9990～0.9999之间;检出限为0.04～0.10μg/L(S/N=3)。本方法已应用于自来水、井水及河水等实际水样的分析,平均加标回收率在76.0%～116.0%之间;相对标准偏差在3.1%～7.2%之间。方法具有操作简单、富集效率高和灵敏度高等特点,可满足水样中菊酯类农药残留的检测要求。     

有序介孔碳-固相微萃取涂层的制备及应用

采用溶剂诱导挥发自组装和提拉法制备了以纯有序介孔碳为涂层的新型固相微萃取装置。利用N2吸附-脱附,扫描电镜对涂层材料的性质进行了表征。优化了萃取分析条件,采用顶空-固相微萃取的方法测定自来水中的甲苯和苯乙烯。与商品化涂层相比较,自制涂层具有萃取容量大、使用寿命长的优点。甲苯、苯乙烯含量在0.5~500μg/L内具有良好的线性,检出限为80 ng/L,RSD均小于12%。方法用于测定自来水中的甲苯与苯乙烯,加标回收率为90.2%和93.5%。     

MIL-101(Cr)/SiO_2涂层搅拌棒吸附萃取-超高效液相色谱测定环境中的邻苯二甲酸酯类

采用MIL-101(Cr)/SiO_2材料作为搅拌棒吸附萃取涂层,运用溶胶凝胶技术制备出有效吸附极性有机物的搅拌棒。通过XRD,SEM,FT-IR对搅拌棒涂层材料进行了表征,并将所制得搅拌棒与超高效液相色谱联用,建立了MIL-101(Cr)/SiO_2涂层搅拌棒吸附萃取-超高效液相色谱法测定环境样品中5种邻苯二甲酸酯。对提取时间、搅拌速率、pH、离子强度和解吸时间等萃取条件进行了优化,富集倍数最高可达到98.8倍。在最优条件下,该方法的线性范围为10.00～4375μg/L,R~2范围为0.9880～0.9998,检出限为0.05～0.095μg/L。该方法成功应用于环境水和土壤中5种邻苯二甲酸酯的检测。     

压电免疫生物传感器快速检测三唑磷农药

采用活化剂碳二亚胺(EDC)和N-羟基琥珀酰亚胺(NHS)对邻巯基苯甲酸(MBA)自组装修饰的石英晶体金电极表面进行活化,再将三唑磷单克隆抗体共价固定于电极表面,建立了一种用于快速检测农药残留的压电免疫生物传感器.采用浸入-干燥法和流动注射法检测目标农药并对实验过程进行分析.两种方法均可在40～60 min内直接检测目标农药,浸入-干燥法的检出限为0.04 mg/L,流动注射法的检出限为1.0 mg/L.使用8 mol/L尿素成功解离了抗体-抗原免疫复合物,实现了免疫传感器的再生.此传感器的选择性好,可以重复使用.     

加速溶剂萃取-固相萃取净化-气质联用法测定稻谷中18种农药残留

建立了加速溶剂萃取-固相萃取净化-气质联用法(ASE/SPE/GC-MS)测定稻谷中18种农药残留的方法.以乙腈为溶剂,样品经加速溶剂萃取(30 m L萃取池中,10.34 MPa压力、80℃条件下,加热5 min,用乙腈静态萃取3 min,循环2次,再用池体积60%的乙腈冲洗萃取池后用氮气吹扫100 s)后,过自制固相萃取柱净化(萃取速率:1滴/秒),洗脱旋蒸后正己烷定容,使用气相色谱-质谱联用仪分析.在优化条件下,18种农药在0.05~1.0μg/m L质量浓度范围内的相关系数R2均大于0.99,浓度与峰面积之间呈良好的线性关系.分别以3倍标准偏差和8倍标准偏差计算检出限和定量限,18种农药的检出限为0.104~0.647 mg/kg,定量限为0.276~1.724 mg/kg.以空白样品为基体进行加标回收试验,平均回收率在82.5%~105.1%之间,相对标准偏差(RSD,n=6)为1.5%~6.4%.方法适用于稻谷中18种农药残留的检测.     

GC-NPD同时测定中草药中有机磷和氨基甲酸酯农药残留量

建立了中草药中有机磷和氨基甲酸酯类农药残留量同时检测的气相色谱分析方法.中药材试样依据正交实验的优化条件,用V(C6H14):V(丙酮)=1:1混合提取剂进行超声波提取,经弗罗里硅土和中性氧化铝层析柱净化后,采用HP-5毛细管柱分离,氮磷检测器同时检测中草药中15种有机磷和7种氨基甲酸酯类农药残留量.22种农药在0.015～1.0 mg/L范围内线性良好,线性相关系数为0.9950～1.000,在0.05、0.1 mg/kg两个添加水平的平均回收率分别为70.6%～128.6%和69.5%～116.1%,相对标准偏差分别为0.98%～18%和0.37%～15%.各种农药的检出限为0.002～0.015 mg/L.方法已用于中草药中有机磷和氨基甲酸酯类农药残留量的同时检测.     

牛奶中32种农药的气相色谱-离子阱串联质谱法测定

建立了牛奶中有机氯、有机磷和拟除虫菊酯3类32种农药残留的气相色谱-离子阱串联质谱(GC-IT-MS/MS)分析方法。针对目标物灵敏度不同选择电子轰击电离源或化学电离源,系统地优化了串联质谱的分析条件,并分析了产生这些影响的机理。在优化条件下,32种农药在25(10)～500(200)μg/L范围内线性关系良好,相关系数均大于0. 994;倍硫磷和毒死蜱的方法检出限(MDL)分别为1. 7μg/kg和2. 8μg/kg,其它30种农药的MDL为0. 026～1. 2μg/kg;当样品的加标浓度水平为50、200μg/kg(有机氯类农药的加标浓度为20、100μg/kg)时,32种目标物的平均加标回收率为71. 5%～116%,相对标准偏差为1. 9%～14%。将方法应用于实际样品的检测,其抗干扰能力强,能减少分析结果的假阳性。     

Preparation and investigation of polymethylphenylvinylsiloxane-coated solid-phase microextraction fibers using sol-gel technology

Summary Poly(methylphenylvinylsiloxane) (PMPVS) coating was first prepared using sol-gel technology and applied for solid-phase microextraction (SPME). The extraction properties of the novel coating for volatile and semi-volatile organic compounds were investigated using a homemade SPME device coupled with GC-FID. The porous surface structure of the coating provided high surface area and allowed for high extraction efficiency. Compared with commercial SPME stationary phase, the new phase showed better selectivity and sensitivity toward the various analytes, due to their inherent multifunctional properties and the features of sol-gel chemistry. Furthermore, PMPVS coating showed good thermal stability and long lifetime.     

固相微萃取新型涂层的制备和特性(英文)

 以聚甲基苯基乙烯基硅氧烷为主要成分 ,采用溶胶 凝胶技术和自由基引发交联反应的方法首次制备了一种固相微萃取新涂层 ,并与气相联用 ,分析了芳香族化合物 ,考察了它的萃取性能。结果表明 :该涂层提供了大的比表面积 ,可获得高的萃取效率。与相应的商用固相微萃取涂层相比 ,该涂层具有更好的灵敏度和选择性 ,且热稳定性好 ,使用寿命长。     

An electropolymerized aniline-based fiber coating for solid phase microextraction of phenols from water

An aniline-based polymer was electrochemically prepared and applied as a new fiber coating for solid phase microextraction (SPME) of some priority phenols from water samples. The polyaniline (PANI) film was directly electrodeposited on the platinum wire surface in sulfuric acid solution using cyclic voltammetry (CV) technique. The efficiency of new coating was investigated using a laboratory-made SPME device and gas chromatography with flame ionization detection for the extraction of some phenols from the headspace of aqueous samples. The scanning electron microscopy (SEM) images showed the homogeneity and the porous surface structure of the film. The results obtained proved the ability of this polymer as a suitable SPME fiber coating for trapping the selected phenols. Influential parameters affecting the extraction process were optimized and an extraction time of 50 min at 50 °C gave maximum efficiency, when the aqueous sample was saturated with NaCl and adjusted at pH 2. This new coating can be prepared easily in a reproducible manner and it is rather inexpensive and stable against most of organic solvents. The PANI thickness can be precisely controlled by the number of CV cycles. At the optimum conditions, the R.S.D. for a double distilled water spiked with phenol and chlorophenols at ppb level were 4.8-17% (n = 3) and detection limits for the studied compounds were between 0.69 and 3.7 ng ml⁻¹, except for phenol and 4-chlorophenol. The optimized method was successfully applied to some real-life water samples.     

Plunger-in-needle solid-phase microextraction with graphene-based sol-gel coating as sorbent for determination of polybrominated diphenyl ethers

A solid-phase microextraction (SPME) device, assembled with a commercially available plunger-in-needle microsyringe, with the plunger coated with graphene via a sol-gel approach, was developed for the gas chromatographic-mass spectrometric determination of polybrominated diphenyl ethers (PBDEs) in environmental samples. This is the first application of graphene-based sol-gel coating as SPME sorbent. Parameters affecting the extraction efficiency were investigated in detail. The new coating exhibited enrichment factors for PBDEs between 1378 and 2859. The unique planar structure of graphene enhanced the π-π interaction with the aromatic PBDEs; additionally, the sol-gel coating technique created a porous three-dimensional network structure which offered larger surface area for extraction. The stainless steel plunger provided firm support for the coating and enhanced the durability of the assembly. The plunger-in-needle microsyringe represents a ready-made tool for SPME implementation. Under the optimized conditions, the method detection limits for five PBDEs were in the range of 0.2 and 5.3 ng/L (at a signal/noise ratio of 3) and the precision (% relative standard deviation, n=5) was 3.2-5.0% at a concentration level of 100 ng/L. The linearities were 5-1000 or 10-1000 ng/L for different PBDEs. Finally, the proposed method was successfully applied to the extraction and determination by gas chromatography-mass spectrometry of PBDEs in canal water samples.     

用于固相微萃取的乙烯基开链冠醚复合涂层的研制

固相微萃取 (SPME)是一种新型的样品预处理技术 [1] ,其核心是 SPME装置中萃取头上的固相涂层 .目前商用 SPME涂层的种类较少 ,热稳定性较差 (推荐使用温度 2 0 0～ 2 80℃ ) ,使用寿命较短(40～ 1 0 0次 ) ,价格偏高 ,限制了其推广应用 .因此发展高选择性、高稳定性和高效的固     

A Hexagonally Ordered Nanoporous Silica-Based Fiber Coating for SPME of Polycyclic Aromatic Hydrocarbons from Water Followed by GC�CMS

A highly porous fiber coating material was prepared and functionalized with 3-amino propyl triethoxysilane (APTES) on hexagonally ordered nanoporous silica (SBA-15). Applicability of this coating was assessed employing a laboratory made solid-phase microextraction (SPME) device and gas chromatography?Cmass spectrometry for the simultaneous sampling and determination of trace polycyclic aromatic hydrocarbons (PAHs) from aqueous sample solutions. A one at the time optimization strategy was applied to investigate and optimize important extraction parameters such as extraction temperature, extraction time, ionic strength and sonication time. In the optimum conditions, the relative standard deviations for deionized water, spiked with selected PAHs were between 3.3 and 7.7% (n = 3), and detection limits for the studied compounds were 4.2 and 26.1 pg mL^?1. No significant change was observed in the extraction efficiency of the new SPME fiber, over 50 extractions. The proposed method was successfully applied to the extraction and determination of PAHs in the waste water samples.     

A Hexagonally Ordered Nanoporous Silica-Based Fiber Coating for SPME of Polycyclic Aromatic Hydrocarbons from Water Followed by GC–MS

A highly porous fiber coating material was prepared and functionalized with 3-amino propyl triethoxysilane (APTES) on hexagonally ordered nanoporous silica (SBA-15). Applicability of this coating was assessed employing a laboratory made solid-phase microextraction (SPME) device and gas chromatography–mass spectrometry for the simultaneous sampling and determination of trace polycyclic aromatic hydrocarbons (PAHs) from aqueous sample solutions. A one at the time optimization strategy was applied to investigate and optimize important extraction parameters such as extraction temperature, extraction time, ionic strength and sonication time. In the optimum conditions, the relative standard deviations for deionized water, spiked with selected PAHs were between 3.3 and 7.7% (n = 3), and detection limits for the studied compounds were 4.2 and 26.1 pg mL⁻¹. No significant change was observed in the extraction efficiency of the new SPME fiber, over 50 extractions. The proposed method was successfully applied to the extraction and determination of PAHs in the waste water samples.

     

Hydroxyfullerene as a novel coating for solid-phase microextraction fiber with sol-gel technology

Hydroxyfullerene (fullerol) as a novel coating for solid-phase microextraction (SPME) fiber was first prepared by a sol-gel technology. The coating procedure involving sol solution composition and conditioning process was presented. A fullerene polysiloxane surface-bonded porous coating on the fused-silica fiber surface was obtained and confirmed by IR spectra and scanning electron microscopy. The coating has stable performance at high temperature (even to 360 degrees C) and solvents (organic and inorganic) because of the properties of fullerene and the chemical binding between the coating and the fiber surface. The extraction properties of the new coatings to less volatile organic compounds, such as polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons and polar aromatic amines were investigated using headspace SPME coupled with GC-electron-capture detection and GC-flame ionization detection. In addition, compared with commercial SPME stationary phases, the new coatings showed higher sensitivity, faster velocities of mass transfer for aromatic compound, and possessed planarity molecular recognition for PCBs. Moreover, this fiber was firm, inexpensive, durable and can be prepared simply. The fiber-to-fiber reproducibility was very good.     

Cobalt oxide nanoparticles as a novel high-efficiency fiber coating for solid phase microextraction of benzene,toluene, ethylbenzene and xylene from aqueous solutions

In this work cobalt oxide nanoparticles were introduced for preparation of a novel solid phase microextraction (SPME) fiber coating. Chemical bath deposition (CBD) technique was used in order for synthesis and immobilization of the Co₃O₄ nanomaterials on a Pt wire for fabrication of SPME fiber. The prepared cobalt oxide coating was characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis. The fiber was evaluated for the extraction of benzene, toluene, ethylbenzene and xylene (BTEX) in combination with GC–MS. A simplex optimization method was used to optimize the factors affecting the extraction efficiency. Under optimized conditions, the proposed fiber showed extraction efficiencies comparable to those of a commercial polydimethylsiloxane (PDMS) fiber toward the BTEX compounds. The repeatability of the fiber and its reproducibility, expressed as relative standard deviation (RSD), were lower than about 11%. No significant change was observed in the extraction efficiency of the new SPME fiber after over 50 extractions. The fiber was successfully applied to the determination of BTEX compounds in real samples. The proposed nanostructure cobalt oxide fiber is a promising alternative to the commercial fibers as it is robust, inexpensive and easily prepared.     

溶胶-凝胶固相微萃取涂层及其在农药残留分析中的应用

利用溶胶-凝胶(sol-gel)技术制备固相微萃取(SPME)涂层材料.通过硅醇盐前驱体与涂层聚合物羟基硅油(OH-TSO)的水解共聚的方法,成功地制备了聚二甲基硅氧烷sol-gel 涂层的SPME 萃取头,并以农药的混合标准水溶液为研究对象,用直接-固相微萃取-气相色谱法(GC)对涂层的性能进行考察,制成的萃取头适用于多种农药残留的萃取分离分析.