基于氧化石墨烯气凝胶固相萃取柱检测有机磷农药北大核心CSCD

以氧化石墨烯气凝胶三维纳米材料作为固相萃取的吸附剂,结合高效液相色谱,对食品中的有机磷农药(辛硫磷、双硫磷、倍硫磷、杀螟硫磷)进行检测分析。首先,利用冷冻干燥的方式制备得到氧化石墨烯气凝胶,通过扫描电镜、红外光谱、比表面积吸附等一系列的实验手段对其形貌及物理特性进行了表征,证明其成功合成。从扫描电镜中可见石墨烯的层状褶皱结构,其表面积为740.51 m^(2)/g。然后,将氧化石墨烯气凝胶直接填充于固相萃取柱中,在未借助任何硅胶等基体的条件下进行萃取研究;通过单因素实验,系统研究了萃取和洗脱条件对有机磷农药萃取回收率的影响。结果显示,在上样体积15 mL、样品溶液pH值4、上样速率1.0 mL/min、洗脱剂1.0 mL乙腈的条件下萃取回收率最高。与商用的萃取材料进行比较,包括碳十八硅胶柱(C18)、阴离子交换柱(SAX)、氨基柱(-NH_(2))和硅酸镁柱(Florisil),氧化石墨烯气凝胶填充的固相萃取柱的萃取回收率有明显提高。实验考察了氧化石墨烯气凝胶直接填充的萃取柱的寿命,结果显示该萃取柱可以重复使用15次,可见解决了分散无基体支撑的石墨烯纳米片容易破碎、堵塞筛板的问题。与液相色谱联用建立分析方法,4种有机磷农药的线性范围较宽,辛硫磷、双硫磷和倍硫磷的线性范围为1~200μg/L,杀螟硫磷的线性范围为2~200μg/L,线性拟合良好(线性相关系数r^(2)≥0.9949),检出限为0.2~0.5μg/L,满足于我国和其他国家限定标准的检测。将该方法应用于实际样品,在苹果皮中未检测到有机磷农药,对其进行加标,回收率为70.5%~93.6%,相对标准偏差≤10.4%。     

固相微萃取在有机磷农药残留分析中的应用

将固相微萃取与其它样品前处理技术进行比较，并对其在有机磷农药残留分析中的应用进行了综述，还就固相微萃取技术及其发展的一些最新动态进行介绍和展望。     

聚合离子液体固载石墨烯复合物的制备及固相萃取有机磷农药的研究

利用1-乙烯基-3-己基咪唑溴盐与氧化石墨烯之间的静电吸引力,将其附着于氧化石墨烯表面,然后经聚合、还原,制备了聚合离子液体-石墨烯复合材料,用SEM、FT-IR、UV-vis等对复合材料进行了表征.将聚合离子液体-石墨烯复合材料用于固相萃取(Solid-phase extraction,SPE)的吸附剂,结合高效液相色谱,研究了此吸附剂对环境水样中4种有机磷农药的萃取性能.对影响SPE效率的参数(吸附剂量、上样体积、上样流速、洗脱剂和洗脱剂体积)进行了优化.在优化条件下,杀螟松、对硫磷、倍硫磷和辛硫磷在5～200 μg/L有良好的线性关系,相关系数(R2)为0.9908～0.9995.将本方法用于环境水样中有机磷农药的测定,加标回收率在80.0％～ 110.0％之间,RSD＜4.5％ (n=3).结果表明,与石墨烯相比,聚合离子液体-石墨烯复合材料作为SPE吸附剂,能降低萃取过程中的团聚现象,对目标物的萃取效能更高;本方法可用于环境水样中有机磷农药残留的测定.     

固相萃取-毛细管气相色谱法测定茶叶中11种残留有机磷农药

应用毛细管柱气相色谱法结合固相萃取分离测定了各种茶叶中11种残留农药.样品用乙腈进行超声萃取,萃取液中的农药经过ODS-C18固相萃取柱富集并净化,用甲醇作淋洗剂,洗脱液中各农药经HP-5石英毛细管色谱柱分离后用氮磷检测器进行检测.各农药在一定浓度范围内保持线性关系,分别对方法的回收率及精密度作了试验,回收率在85.3%～100.6%之间,相对标准偏差(n=7)在3.5%～8.4%之间,用此方法分析了9种茶叶样品并列表给出其农药残留量.     

血浆中有机磷农药的固相萃取－气相色谱法测定

建立了固相萃取、 GC－ FPD（火焰光度检测器）测定血浆中有机磷农药含量的方法。血样经固相萃取, GC－ FPD分析,杂质干扰少,血中有机磷农药提取回收率在 74％以上, RSD在 7.8％～ 20％。检出限：敌敌畏、乐果为 10 μ g /L;甲拌磷、对硫磷为 5 μ g/L 。经实际中毒病人样品分析,证明该法操作简便、准确可靠,灵敏度高。     

固相萃取-气质联用法测定啤酒中9种有机磷农药残留

建立啤酒中9种有机磷农药的固相萃取-气质联用分析方法.采用C18固相萃取小柱对啤酒中的有机磷农药进行提取、净化,用乙酸乙酯洗脱后供气相色谱-质谱分析,用基质匹配标准校正方法补偿基质效应.当添加浓度为50 μg/kg和100μg/kg时,平均回收率为80.3%～95.0%;测量结果的相对标准偏差为1.97%～8.28%(n=6);方法的检出限为1.20～15.3μg/kg.该方法可用于啤酒中痕量有机磷农药残留的测定.     

固相微萃取-气相色谱法测定红葡萄酒中残留的有机磷农药

采用溶胶-凝胶包埋技术制备了耐高温固相微萃取头(SPME),用该萃取头与气相色谱-热离子化检测器联用对红葡萄酒中的12种有机磷农药残留进行了测定。实验中对搅拌速度、萃取时间、盐浓度等条件进行了优化。结果表明,在样品用量25 mL,搅拌速度1250 r/min,盐浓度 150 g/L,萃取时间30 min的条件下,绝大多数组分峰面积的相对标准偏差（RSD）在5%以下,各种有机磷农药的检测限为5 ng/L到0.38 μg/L。     

分散固相萃取-气相色谱法测定对虾中12种有机磷农药残留

建立了分散固相萃取-气相色谱测定对虾中12种有机磷农药残留的分析方法。样品经V(冰乙酸):V(乙腈)=1:99溶液提取,采用乙二胺-N-丙基硅烷(PSA)、C18与石墨炭黑(GCB)为吸附剂进行分散固相萃取净化。以DB-17毛细管色谱柱分离,GC-FPD(P)检测。方法在0.01~0.50μg/mL范围内线性关系良好,相关系数(r2)均不低于0.9971,12种有机磷农药的方法检出限均为0.01 mg/kg。在0.01~0.10 mg/kg的添加水平下,平均加标回收率为80.7%~101.2%,相对标准偏差为3.7%~7.6%。     

固相萃取-气相色谱法测定茶叶中多种有机磷农药

建立了固相萃取-气相色谱法同时测定茶叶中16种有机磷农药残留的方法.样品用丙酮超声提取后,经自制的N-丙基乙二胺(PSA)/活性炭固相萃取柱净化,以混合溶剂乙腈/甲苯(V(乙腈)∶V(甲苯)=1∶3)洗脱,采用气相色谱-氮磷检测器(GC-NPD)测定.方法的回收率在62.8%～109.1%之间,相对标准偏差小于14.7%1,6种有机磷农药的检出限在0.01～0.16 mg/kg之间.方法快速简便、经济实用。     

血浆中有机磷农药的固相萃取—气相色谱法测定

建立了固相萃取,GC－FPD（火焰光度检测器）测定血浆中有机磷农药含量的方法,血样经固相萃取,GC－FPD分析,杂质干扰少,血中有机磷农药提取回收率在74％以上,RSD在7．8％－20％,检出限,敌敌畏,乐果为10ug/L,甲拌磷,对硫磷为5ug/L,经实际中毒病人样品分析,证明该法操作简便,准确可靠,灵敏度高。     

Solid-Phase Microextraction Gas Chromatography for Determination of Some Organophosphorus Pesticides

A simple and rapid solid-phase microextraction (SPME) method is presented based on activated charcoal–PVC fiber for determination of some organophosphorus pesticides from aqueous samples in direct mode SPME. After optimization of the experimental variables affecting SPME of the target compounds from aqueous solutions, the proposed method was applied to determine pesticides in fruit juice. The analytes in this procedure were preconcentrated for 15 min on the SPME fiber and subsequently desorbed by heating the fiber at 200 °C for 5 min in the GC injection port. Separation was on a capillary column GC followed by flame ionization detection. Recoveries of the pesticides studied in aqueous samples ranged 42%–63% and repeatability for all analytes was < 9% for a single fiber. Fiber-to-fiber reproducibility was < 18%.     

Bamboo Charcoal as Solid-Phase Extraction Adsorbent for the Determination of Organophosphorus Pesticides in Water Samples by High-Performance Liquid Chromatography

In this paper, bamboo charcoal was successfully developed for the solid-phase extraction adsorbent for the determination of six organophosphorus pesticides in water samples. After the bamboo charcoal was pretreated and packed in the solid-phase extraction cartridge, the organophosphorus pesticides in water samples were carried out the solid-phase extraction. To establish a perfect solid-phase extraction procedure, the experimental conditions including the eluent, eluent volume, pH of the sample, flow rate of the sample, and loading volume of the sample were all investigated. When 100 mL water samples in the pH range of 6–7 were loaded with the flow rate of 2.5 mL · min^?1 and then eluted with 10 mL acetonitrile, the proposed extraction method was validated by the recovery, correlation coefficient (R²), repeatability (RSD, n = 7) and LODs, which were 69.6–93.4%, 0.9982–0.9998, 2.9–5.6%, and 0.08–1.04 µg · L^?1, respectively. Furthermore, the analysis of the tap, snow, and river water samples demonstrated the feasibility of the proposed SPE method for real water samples. Based on the aforementioned factors, it could be concluded that bamboo charcoal was a good solid-phase extraction adsorbent, and this proposed solid-phase extraction method was suitable for the effective enrichment and determination of the organophosphorus pesticides in water samples.     

Determination of Tetracyclines in Milk by Graphene-Based Solid-Phase Extraction and High-Performance Liquid Chromatography

A graphene-based solid-phase extraction (SPE) column was prepared for the isolation of tetracyclines from milk followed by determination by high-performance liquid chromatography. Graphene provided better separation for tetracyclines than amine-modified graphene and carboxyl-modified graphene. The optimized graphene-based SPE column showed high absorption capacities (greater than 4,660?ng) and high recoveries (exceeding 92%) for tetracycline, oxytetracycline, chlortetracycline, and doxycycline and was successfully reused at least fifty times. The limits of detection in milk were from 10 to 20?ng/mL, with recoveries between 82.3 and 103.6%. Furthermore, the system showed superior performance than two commercial SPE cartridges with respect to recovery, purification, and reusability. Therefore, this approach is suitable for the determination of tetracyclines in milk.     

加速溶剂提取-气相色谱法测定土壤中3种有机磷和9种有机氯农药

提出了气相色谱法测定土壤中3种有机磷和9种有机氯农药含量的方法。样品经粉碎后用正己烷-丙酮(1+1)混合溶剂经加速溶剂萃取仪在60℃静态萃取10min。采用Rtx-1701色谱柱分离,火焰光度检测器测定3种有机磷农药;采用Rtx-CLPⅡ色谱柱分离,电子捕获检测器测定9种有机氯农药。12种有机农药的质量浓度均在5.0～80μg·L-1范围内呈线性,方法的检出限(3s)在0.02～0.40μg·kg-1之间。以空白石英砂样品为基体,进行加标回收试验,回收率在78.5%～108%之间,相对标准偏差(n=7)在4.2%～9.9%之间。     

微波辅助萃取/气相色谱-质谱联用分析蔬菜中的有机磷农药

建立了微波辅助萃取（MAE）/气相色谱-质谱联用法（GC-MS）测定蔬菜样品中二嗪磷、水胺硫磷的分析方法，研究了不同溶剂的萃取效率。选择二氯甲烷为萃取溶剂，采用二因素三水平的正交设计实验优化了萃取溶剂体积和萃取时间。方法的线性范围分别为二嗪磷和对硫磷4ng/g-400ng/g，水胺硫磷20ng/g-400ng/g，检出限分别为二嗪磷和对硫磷4ng/g-400ng/g、水胺硫磷20ng/g-400ng/g，检出限分别为二嗪磷0.29ng/g、对硫磷1.70ng/g、水胺硫磷2.30ng/g。测定200.0ng/g和50.0ng/g加标蔬菜样品，回收率为72.2%-102.0%,RSD为1.5%-11.0%。与传统的机械振荡萃取法相比，不仅萃取效率相当，而且还具有省时省溶剂的优点。     

Developments in the Determination of Organophosphorus Pesticides

Abstract

In this paper, a review is given of some recent developments in organophosphorus pesticides residue methodology. Enrichment on XAD-resins or C₁₈ bonded phases, clean-up by gel permeation and determination by high-performance liquid chromatography (HPLC) with specific detectors can be considered as the major fields of development in the past years.

Despite of the progress made, there is still a further need for procedures which reduce handling time, e.g. by automation, and/or increase specificity of the HPLC determination in matrices of practical interest, such as food, animal and human tissues and environmental samples.     

水样中痕量有机磷农药的膜萃取-气相色谱法测定

制作了涂渍植物来源的酶和不同化合物的萃取膜，萃取富集了水样中的有机磷农药和农药中间体残留。实验表明：涂有不同物质的萃取膜对不同农药有选择性地富集。利用戊二醛膜对河流水样中的硫代磷酸三甲酯和精胺进行富集，用气相色谱－火焰光度检测器检测，回收率在68％－103％之间；检测限为0.1μg/L。方法可满足水体中痕量有机磷农药残留检测的要求。     

固相萃取气相色谱法检测烟叶中有机磷类杀虫剂残留

用固相萃取气相色谱法检测烟叶中的有机磷类杀虫剂多残留。烟叶样品经乙腈超声提取、硅胶固相萃取柱净化后,用气相色谱火焰光度检测器检测。13种有机磷杀虫剂的回收率分别为79.32%～98.37%,相对标准偏差分别为2.48%～4.76%,检出限为0.02～0.08μg/g。该方法灵敏、准确,适用于烟叶中有机磷杀虫剂多残留分析。     

超声辅助固相萃取/离子阱气相色谱-质谱联用测定蔬菜中有机磷农药残留

通过超声辅助固相萃取提取并富集蔬菜中残留的乐果和氧化乐果等9种有机磷农药,采用离子阱二级质谱定性并定量检测其含量,建立了气相色谱-质谱联用测定蔬菜中有机磷农药残留的分析方法.结果表明,所建立的方法简单,快速,灵敏度高.9种有机磷农药的检出限为0.02～0.04 μg/mL,添加回收率为75.07％～99.47％.