加速溶剂萃取-凝胶色谱净化-气质联用测定土壤中15种有机氯农药残留的方法研究

建立了加速溶剂萃取-凝胶色谱净化-气质联用同时测定土壤中15种有机氯农药的分析方法。优化了凝胶色谱(GPC)净化的条件,比较了凝胶色谱净化及浓硫酸净化法对15种有机氯回收率的影响。结果表明,采用GPC净化能够有效避免浓硫酸净化对氯丹、异狄氏剂、硫丹、甲氧滴滴涕等农药回收率的影响,GPC净化的最佳收集时间为10~15 min,15种有机氯农药的回收率为56%~122%。15种有机氯农药在0.03~6.0 mg/L范围内具有较好的线性,相关系数达0.999以上,方法的检出限为0.1~5.0μg/kg,定量下限为0.4~16.0μg/kg。采用该方法对实际样品进行加标回收率实验,土壤样品的加标回收率为68%~122%,相对标准偏差为1.2%~5.9%。该方法简单、快捷、灵敏度高,已用于实际土壤样品的检测。     

超高效液相色谱-串联质谱法同时测定血液中115种农药

建立了超高效液相色谱-串联质谱法(UPLC-MS/MS)一针进样同时测定血液中115种农药的方法。血液样品与提取剂甲醇按1∶5体积比进行蛋白沉淀,涡旋振荡2 min,以12 000 r/min离心10 min,取上清液进行UPLC-MS/MS分析。质谱分析采用电喷雾离子源(ESI),正离子模式和负离子模式同时切换采集。结果表明,115种目标农药在1～200 ng/mL质量浓度范围内线性关系良好(r0.99),13%的目标农药检出限(S/N≥3)为0.2 ng/mL,其余目标物均为0.1 ng/mL,所有目标农药的定量下限(S/N≥10)均为1 ng/mL。在10、50、100 ng/mL加标水平下,方法的基质效应为81.8%～115%,目标农药的回收率为80.4%～109%,日内精密度(Intra-RSD)为1.6%～11%,日间精密度(Inter-RSD)为1.9%～13%。该方法简便快速、灵敏度高、稳定性好,适用于血液样品中多农药的定性定量分析。     

高效液相色谱-串联质谱法测定土壤中的氯酸盐和高氯酸盐北大核心CSCD

针对土壤样品的分析,建立了一种同时测定氯酸盐和高氯酸盐含量的高效液相色谱-串联质谱(LC-MS/MS)法。样品经过超声提取、高速离心去除杂质,上清液过固相萃取柱及滤膜净化,用液-质联用仪测定,内标法定量。氯酸盐在2.00~200 ng/mL浓度范围内线性关系良好,相关系数为0.9997,检出限为6.0μg/kg,定量限为20.0μg/kg,加标回收率在92.0%~102.5%,相对标准偏差(RSD)为2.9%;高氯酸盐在1.00~100 ng/mL浓度范围内线性关系良好,相关系数为0.9996,检出限为4.0μg/kg,定量限为10.0μg/kg,加标回收率在94.6%~108.0%,RSD为3.6%。该方法操作简单、测定结果稳定,可用于土壤中氯酸盐和高氯酸盐含量的测定。     

滤过型萃取柱-超高效液相色谱-串联质谱法同时测定水果中11种农药残留

建立了超高效液相色谱-串联质谱测定水果中杀虫剂、杀菌剂、除草剂等11种常见农药的方法.水果样品经乙腈提取,提取液经滤过型萃取柱(m-PFC)净化,正离子多反应模式(MRM)监测,外标法定量.水果中11种农药的检出限为1~3µg/kg,在1.0~100.0 ng/mL的范围内线性关系良好,相关系数r不低于0.9969.在样品基质中分别添加5、20、50µg/kg的标准品进行加标回收试验,11种农药的平均回收率为88.9%~110.1%,相对标准偏差(RSD)为2.7%~8.5%(n=6).方法操作简单、灵敏度高,能够准确测定水果中11种农药残留.     

TurboFlow在线净化/液相色谱-串联质谱法测定水果蔬菜中多菌灵、吡虫啉、啶虫脒与甲基硫菌灵的残留量

建立了TurboFlow在线净化/液相色谱-串联质谱同时测定水果蔬菜中多菌灵、吡虫啉、啶虫脒和甲基硫菌灵残留的方法。样品用乙腈提取,经Cyclone-p在线净化柱净化后,将富集的分析物洗脱转至Betasil Phenyl-hexyl C18分析柱,经色谱分离后,电喷雾串联质谱检测。结果表明,4种农药在1~50 ng/mL范围内呈良好线性,相关系数均大于0.999 7。方法的定量下限(LOQ)为10μg/kg。4种农药在3个水平的加标回收率为80.3%~109.9%,相对标准偏差为1.5%~7.8%。     

固相萃取-气相色谱法检测血清中有机氯农药残留的研究

建立了血清中DDTs和BHCs共8种有机氯农药残留的固相萃取-气相色谱检测方法。样品经超声酸化沉淀蛋白后,采用正己烷-丙酮(9∶1)经Cleanert ODS C18N固相萃取小柱提取,Florisil固相萃取小柱净化,氮气吹干,以500μL正己烷定容,气相色谱-电子捕获检测器(GC-ECD)进行定量分析。结果表明,方法的线性范围2~200 ng/m L,相关系数(r)为0.996 4~0.999 0,检出限(LOD)为0.1~0.9 ng/m L,定量下限(LOQ)为0.4~3.0 ng/m L。8种农药的回收率为80.5%~112.7%,相对标准偏差(RSD)为2.1%~7.9%。该方法具有较高的准确度和精密度,适用于血清样品中痕量有机氯农药的检测。     

盐析辅助液液萃取交联聚维酮净化-靶向单一离子监测/高分辨质谱法测定蜂蜜中新烟碱类农药残留

基于盐析辅助液液萃取(LLE)交联聚维酮(PVPP)净化技术,建立了蜂蜜中7种新烟碱类农药的靶向单一离子监测(TSIM)/高分辨质谱检测方法。样品用乙腈基于盐析辅助LLE-PVPP提取净化,采用BEH C18色谱柱为分析柱,甲醇-水体系(两相均含0.1%甲酸和5 mmol/L甲酸铵)作为流动相,梯度洗脱,采用高分辨质谱TSIM模式检测目标化合物,内标法定量。结果表明,盐析辅助LLE-PVPP净化技术可实现提取净化一步式样品制备,TSIM扫描模式则显示了更宽的线性动态范围和更高的灵敏度与准确度。7种新烟碱类农药在0.01~100μg/L或0.02~100μg/L范围内具有良好的线性关系(r20.999);方法检出限为0.03~0.07μg/kg,定量下限为0.1~0.2μg/kg。在0.2、2、20μg/kg 3种加标水平下,7种新烟碱类农药在蜂蜜中的平均回收率为84.8%~112.7%,日内精密度(RSDr)为0.9%~5.7%,日间精密度(RSDR)为3.7%~9.7%。该方法前处理简单快速、成本较低,灵敏度高、重现性好,可广泛应用于蜂蜜中新烟碱类农药残留的快速检测。     

QuEChERS/超高效液相色谱-串联质谱测定人全血中24种磺酰脲类除草剂

建立了QuEChERS/超高效液相色谱-串联质谱测定人全血中24种磺酰脲类除草剂的方法。对QuEChERS方法进行优化,样品加入NaCl和无水Na₂SO₄并取上层清液经Simple-QuEChERS Nano净化柱净化。采用EclipsePlus C18 RRHD色谱柱分离,以乙腈-水（含0.1‰甲酸）为流动相进行梯度洗脱,在多反应监测（MRM）模式下进行检测,内标法定量。在各自线性范围内,24种磺酰脲类除草剂线性关系良好（r> 0.995）;检出限为0.1～0.2 ng/mL,定量限为0.2～0.5 ng/mL。加标回收率为93.4%～112.3%,日内相对标准偏差（RSD）为0.6%～8.1%,日间RSD为3.3%～9.7%。方法已用于实际案例中磺酰脲类除草剂的检测。     

凝胶渗透色谱-固相萃取净化/气相色谱-串联质谱法测定动物性食品中167种农药残留

建立了肉类、水产类等动物性食品中167种农药残留的气相色谱-串联质谱检测方法。样品匀浆后,采用乙腈提取,以凝胶渗透色谱和Carb-NH2萃取柱联合净化,气相色谱-串联质谱检测,外标法定量。167种农药的响应在1~200μg/L质量浓度范围内线性良好,相关系数在0.994以上,各农药的检出限为0.3~3μg/kg,定量下限为1~10μg/kg。以猪肉样品作为代表性基质,进行0.01,0.04 mg/kg 2个水平的加标回收实验,回收率为66.4%~111.5%,相对标准偏差为1.3%~17.8%。本方法准确可靠,灵敏度高,样品净化效果好,能够满足动物性食品中农药多残留的痕量分析要求。     

QuEChERS结合UPLC-M S/M S检测血液中苯丙胺类及其相关9种物质

对QuEChERS前处理方法从提取、分离、净化等方面进行优化以减弱样本中的基质效应,提高灵敏度;使用提取试剂(含0.1%甲酸的乙腈:甲醇=70:30,V/V)进行提取,加入无水硫酸镁、硼酸钠、研磨珠进行提取分离,使用混合净化剂(十八烷基硅烷(C18):乙二胺-N-丙基硅烷(PSA)=1:2,m/m)进行净化,UPLC-MS/MS测定,外标法定量。结果表明:在优化条件下,苯丙胺类及其相关9种物质的色谱峰分离良好,且各标准化合物的线性相关系数均大于0.991,检出限(LODs)为0.3~1.0 ng/mL,定量限(LOQs)均为2.5 ng/mL;血液添加标准品样本在低(20 ng/mL)、中(100 ng/mL)、高(400 ng/mL)3个浓度的加标回收率为80.1%~103.1%,精密度相对标准偏差(RSD)为1.5%~8.6%;临床4份检测样本中有3份检出苯丙胺类阳性,准确率为71.5%~99.1%。所建立的QuEChERS方法与UPLC-MS/MS结合的分析方法可应用于血液样本中苯丙胺类及其相关9种药物的同时检测分析。     

应用搅拌棒吸附萃取-热脱附-气相色谱-质谱测定烟叶和茶叶中拟除虫菊酯类农药残留

应用搅拌棒吸附萃取(SBSE)技术分别萃取烟叶和茶叶中的5种拟除虫菊酯,并利用热脱附系统将萃取到的物质进行热脱附,然后通过气相色谱-质谱联用仪(GC-MS)进行分析测定。实验过程中对影响SBSE的因素及影响热脱附的条件进行了优化。在优化条件下,采用外标法分别对烟叶和茶叶中的5种拟除虫菊酯类农药残留进行了定量分析。结果表明,烟叶中5种拟除虫菊酯的检出限范围为3.3~11.4 ng,加标回收率为94.8%~103.4%,6次测定的相对标准偏差（RSD）为5.3%~8.6%;茶叶中5种拟除虫菊酯的检出限范围为4.2~10.5 ng,加标回收率为98.2%~110.1%,6次测定的RSD为5.0%~9.6%。实验证明该法具有较高的准确度、灵敏度和较好的重现性,可用于烟叶和茶叶中拟除虫菊酯类农药残留的快速分析测定。     

Novel solvent‐free microwave‐assisted extraction coupled with low‐density solvent‐based in‐tube ultrasound‐assisted emulsification microextraction for the fast analysis of organophosphorus pesticides in soils

A novel and rapid solventless microwave‐assisted extraction coupled with low‐density solvent‐based in‐tube ultrasound‐assisted emulsification microextraction has been developed for the efficient determination of nine organophosphorus pesticides in soils by GC analysis with microelectron capture detection. A specially designed, homemade glass tube inbuilt with a scaled capillary tube was used as an extraction device to collect and measure the separated extractant phase easily. Parameters affecting the efficiencies of the developed method were thoroughly investigated. From experimental results, the following conditions were selected for the extraction of organophosphorus pesticides from 1.0 g of soil sample to 5 mL of aqueous solution under 226 W of microwave irradiation for 2.5 min followed by ultrasound‐assisted emulsification microextraction with 20 μL toluene for 30 s and then centrifugation at 3200 rpm for 3 min. Detections were linear in the range of 0.25–10 ng/g with detection limits between 0.04 and 0.13 ng/g for all target analytes. The applicability of the method to real samples was assessed on agricultural contaminated soils and the recoveries ranged between 91.4 and 101.3%. Compared to other methods, the present method was shown to be highly competitive in terms of sensitivity, cost, eco‐friendly nature, and analysis speed.     

非衍生化高效液相色谱-串联质谱法快速检测生物体液中草甘膦、草铵膦及代谢物

建立了一种非衍生化高效液相色谱-串联质谱快速检测生物体液中草甘膦、草铵膦及其代谢物等8种极性农药的方法。8种极性农药经Metrosep A Supp 5阴离子色谱柱(150 mm×4.0 mm,5μm)分离,以纯水-200 mmol/L碳酸氢铵溶液(含0.1%氨水)为流动相进行梯度洗脱,负离子多反应监测(MRM)模式进行检测。实验结果表明,8种极性农药在0.5~50 ng/mL范围内线性关系良好(r²>0.99),检出限(S/N≥3)为0.08~0.3 ng/mL,定量下限(S/N≥10)为0.3~1 ng/mL。方法的基质效应为86.5%~106%,目标化合物的回收率为81.5%~114%,日内相对标准偏差(RSD)为0.30%~2.8%,日间RSD为0.50%~5.3%。该方法无需复杂的衍生化过程,简便快速、灵敏度高、稳定性好,适用于生物体液中8种极性农药的检测。     

QuEChERS提取-超高效液相色谱-串联质谱法测定蔬菜中氨基甲酸酯类农药的残留量

将蔬菜样品粉碎匀浆后于-20℃保存备用。取此样品10.00g与含1.3%(体积分数)甲酸溶液的乙腈10mL充分混匀后超声提取20min,加入无水硫酸钠8.2g作为脱水剂,氯化钠3.0g作为盐析剂,混合后离心5 min。取出上清液并保留。对留下的样品按上述方法重复提取1次。将2次所得上清液合并,并从中分取2.0mL溶液,加入吸附剂N-丙基乙二胺(PSA)0.4g,C180.25g和石墨化碳黑(GCB)8.2mg,涡旋振荡2min进行净化处理,随即离心2min,取上清液经0.22μm滤膜过滤。取滤液,按超高效液相色谱-串联质谱法测定其中6种氨基甲酸酯类农药的残留量。用Agilent Poroshell 120EC-C18色谱柱为固定相,进样量为5μL。用由不同比例的(A)20mmol·L^-1乙酸铵溶液(每升中含乙酸1mL)和(B)乙腈组成混合液作为流动相进行梯度洗脱。串联质谱分析选择电喷雾离子源和多反应监测模式。所测定的6种氨基甲酸酯类农药的工作曲线的线性范围均为0.200~100μg·L^-1,并测得其检出限(3S/N)为0.08~0.38μg·kg^-1。按标准加入法进行回收试验,测得回收率为81.0%~111%,测定值的相对标准偏差(n=6)为2.8%~4.9%。     

超高效液相色谱-串联质谱同时检测血液中29种农药

本文采用超高效液相色谱-串联质谱法(UPLC-MS/MS)和固相萃取法(SPE)建立了血液中29种农药同时筛查、定性、定量分析的方法,血液经4%磷酸水溶液稀释后,震荡10min,以8000r·min-1转速离心10min,取上清液过3mL甲醇和3mL水活化好的Oasis Prime HLB(3cc,60mg)固相萃取小柱,使用3mL5%甲醇水淋洗,3mL乙腈甲醇混合溶剂(90:10)洗脱,接收洗脱液后在40℃条件下氮吹仪吹干,使用0.5mL初始流动相复溶,震荡10s后,过0.22μm水膜,装液质小瓶后进样分析。采用ACQUITY UPLC HSS C18色谱柱(150 mm×2.1mm,1.8μm)分离,流动相为0.1%甲酸乙腈-水/甲酸/甲酸铵(5mmol,pH=3),梯度洗脱,电喷雾电离正离子模式(ESI+),多反应选择离子监测模式(MRM)检测。29种农药的检出限为0.1 ng·mL^-1~5 ng·mL^-1,定量限为0.5 ng·mL^-1~10 ng·mL^-1,回收率为62.4%~97.4%,基质效应为82.8%~109%,相对标准偏差小于10.3%,相关系数均大于0.99,线性关系良好范围为10 ng·mL^-1~1000ng·mL^-1。本文方法灵敏度高,可以对血液中29种农药成分进行筛查、定性、定量分析,能够满足实际血液样品中农药成分检测的需求。     

Determination of Atrazine,Simazine, Alachlor,and Metolachlor in Surface Water Using Dispersive Pipette Extraction and Gas Chromatography–Mass Spectrometry

Four commonly found pesticides (alachlor, atrazine, metolachlor, and simazine) in surface water were determined using dispersive pipette extraction followed by gas chromatography–mass spectrometry. The rapid mixing and equilibrium between the dispersive pipette extraction adsorbent and water sample resulted in fast and efficient extraction. Using only 5?mL of water sample, the estimated time consumption for extraction of each sample was less than 5?min. Method validation was performed to evaluate accuracy, precision, linearity, the limits of detection, and the limits of quantitation. Average recovery of above 90% was obtained with relative standard deviations below 10%, which indicated good accuracy and precision of the dispersive pipette extraction method. Coefficients of determination were all above 0.9901 and showed good linearity. For the four pesticides studied using the current method, the limits of detection ranged from 7 to 40?ng?L^?1, and limits of quantitation were from 20 to 130?ng?L^?1. Method validation results supported the application of the current method for drinking water safety monitoring per National Primary Drinking Water Regulations established by the US Environmental Protection Agency. Water samples from Lake Lanier and Stone Mountain Lake (Georgia, USS) were analyzed with this method as a preliminary work for a larger scale drinking water quality study in the future. Trace amounts of simazine and atrazine were found in lake water samples, but both were below the regulation levels of the US Environmental Protection Agency.     

高效液相色谱-分段检测法同时测定烟草中14种多酚类化合物

利用高效液相色谱-二极管阵列检测器(HPLC-DAD),建立了同时分析烟草中新绿原酸、绿原酸、隐绿原酸、东莨菪苷、咖啡酸、七叶亭、对香豆酸、阿魏酸、莨菪亭、7-羟基香豆素、芦丁、槲皮苷、山奈酚-3-O-芸香糖苷和槲皮素14种多酚化合物的方法。称取0.02 g烟末,加入5 mL 50%甲醇,超声萃取30 min,取上清液过水相滤膜后,采用Agilent SB-C18柱(3.0 mm×150 mm,1.8μm)进行分离,以0.05 mol/L磷酸二氢钾水溶液和甲醇为流动相,采用分段式检测,获得14种多酚类化合物在各自最佳检测波长下的信号,实现了良好分离。结果表明,14种多酚类化合物的色谱峰面积与其质量浓度呈良好的线性关系,相关系数r2>0.9997,检出限为0.01~0.15μg/mL,定量下限为0.03~0.50μg/mL,日内相对标准偏差(RSD)为0.70%~3.6%,日间RSD为4.0%~6.4%,加标回收率为95.2%~109%。该方法具有良好的灵敏度、精密度和回收率,适合于烟草样品中多种多酚类化合物的同时测定。     

Direct determination of five fluoroquinolones in chicken whole blood and in veterinary drugs by HPLC

A direct, accurate, and sensitive chromatographic analytical method for the quantitative determination of five fluoroquinolones (enoxacin, ofloxacin, norfloxacin, ciprofloxacin, and enrofloxacin) in chicken whole blood is proposed in the present study. For quantitative determination lamotrigine was used as internal standard at a concentration of 20 ng/microL. The developed method was successfully applied to the determination of enrofloxacin, as the main component of commercially available veterinary drugs. Fluoroquinolone antibiotics were separated on an Inertsil (250 x 4 mm) C8, 5 microm, analytical column, at ambient temperature. The mobile phase consisted of a mixture of citric acid (0.4 mol L(-1))-CH3OH-CH3CN (87:9:4% v/v) leading to retention times less than 14 min, at a flow rate 1.4 mL min(-1). UV detection at 275 nm provided limits of detection of 2 ng/mL per 20 microL injected volume for enoxacin, norfloxacin, and ciprofloxacin, 0.4 ng/mL for ofloxacin, and 4 ng/mL for enrofloxacin. Preparation of chicken blood samples is based on the deproteinization with acetonitrile while the pharmaceutical drug was simply diluted with water. Peaks of examined analytes in real samples were identified by means of a photodiode array detector. The method was validated in terms of within-day (n=6) precision and accuracy after chicken whole blood sample deproteinization by CH3CN. Using 50 microL of chicken blood sample, recovery rates at fortification levels of 40, 60, and 80 ng ranged from 86.7% to 103.7%. The applicability of the method was evaluated using real samples from chicken under fluoroquinolone treatment.     

Simultaneous determination of tandospirone and its active metabolite, 1‐[2‐pyrimidyl]‐piperazine in rat plasma by LC–MS/MS and its application to a pharmacokinetic study

A rapid, sensitive and selective liquid chromatography–tandem mass spectrometry method for the detection of tandospirone (TDS) and its active metabolite 1‐[2‐pyrimidyl]‐piperazine (1‐PP) in Sprague–Dawley rat plasma is described. It was employed in a pharmacokinetic study. These analytes and the internal standards were extracted from plasma using protein precipitation with acetonitrile, then separated on a CAPCELL PAK ADME C₁₈ column using a mobile phase of acetonitrile and 5 mm ammonium formate acidified with formic acid (0.1%, v/v) at a total flow rate of 0.4 mL/min. The detection was performed with a tandem mass spectrometer equipped with an electrospray ionization source. The method was validated to quantify the concentration ranges of 1.000–500.0 ng/mL for TDS and 10.00–500.0 ng/mL for 1‐PP. Total time for each chromatograph was 3.0 min. The intra‐day precision was between 1.42 and 6.69% and the accuracy ranged from 95.74 to 110.18% for all analytes. Inter‐day precision and accuracy ranged from 2.47 to 6.02% and from 98.37 to 105.62%, respectively. The lower limits of quantification were 1.000 ng/mL for TDS and 10.00 ng/mL for 1‐PP. This method provided a fast, sensitive and selective analytical tool for quantification of tandospirone and its metabolite 1‐PP in plasma necessary for the pharmacokinetic investigation.     

Application of a novel sol-gel polydimethylsiloxane-poly(vinyl alcohol) solid-phase microextraction fiber for gas chromatographic determination of pesticide residues in herbal infusions

A simple and environmentally friendly methodology for headspace solid-phase microextraction (HS-SPME) using a new fiber coated with polydimethylsiloxane-poly(vinyl alcohol) (PDMS/PVA) is reported for the trace determination of organochlorine (OCP) and organophosphorus (OPP) pesticides in herbal infusions of Passiflora L. by GC-ECD. The capacity of the PDMS/PVA coating for the pesticides was compared to that of commercial PDMS fibers, with advantageous results. The effects of parameters such as the sample ionic strength, dilution of the infusion, extraction temperature and time were investigated. The optimized conditions for the determination of OCP and OPP in Passiflora L. infusions were extraction time and temperature, respectively, of 38 min and 67.5 degrees C, with 5 min of sample/headspace equilibration time. The analytical curves for the range between 0.04 ng mL(-1) to 6 ng mL(-1) of each compound presented a good quality (correlation coefficients of 0.921 or better). The detection limits for the OCP and OPP in these matrices varied from 0.01 ng mL(-1) (beta-endosulfan) to 1.5 ng mL(-1) (malathion). The sensitivity of studied methodology was adequate, as well as its accuracy (78.7-91.5%) and precision (R.S.D. = 1.2-14.2%).