Solid phase extraction method for rapid isolation and clean-up of some synthetic pyrethroid insecticides from human urine and plasma.

A simple and rapid method for the isolation of seven synthetic pyrethroid insecticides (methothrin, fenpropathrin, cyhalothrin, permethrin, cypermethrin, fenvalerate, deltamethrin) with a solid phase extraction (SPE), utilizing Sep-Pak C18 cartridges, from human urine and plasma is presented. The detection of the insecticides was performed using a wide bore capillary gas chromatograph (GC) with flame ionization detection (FID). The insecticide-containing samples mixed with 70% methanol were directly applied to the cartridges and eluted with 2 ml chloroform. The recoveries using the cartridges were between 90-102% for urine and 81-93% for plasma. Mixing samples with 70% methanol prior to extraction, seems very useful for the screening of synthetic pyrethroid insecticides.     

用Sep—Pak C18固相萃取柱快速提取净化氨基甲酸酯类农药

本文介绍了一种应用Sep—Pak C_(18)固相萃取柱从各类生物检材中快速提取净化9种氨基甲酸酯类农药的方法,并用大口径毛细管气相色谱进行分析。9种药物包括:速灭威、叶蝉散、灭多虫、灭除威、灭杀威、残杀威、巴沙、呋喃丹、西维因。萃取前,水基质检材用蒸馏水稀释;脏器检材加0.4N高氯酸溶液。用3ml氯仿/异丙醇(9:1)洗脱药物。水基质检材的回收率(尿、血浆、全血)在80—100％之间;脏器检材的回收率(肝、肾、脑)在66—100％之间。Sep—Pak C_(18)小柱用于尿和血浆样品时可反复使用。     

Rapid isolation with Sep-Pak C18 cartridges and wide-bore capillary gas chromatography of organophosphate pesticides

A simple and rapid method for isolation of eleven organophosphate pesticides with Sep-Pak C18 cartridges from human urine and plasma, is presented. The detection of the pesticides was made by wide-bore capillary gas chromatography (GC) with flame ionization detection. The pesticide-containing samples, after mixing with water, were directly applied to the cartridges and eluted with chloroform/isopropanol (9:1). The recoveries with use of the cartridges were excellent for most pesticides. Separation of each pesticide peak from each other and from impurities on the gas chromatograms was also satisfactory with use of non-polar and slightly polar capillary columns. The isolation method with use of the cartridges, together with the wide-bore capillary GC, seems very useful in forensic and environmental chemistry and clinical toxicology.     

Rapid extraction and capillary gas chromatography for diazine herbicides in human body fluids

A simple and rapid method for the extraction of four diazine herbicides (terbacil, bromacil, norflurazon and PAC) from human whole blood, plasma and urine with use of Bond Elut C₁₈ cartridges is presented. Whole blood, plasma and urine samples containing the herbicides, after mixing with distilled water, were loaded on Bond Elut C₁₈ cartridges and the herbicides were eluted with chloroform/methanol (9:1). They were detected by capillary gas chromatography with flame ionization detection (FID) with splitless injection. Separation of the four diazine herbicides from each other and from impurities was generally satisfactory with the use of an intermediately polar DB-17 capillary column. The recovery of all compounds, which had been added to whole blood, plasma and urine, was > 89%. The calibration curve for the herbicides, which has been added to whole blood, plasma and urine, showed linearity in the range 1.6–100 ng on column. Their detection limits were 1.2–1.4 ng on column for whole blood and plasma, and 1.1–1.2 ng on column for urine.     

An analytical method for the rapid screening of organophosphate pesticides in human biological samples and foodstuffs

Gas chromatography with nitrogen/phosphorus sensitive detection (GC/PND) and electron impact mass spectrometry (GC/MS) with selected ion monitoring provides a simple, rapid and sensitive method for the determination of organophosphate pesticides (OPs). A selective single-step extraction of 23 different OPs in urine, blood, serum and food samples (baby food, soft drinks and instant soups suspected of contamination from a blackmailing scare) is described. The OPs were extracted with 1ml toluene (with and without addition of mevinphos as internal standard), using a 0.7ml aliquot of urine, blood or serum sample. Food samples (0.2g) were homogenised with water (0.5ml) before extraction. An amount of 1microl of the toluene phase (extraction supernatant) was analysed directly by GC/PND and GC/MS.The method was validated using spiked human serum. The OPs were mixed with serum containing 10mg/ml disodium ethane diamine tetraacetic acid disodium salt (EDTA disodium salt) and stored up to 10 days at 4 and -20 degrees C, respectively. The recovery rates of OPs in freshly spiked human plasma ranged between 50% (dimethoate) and 133% (dialifos). OPs in plasma proved to be stable at -20 degrees C. Their levels decreased only slightly after storage at 4 degrees C.     

固相萃取同时提取尿中的39种药毒物

目的建立固相萃取方法同时提取尿中的39种药毒物并用高效液相色谱法进行分析。方法以多沙普仑为内标,1ml尿样经Oasis小柱固相萃取,用HPLC进行分析。结果39种药毒物可同时从尿中提出,内源性物质不干扰测定。其绝对回收率除吗啡外均大于70％;天内及天间精密度均小于10％;检测限1-15ng／ml;线性相关系数在0.9977以上。结论本法快速、简便、重现性好,空白干扰小,可用于实际案例的药物毒物筛选。     

水和生物体液中3种镇痛麻醉药中空纤维膜液相微萃取

目的研究采用中空纤维膜液相微萃取(hollowfiber liquid phase microextraction,HF-LPME)法提取水和生物体液中的哌替啶,氯胺酮,曲马多。方法样品调节至pH11.5和盐饱和,磁力搅拌器转速为600转/min,内标为盐酸萘福泮,取4μl甲苯,注入到聚偏氟乙烯中空纤维膜中,萃取20min,抽回1μl甲苯进入GC中进行分析。结果血浆、尿、水相关系数R2:哌替啶分别为0.9935、0.9981、0.9997,氯胺酮分别为0.9906、0.9913、0.9927,曲马多分别为0.9741、0.9913、0.9970;检测限:水、尿中哌替啶、氯胺酮、曲马多均为0.01μg/ml,血浆中哌替啶、氯胺酮、曲马多均为0.05μg/ml;血浆、尿、水日内RSD:哌替啶分别为13.0%、7.3%、4.6%,氯胺酮分别为15.1%、13.6%、1.4%,曲马多分别为3.7%、4.3%、9.0%;血浆、尿、水日间RSD:哌替啶分别为15.1%、13.5%、12.2%,氯胺酮分别为12.3%、5.3%、6.0%,曲马多分别为7.1%、15.5%、11.9%;血浆、尿、水相对回收率:哌替啶分别为109.80%、93.49%、97.57%,氯胺酮分别为91.09%、101.80%、100.40%,曲马多分别为106.40%、92.94%、113.32%。结论中空纤维膜液相微萃取用于水和生物体液中的哌替啶,氯胺酮,曲马多的分析,所需有机溶剂少,避免残留和交叉污染,集萃取,富集,进样于一步完成,简单,高效,实用。     

Rapid isolation with Sep-Pak C18 cartridges and wide-bore capillary gas chromatography of some butyrophenones

A simple and rapid method for isolation of five butyrophenones with Sep-Pak C18 cartridges from human samples, and their wide-bore capillary gas chromatography (GC), are presented. The GC was made by both flame ionization and electron capture detections. The drugs contained in alkaline samples were directly applied to the cartridges and eluted with chloroform/isopropanol (9:1). The recoveries with use of the cartridges were excellent for most drugs in both urine and plasma samples. We can recommend the Sep-Pak C18 cartridges for isolation of butyrophenones because of simplicity and rapidity, and also wide-bore capillary GC because of high sensitivity and low decomposition of drugs during passage through the column.     

Simultaneous identification and quantification of several opiates and derivatives by capillary gas chromatography and nitrogen selective detection

A capillary column gas chromatographic method is described for the simultaneous determination of morphine, codeine, heroin, 3- and 6-monoacetylmorphine, nalorphine, naloxone, ethylmorphine, and naltrexone. The drugs were extracted from 2 ml plasma, urine, or other biological samples, including tissue under alkaline conditions in chloroform-isopropanol-n-heptane (50:17:33, v/v), with levallorphan as an internal standard. The drugs were extracted into acid and then reextracted into chloroform after the acid had been alkalinized. After derivatization with trifluoroacetic anhydride, an aliquot was injected into a 25m capillary column equipped with a nitrogen phosphorus detector. The lower limits of detectability, extraction recovery, and the within-run and day-to-day precision of results were determined for each drug. Our results indicate that the procedure is suitable for use in overdose screening and therapeutic drug monitoring.     

Rapid isolation with Sep-Pak C18 cartridges and capillary gas chromatography of triazine herbicides in human body fluids.

A simple and rapid method, for the isolation of eight triazine herbicides from human serum and urine, using Sep-Pak C18 cartridges is presented. After mixing with distilled water, serum and urine samples containing the herbicides, were loaded on Sep-Pak C18 cartridges and eluted with either chloroform only or chloroform/methanol (9:1). The herbicides were detected by capillary gas chromatography with both flame ionization detection (FID) and nitrogen-phosphorus detection (NPD). Separation of eight triazine herbicides from each other and from impurities was generally satisfactory with the use of a non-polar DB-1 capillary column. Recovery of most compounds was excellent for both chloroform and chloroform/methanol (9:1) as elution solvents. Backgrounds were cleaner and evaporation time was shorter for the chloroform only than for the chloroform/methanol (9:1). The NPD gave sensitivity more than 10-20 times higher than that of FID.     

血尿肝中毒鼠强硅藻土提取GC／NPD检测法

目的建立硅藻土提取气相色谱测定血、尿、肝中毒鼠强的方法。方法原尿液、血液用水稀释、肝匀浆用6％高氯酸沉淀蛋白的上清液倒入硅藻土小柱中，血和尿用苯洗脱，肝用三氯甲烷洗脱，挥干洗脱液，用甲醇定容至0．1ml。结果血提取率98．4％，尿提取率95．6%，肝提取率98．1％。相对标准偏差低于3．2％，检出限低于20ng／ml（g）。结论该法简便、快速，提取率高，适合作为常规毒物分析方法。     

A single-column procedure on Bond Elut Certify for systematic toxicological analysis of drugs in plasma and urine.

A single-column solid-phase extraction procedure was developed for the screening of acidic, neutral, and basic drugs from plasma. The recoveries of all 25 tested drugs exceeded 82%. After the plasma had been diluted with phosphate buffer (pH 6.0), the drugs were extracted using a single Bond Elut Certify column. The acidic and most of the neutral drugs were eluted by acetone/chloroform (1:1) and the basic drugs were eluted by 2% ammoniated ethyl acetate. Some neutral drugs appeared in both fractions. The two fractions were collected separately and evaporated until approximately 100 microL of solvent remained in the tube. Both fractions were analyzed separately on a gas chromatograph equipped with a wide-bore capillary column and a flame ionization detector. The procedure could also be used for urine samples.     

Application of solvent microextraction to the analysis of amphetamines and phencyclidine in urine

A fast and simple method to detect some commonly abused illicit drugs, amphetamine, methamphetamine, 3,4-methylendioxy-amphetamine (MDA), 3,4-methylendioxy-methamphetamine (MDMA), 3,4-methylendioxy-N-ethylamphetamine (MDEA) and phencyclidine (PCP) in urine using solvent microextraction (SME) combined with gas chromatography (GC) analysis has been developed. The extraction is conducted by suspending a 2 microl drop of chloroform in a 2 ml urine sample. Following 8 min of extraction, the organic solvent is withdrawn into the syringe and injected into a GC with a pulsed discharge helium ionization detector (PDHID). The effects of different extraction solvents and times, pH and sample preparation were studied. The optimized method was capable of detecting drugs in urine at concentrations below Substance Abuse and Mental Health Services Administration (SAMHSA) established cut-off values for preliminary testing. Good linearity and reproducibility of extraction were obtained. The limits of detection were 0.5 microg/ml for amphetamine, 0.1 microg/ml for methamphetamine and MDA, 0.05 microg/ml for MDMA, 0.025 microg/ml for MDEA and 0.015 microg/ml for PCP. Relative standard deviation (R.S.D.) values ranged between 5 and 20% for the studied drugs.     

Rapid isolation of benzodiazepines with Sep-Pak C18 cartridges

A rapid method for isolation of various benzodiazepines from human samples with Sep-Pak C18 cartridges before wide-bore capillary gas chromatography is described. The drugs dissolved in alkaline samples were directly applied to the cartridges and eluted with hexane/isopropanol (9:1). The recoveries were excellent for all drugs in urine samples, but were somewhat lower for some drugs in plasma samples. The latter problem could be easily circumvented by using a deproteinization process before their application to the cartridge. We can recommend the Sep-Pak C18 cartridges for isolation of benzodiazepines because of their simplicity and rapidity.     

人血、尿中碘解磷定的高效液相色谱分析

目的建立人血、尿中碘解磷定的高效液相色谱分析方法,用于法医学鉴定和指导临床合理用药。方法以空白人血浆和尿液分别添加标准碘解磷定对样品的前处理方法、仪器测试条件、定性、定量分析方法进行考察和优化。对疑似有机磷中毒抢救或死亡者血、尿中的碘解磷定浓度进行测定。结果血、尿中碘解磷定浓度的线性范围是0.5~8.0μg/m l;定量检测的浓度限为0.5μg/m l;日内、日间精密度RSD≤5.3%(n=5);回收率:血≥(96.7±2.9)%;尿≥(93.7±3.8)%。结论所建分析方法快速、准确,适应于法医学鉴定和临床救治中碘解磷定血、尿浓度监测等相关研究。     

血液和尿液中草甘膦的净化富集及检测

目的建立血液、尿液中草甘膦的净化富集及定性定量方法。方法取适量血、尿样品,用80%甲醇水溶液稀释,经Agilent Accu Bond NH2（弱阴离子交换柱）净化富集,用3m L 5%氨水溶液洗脱后进行ESI/LC/MRM对草甘膦的定性及阴离子色谱法（IC）的定量检验分析。结果血液、尿液中草甘膦的IC法检验回收率均大于90%,方法的线性范围均在1-100μg/m L,血检测限为0.1μg/m L,尿液为0.08μg/m L。血液、尿液中草甘膦的LC/MRM的方法检测限均在5ng/m L左右。结论建立的血、尿中草甘膦的前处理方法和LC/MRM定性分析及IC定量分析方法,可满足司法检验要求。     

苯并二氮类药物及其主要代谢物的薄层色谱分析

目的建立饮料、血、尿中 11种常见苯并二氮类药物及尿中 7种主要代谢物的薄层色谱分析法(HPTLC)。方法分析物采用GDX10 1树脂进行固相萃取 ,乙醚作为洗脱溶剂。苯 :丙酮 (10∶6)等作为展开体系 ,改良碘化铋钾显色。结果所建方法绝对灵敏度 0 3～ 0 6μg,尿检出限 0 4～ 1 0 μg/ml、血检出限 0 6～ 1 0 μg/ml、饮料检出限 0 4～ 0 8μg/ml。结论HPTLC法简便、快速 ,适合作为常规毒物分析方法     

血中精神药物的气相色谱-质谱分析

目的建立人血中精神药物的GC-MS测定方法。方法样品在pH12条件下用乙醚萃取,SKF_525A为内标。以DB-5MS石英毛细管柱、EI源、不分流进样测定人血中四种精神药物。结果人血中四种精神药物与内标物分离良好,血药浓度在0.2-1.0μg,／ml范围内呈线性关系,R2≥0.9728,最低检出限为0.01μg(S／N≥3),血中精神药物的最低检出浓度为0.05μg／ml(S／N≥3),提取率72.5％～89.3％,RSD≤5.17％。四种精神药物日内差RSD≤3.7％(n=5)。结论本法可用于精神药物的血药浓度监测。     

生物检材中苯丙胺类兴奋剂和氯胺酮的LC-MS/MS分析

目的建立生物检材中苯丙胺类兴奋剂和氯胺酮的液相色谱-串联质谱(LC-MS/MS)分析方法。方法生物检材包括血液、尿液和毛发,采用稀释法和液液提取的前处理方法,应用两个不同的液相柱,优化LC-MS/MS分析方法,并考察了血液和尿液基质的离子抑制作用。结果同时分析苯丙胺和MDA,液相1在3m in内完成,液相2可用于确认分析或复杂基质分离。尿液稀释法检材用量少,前处理简便快速。毛发中苯丙胺类兴奋剂和氯胺酮的最低检测限(LOD)为0.005~0.05ng/mg。对送检案例检材产妇头发和胎毛进行苯丙胺类兴奋剂和氯胺酮的分析。结论本方法可用于生物检材中苯丙胺类兴奋剂和氯胺酮的同时分析,血、尿等生物检材的离子抑制作用是影响本方法灵敏度的主要原因。     

快速溶剂萃取-凝胶色谱净化-LC／MS／MS相结合测定血中的杀参毒素类农药

目的建立血中杀参毒素类农药残留的快速分析方法。方法取一定量的Al2O3放入萃取池中做吸附剂,通过快速溶剂萃取仪萃取血液中杀参毒素类农药,同时达到在线净化的效果,后运用凝胶色谱净化联用仪进一步净化浓缩到2ml,提取液经LC／MS／MS进行检验。结果杀虫双在1．2×10g／ml～1．2×10^-6g／ml范围内线性关系良好,检出限为0．04ppb,杀虫眯为1．2×10^-6g／ml～7．2×10g／ml,检出限为0．34ppm。2种杀参毒素农药的平均回收率为89％、90％,相对标准偏差为1．9％、3％。结论整个方法简便、快速、准确、重现性好、灵敏度高,杂质干扰少。