HS-SPME-GC/MS法检测尿液及毛发中苯丙胺类毒品

目的采用顶空固相微萃取（HS-SPME）、GC/MS分析方法,对生物样品中苯丙胺（AM）、甲基苯丙胺（MAM）、3,4-亚甲二氧基苯丙胺（MDA）和3,4-亚甲二氧基甲基苯丙胺（MDMA）4种苯丙胺类毒品进行定性定量分析。方法在碱性和饱和盐处理状态下,采用100μm聚二甲基硅氧烷（PDMS）萃取纤维,于顶空瓶中进行生物样品AM、MAM、MDA、MDMA 4种毒品萃取,以2-甲基苯乙胺为内标,经气-质联用选择离子检测（GC/MS/SIM）模式进行定性定量分析。对HS-SPME条件优化,对方法的精密度、准确度和检出限进行测定。结果 AM、MAM、MDA、MDMA 4种毒品尿液中的最低检出限为5ng/mL,毛发中的最低检出限为0.5ng/mg。尿液中线性关系范围为0.05μg/mL~5μg/mL,r〉0.991,回收率为82%~108%,RSD为2.6%~6.1%（n=5）;毛发中线性关系范围为5ng/mg~500ng/mg,r〉0.992,回收率为80%~113%,RSD（%）为1.4%~6.8%（n=5）。结论 HS-SPME-GC/MS各项定量参数符合分析要求。该方法简单、灵活、经济、快速、无溶剂,适用于生物检材中该类毒品的分析。     

生物检材中阿维菌素的HPLC—MS／MS分析

目的建立生物检材包括血、肝组织、胃组织中阿维菌素（Avermectins）的HPLC—MS／MS分析方法。方法采用Oasis HLB固相萃取柱进行提取,以XTerra^TM RP18柱（2．1mm×100mm,3．5μm）色谱柱分离,以甲醇-0．1％冰醋酸水溶液（75：25）为流动相,流速为0．2mL／min。结果线性范围10ng／mL～3μg／mL,最小检出限为0．1ng／mL。结论本方法准确、快速,可用于生物检材血中阿维菌素的定性定量分析,肝及胃组织中阿维菌素的定性分析。     

HPLC-MS/MS法检测生物样品中的手性苯丙胺类药物和司来吉兰

目的建立全血、尿液中手性甲基苯丙胺、手性苯丙胺和司来吉兰同时分析检测的方法。方法全血、尿液经Oasis PRiME MCX固相萃取柱前处理,采用Phenomenex Lux AMP(150×3.0mm,3μm)手性液相色谱柱,以甲醇-5mmol/L碳酸氢铵水溶液(p H=11)为流动相,梯度洗脱,流速为0.35m L/min,以正离子多反应监测(MRM)模式检测,扫描时间21min。结果甲基苯丙胺两种对映异构体、苯丙胺两种对映异构体和司来吉兰在1-500ng/m L的范围内线性关系良好(各物质r~2 0.99);甲基苯丙胺两种对映异构体的检出限为0.05ng/m L,定量限为0.1ng/m L,苯丙胺两种对映异构体和司来吉兰的检出限为0.1ng/m L,定量限为0.5ng/m L;在低(5ng/m L)、中(50ng/m L)、高(200ng/m L)三个添加浓度下,各目标物的绝对回收率和基质效应均在可接受的范围内,日内精密度和日间精密度均小于12.61%。应用该方法对口服司来吉兰的比格犬的血液和尿液进行检测,结果表明仅存在司来吉兰原体、代谢物R-甲基苯丙胺和R-苯丙胺。结论本研究建立了全血、尿液中手性甲基苯丙胺、手性苯丙胺和司来吉兰的HPLCMS/MS定性、定量分析检测方法,该方法操作方便,灵敏度高,可为司法实践中法医毒物鉴定提供一定参考。     

快速溶剂萃取法提取血中的有机磷类农药

目的建立生物检材血液中有机磷类农药的快速溶剂萃取方法。方法通过优化快速溶剂萃取各参数，提取血中的有机磷类农药，同时达到在线净化的效果，然后进行GC／FPD分析检测。结果血中5种常见有机磷类农药的平均回收率均在70％以上，在0．05μg／mL-5μg／mL浓度范围内线性关系良好，检测限（S／N=10）均低于20ng／mL。结论该方法优于其它传统提取方法，快速、简便、高效且操作自动化，可广泛应用于生物检材血液中有机磷类农药的检验鉴定。     

芬氟拉明和苯丙胺类兴奋剂的固相微萃取

用固相微萃取技术从血中提取芬氟拉明、苯丙胺和甲基苯丙胺。在 70℃条件下用 10 0 μm聚二甲基硅氧烷萃取头吸附 15min。重氢甲基苯丙胺作内标 ,采用柱前衍生化的进样方式 ,气质联用仪测定。选择离子m /z2 6 8(芬氟拉明 )、m/z2 40 (苯丙胺 )、m /z2 5 4(甲基苯丙胺 )和m/z2 5 8(重氢甲基苯丙胺 ,内标 )的峰面积比定量。血中检测浓度可达 0 0 1～ 0 0 3μg/g。通过解剖例中芬氟拉明的实际测定 ,证明这是一个从血液中提取分析苯丙胺类衍生物的快速准确的方法     

LC-MS／MS法测定人血浆中盐酸洛哌丁胺

目的建立人血浆中盐酸洛哌丁胺的液相色谱-质谱联用测定法（LC-MS／MS）。方法血浆样品中盐酸洛哌丁胺与盐酸小檗碱（内标）经甲醇液．液提取后,采用ZORBAXSB—C18色谱柱（2．1mm×150mm×5μm）,柱温35℃,流动相为乙腈：0．1％甲酸（60：40,V／V）,流速为0．4mL／min,进样量10μL。电喷雾离子源（ESI）,正离子检测,以多反应监测（MRM）方式进行定量分析,用于监测的离子为m／z477→266（盐酸洛哌丁胺）和m／z366→292（内标）。结果盐酸洛哌丁胺的检测下限为0．2ng／mL（S／N=3）,在浓度0．5～500ng／mL范围内线性良好（r=0．9982）,低、中、高浓度（1ng／mL、20ng／mL、400ng／mL）的平均回收率分别为84．6％,88．5％和90．2％,日内与日问RSD分别小于6％与7％。结论LC—MS／MS法可用于盐酸洛哌丁胺的定性定量分析。     

HPLC／MS检测生物样品中的丁丙诺啡

目的建立了生物样品中丁丙诺啡的高效液相色谱-电喷雾串联质谱检测方法。方法样品经固相萃取提取净化、反相液相色谱分离后进行质谱检测，根据保留时间及特征离子进行定性分析，以母离子m／z468进行定量分析。结果在10-500ng／ml（ng／g）范围内峰面积与质量浓度的线性关系良好（r^2〉0．993）。在50、100、500ng／ml（ng／g）3个添加水平，尿、血、肝中丁丙诺啡的平均回收率为74％～94％，日内测定结果的相对标准偏差小于8％，日间测定结果的相对标准偏差小于10％。结论该方法简单、灵敏，特异性强，适用于生物样品中丁丙诺啡的分析检验。     

SPE—GC／MS、GC／NPD法检测血液中苯丙胺类毒品

目的利用GC／MS、GC／NPD与固相萃取（SPE）技术相结合,建立血液中苯丙胺类毒品的定性定量分析方法。方法采用Bond—ElutCerti{y固相柱、甲醇淋洗、二氯甲烷／异丙醇／氨水（78／20／2）洗脱固相萃取分离提取,比较了不同PH体系、稀释状态、洗脱溶剂对提取回收率的影响,建立血液中苯丙胺类毒品的GC／MS、GC／NPD定性定量分析方法。结果以GC／NPD分析AM、MA、MDA和MDMA浓度在15ng／mL-2000ng／mL、10ng／mL～1600ng／mL、20ng／mL-3000ng／ml、20ng／mL-3000ng／mL范围内线性关系良好,AM、MA、MDA和MDMA的检测限分别为10ng／mL、8ng／mL、15ng／mL、15ng／mL,方法平均回收率大于85％,标准偏差小于5％,GC／MS-Scan检测限分别为40ng／mL、32．0ng／mL、60．0ng／mL、60．0ng／mL。结论此方法可满足苯丙胺类毒品滥用者的血液定性定量分析。     

顶空固相微萃取与气质联用快速检测尿液中氯胺酮及去甲基氯胺酮

目的建立利用顶空固相微萃取（HS／SPME）结合气相色谱／质谱联用技术（GC／MS）快速检测吸毒人员尿液中氯胺酮（KT）及其主要代谢物去甲基氯胺酮（NK）的方法。方法样品瓶中加入尿样、6mol／L氢氧化钠溶液、固体氯化钠、SKF525A（内标），85℃下加热搅拌，用100μm聚二甲基硅氧烷（PDMS）萃取头顶空萃取10min，GC／MS（EI-SIM）检测。结果尿液中NK和KT浓度在0．1～2．0μg／ml范围内呈现线性关系，相关系数分别为（r^2）0．9991和0．9945，检测限（D／N=3）分别为0．87ng／ml和2．76ng／ml，定量限（S／N=10）分别为2．90ng／ml和18．52ng／ml。1ml尿液加标600ng，NK回收率在85．5％～110．1％，RSD〈13．2％（n=6）；KT回收率在77．5％～109．6％，RSD〈511．99％（n=6）。结论建立的方法简单、快速、灵敏、准确，适合尿液等生物检材中NK及KT的快速定性定量分析。     

血,尿中甲基苯丙胺以及代谢产物苯丙胺的分析研究

介绍了血、尿中甲基苯丙胺及其代谢产物苯丙胺的GC/MS，GC/FID和GC/NPD的定性定量分析方法．样品以4-苯基丁胺为内标，用200μl环己烷直接提取进样或提出物经微波照射快速衍生化后分析．方法简便、快速，回收率高于80％．检出限为2～5ng/ml．建立了体内甲基苯丙胶和苯丙胺的d/l光学对映体测定方法，可用于判断毒品来源及毒作用．     

分子印迹固相萃取法在血中苯丙胺类毒品分析中的应用

目的建立分子印迹固相萃取（MISPE）、GC/MS分析方法,用于血液中苯丙胺类毒品检测。方法 10mmol/L醋酸铵缓冲液（pH8.0）4倍稀释空白添加血液,1mL甲醇,1mL10mmol/L醋酸铵缓冲液（pH8.0）活化苯丙胺类分子印迹固相萃取柱;2×1mL去离子水、1mL60%的乙腈去离子水、1mL1%醋酸乙腈洗涤杂质;2×1mL1%甲酸/甲醇洗脱,洗脱液挥干定容,经GC/NPD、GC/MS分析检测。结果各种苯丙胺类毒品回收率均在90%以上,在20～5 000ng/mL浓度范围内线性关系良好,r2为0.995 7～0.998 9,LOQ在16～30ng/mL之间,LOD在8～15ng/mL之间。结论本方法回收率高,净化效果显著,稳定性好,杂质干扰少,可用于血液中低浓度苯丙胺类毒品的分析检测。     

甲基苯丙胺滥用与司来吉兰服用的区分:尿液中甲基苯丙胺和苯丙胺的手性分析

目的考察司来吉兰及其代谢物在尿液中的含量变化,并结合实际案例探讨手性分析区分甲基苯丙胺滥用与司来吉兰服用的可行性。方法采用CHIROBIOTICTM V2手性液相色谱柱对尿液样品进行手性分离和液相色谱-串联质谱(LC-MS/MS)法测定,并对司来吉兰服药志愿者尿样、疑服用司来吉兰的涉毒人员尿样进行甲基苯丙胺和苯丙胺的手性分析。结果服用5 mg司来吉兰后,尿液中司来吉兰的检出时限仅为7h。尿液中R(-)-甲基苯丙胺和R(-)-苯丙胺约在7h质量浓度最高,分别为0.86μg/m L和0.18μg/m L,并在80 h和168 h后无法检出。应用该方法成功分析了疑服用司来吉兰的涉毒人员尿液中甲基苯丙胺和苯丙胺的来源。结论甲基苯丙胺和苯丙胺的手性分析以及司来吉兰代谢物检测可区分甲基苯丙胺滥用与司来吉兰服用。     

尿中苯丙胺、甲基苯丙胺、MDA和MDMA的固相微萃取和GC/MS/SIM测定

目的研究固相微萃取(SPME)用于尿中苯丙胺(AMP)、甲基苯丙胺(MET)、3,4-亚甲二氧基苯丙胺(MDA)和3,4-亚甲二氧基甲基苯丙胺(MDMA)的提取。方法样品调节至碱性和用盐饱和后用顶空SPME,内标为MET-d5。萃取纤维为100μm聚二甲基硅氧烷(PDMS)。用气质联用选择离子检测(GC/MS/SIM)。结果0.2μg/ml加标尿样,AMP、MET、MDA和MDMA的富集倍数分别为22,60,13和47。检出限(S/N=3)为0.4～9.5ng/ml。线性范围为0.05～1μg/ml。0.2、0.5和1.0μg/ml加标尿样,相对回收率77.9%～112.4%,变异系数2.7%～18.0%(n=5)。用该方法分析5个案件样品,和常规液液萃取结果接近。结论顶空SPME法用于尿中AMP、MET、MDA和MDMA等化合物的分析,无需有机溶剂,富集效率高,提取-富集-进样一体化,简单方便实用。     

Forensic toxicologic analysis of methamphetamine and amphetamine optical isomers by high performance liquid chromatography

Optical isomers (d and l) and racemic compounds (dl) of methamphetamine (MAMP) and amphetamine (AMP), and biologic materials including those substances, could be analyzed by high performance liquid chromatography. Examining the temperature for the analysis, 40 degrees C was the optimal condition in the reproducibility of separated MAMP-isomers. The reproducibility at the temperature did not vary significantly. The measured values of optical isomers were 0.116 +/- 0.012, 1.082 +/- 0.070 and 8.984 +/- 0.136 for the mixing ratios (l/d) of 0.111, 1.000, and 9.000, respectively. The detection limit for both d- and l-isomers was 25 ng. The analytic result of hair specimens from two stimulant abusers by the present method indicates that they contained only d-MAMP and d-AMP, which is believed to have the strongest pharmacologic effect among the optical isomers of MAMP. The coefficient of variation in the analysis of five replicate standards, prepared by adding 1,000 ng each of racemate MAMP and AMP to hair, was less than 4%. The measured value against l/d = 1.000 was 1.040 +/- 0.040 in MAMP and 0.980 +/- 0.030 in AMP. The detection limit for both racemate MAMP and AMP accumulated in hair was 250 ng. The analysis of the optical isomers by our method would contribute to identifying the smuggling routes or the illicit method.     

小鼠各脏器及血中甲基苯丙胺的分布

目的通过给小鼠腹腔注射甲基苯丙胺(MAMP),建立小鼠急性染毒模型。方法运用GC/NPD技术,系统地进行了染毒小鼠模型各脏器及血中甲基苯丙胺(MAMP)的定性定量测定。采用1-萘胺作为内标,样品处理时采取加盐酸成盐后,又碱化,用有机溶剂萃取浓缩挥发。结果回收率高于80%。血、各脏器中最低检出限为2～5ng/ml。结论脑、肾、脾组织可以用于法庭科学分析。     

Evaluation of ephedrine, pseudoephedrine and phenylpropanolamine concentrations in human urine samples and a comparison of the specificity of DRI amphetamines and Abuscreen online (KIMS) amphetamines screening immunoassays

The purpose of this study was to evaluate the ability of two amphetamine class screening reagents to exclude ephedrine (EPH), pseudoephedrine (PSEPH), and phenylpropanolamine (PPA) from falsely producing positive immunoassay screening results. The study also sought to characterize the prevalence and concentration distributions of EPH, PSEPH, and PPA in samples that produced positive amphetamine screening results. Approximately 27,400 randomly collected human urine samples from Navy and Marine Corps members were simultaneously screened for amphetamines using the DRI and Abuscreen online immunoassays at a cutoff concentration of 500 ng/mL. All samples that screened positive were confirmed for amphetamine (AMP), methamphetamine (MTH), 3,4-Methylenedioxyamphetamine (MDA), 3,4-Methylenedioxymethamphetamine (MDMA), EPH, PSEPH, and PPA by gas chromatography/mass spectrometry (GC/MS). The DRI AMP immunoassay identified 1,104 presumptive amphetamine positive samples, of which only 1.99% confirmed positive for the presence of AMP, MTH, MDA, or MDMA. In contrast, the online AMP reagent identified 317 presumptive amphetamine positives with a confirmation rate for AMP, MTH, MDA, or MDMA of 7.94%. The presence of EPH, PSEPH, or PPA was confirmed in 833 of the 1,104 samples that failed to confirm positive for AMP, MTH, MDA, or MDMA; all of the 833 samples contained PSEPH. When compared to the entire screened sample set, PSEPH was present in approximately 3%, EPH in 0.9%, and PPA in 0.8% of the samples. The results indicate that cross reactivities for EPH, PSEPH, and PPA are greater than reported by the manufacturer of these reagents. The distribution of concentrations indicates that very large concentrations of EPH, PSEPH, and PPA are common.     

Simultaneous quantitative analysis of methamphetamine and 4-hydroxymethamphetamine in body fluids by gas chromatography/mass spectrometry

Pentodeuterated 4-hydroxymethamphetamine (HMAMP-d5), 1-(4-hydroxyphenyl)-2-(methyl-d3-amino)-propane-1,2-d2 of high quality was prepared and proved to be a most useful internal standard for quantitative analyses of 4-hydroxymethamphetamine (HMAMP), a main metabolite of methamphetamine (MAMP). Highly reliable results were obtained by gas chromatography/mass spectrometry. Simultaneously we determined also MAMP, amphetamine (AMP), 4-hydroxyamphetamine (HAMP), and HMAMP in body fluids, using two internal standards, HMAMP-d5 for HMAMP and HAMP and pentodeuterated methamphetamine, 1-phenyl-2-(methyl-d3-amino)-propane-1,2-d2, for MAMP and AMP.     

Simultaneous analysis of amphetamine, methamphetamine, and 3, 4-methylenedioxymethamphetamine (MDMA) in urine samples by solid-phase extraction, derivatization, and gas chromatography/mass spectrometry

A rapid and effective solid-phase extraction procedure using Bond Elute Certify bonded silica sorbent cartridges was adopted to extract amphetamine, methamphetamine, and 3,4-methylenedioxymethamphetamine (MDMA or Ecstasy) from urine samples. The extract was derivatized with trichloroacetic anhydride prior to gas chromatography/mass spectrometry (GC/MS) analysis with selected ion monitoring of the following ions: 190, 91, 188; 204, 91, 202; 162, 135, 202; 194, 123; and 211, 209 for the derivatized amphetamine, methamphetamine, MDMA, d5-amphetamine, and d9-methamphetamine, respectively. The first of the ions listed for each compound was used for quantitation. The compound d5-amphetamine was used as the internal standard for amphetamine, and d9-methamphetamine was used for methamphetamine and MDMA. Results showed a higher than 65% recovery and a reproducibility with less than a 5% coefficient of variation. When a sample size of 2 mL was used, the lowest detectable concentration was about 50 ng/mL, and a near-perfect fit can be obtained (within the 250 to 4000-ng/mL concentration range studied) using a second-order polynomial model.     

Distribution and optical purity of methamphetamine found in toxic concentration in a civil aviation accident pilot fatality

Toxicological evaluation of postmortem samples collected from a pilot involved in a unique fatal civil aircraft accident is described in this paper. A one-occupant airplane was substantially damaged upon colliding with terrain in poor visibility. Remains of the pilot were found outside the aircraft. Pathological examination revealed multiple blunt force injuries and vascular congestion. The fluorescence polarization immunoassay disclosed 8.0 microg/mL amphetamines in urine. Gas chromatographic/mass spectrometric analyses determined the presence of methamphetamine (1.13 microg/mL in blood and 59.2 microg/mL in urine) and amphetamine (0.022 microg/mL in blood and 1.50 microg/mL in urine). Methamphetamine was distributed throughout the body, including the brain. The amount of methamphetamine in gastric contents was 575-fold higher than that of amphetamine. The (+)- and (-)-forms of methamphetamine were present in equal proportions in gastric contents. The methamphetamine concentration found in blood was in the range sufficient to produce toxic effects, causing performance impairment.