不同前处理模式下检验地芬尼多死亡结果比较

目的建立一种前处理优化条件下血中地芬尼多的液相色谱-串联质谱的检测方法。方法比较了血中三种不同的前处理方式(LLE、PP、SPE)的基质效应,采用液相色谱-串联质谱仪分析,多反应检测扫描模式(MRM)检测地芬尼多,采用外标法定量。结果采用SPE小柱的前处理方式最优。血中地芬尼多在1.0ng/m L～100ng/m L浓度范围内线性关系良好,回归方程为y=8.18×10~4x+18330(r=0.998),定量限在0.3ng/m L。地芬尼多在1ng/m L添加水平,回收率95.0%,精密度6.0%。结论本研究比较了几种不同的前处理方法,从中选择较为简便、基质干扰小的一种可用于血中地芬尼多的定性定量检测,同时测定了几起死亡案件中地芬尼多的血浓度,为侦查办案提供参考。     

甲氰菊酯在家兔体内的死后分布研究

目的建立甲氰菊酯家兔灌胃染毒致死模型和生物检材中甲氰菊酯的气相色谱和气相色谱-质谱联用检测方法,研究甲氰菊酯在家兔体内的死后分布规律。方法家兔6只,甲氰菊酯经口灌胃染毒,死亡后迅速解剖,取心血、外周血、肝等组织,气相色谱和气相色谱-质谱联用法检测甲氰菊酯含量;部分组织经甲醛固定,HE染色,光镜观察其病理改变。结果家兔染毒后2～3h出现中毒表现,染毒后4.5～8h死亡。气相色谱和气相色谱-质谱联用法均检测到甲氰菊酯。甲氰菊酯在家兔体内死后分布为胃壁（458.92±32.82）μg/g、肾（46.47±6.30）μg/g、肝（35.79±20.11）μg/g、大脑（28.77±10.52）μg/g、心（26.49±4.10）μg/g、脾（22.23±5.37）μg/g、胆汁（10.87±1.42）μg/mL、肺（10.32±0.78）μg/g、周围血（8.14±1.12）μg/mL和心血（8.20±1.83）μg/mL。结论甲氰菊酯的灌胃染毒致死模型、气相色谱和气相色谱-质谱联用检测方法及死后分布规律可应用于甲氰菊酯中毒死亡案件的法医学鉴定及法医毒物动力学研究。     

GC/MS快速测定生物样本中地芬尼多及代谢物

正盐酸地芬尼多,化学名α,α-二苯基-1-哌啶丁醇盐酸盐,又名眩晕停,常用于治疗眩晕症、晕车晕船等[1]。有文献曾报道地芬尼多超剂量致小儿中毒的病例[2]。本文采用GC/MS快速测定法对人体生物检材中地芬尼多进行检测,为同行进行相关检验时借鉴。1样本与检验1.1样本及前处理送检某服用盐酸地芬尼多过量致死者心血、尿液、胃内容物、肝组织样本。其中取心血0.5m L、尿液     

血液中64种常见有机氯菊酯类农药的快速筛查

目的建立人体血浆中64种有机氯菊酯类农药多残留的气相色谱（GC）快速筛查分析方法。方法空白人体静脉抗凝血用乙腈沉淀蛋白,乙酸乙酯∶环己烷（v/v,3∶1）进行液液萃取净化,使用HP-5色谱柱,采用气相色谱进行定性、定量分析。对方法进行优化并进行方法学评价。结果 64种农药在0.001~0.1μg/mL范围内线性关系均良好,相关系数在0.990 1~0.999 9之间。检出限在0.001~0.15μg/mL范围内,方法定量限在0.001~0.5μg/mL之间,回收率总体于80%~110%之间,相对标准偏差小于15%,方法检出限总体于0.01μg/mL以下,日内精密度在1.5%~11.5%之间,日间精密度在2.9%~13.9%之间。结论本文建立的人体血浆的农药多残留快速筛查测定法,符合农药残留分析方法的要求,可在相关研究和实践中选用。     

SPE/UPLC法检测血中吗啡、苯丙胺类及氯胺酮

目的建立SPE/UPLC方法在同一条件下同时检测血中吗啡、苯丙胺类及氯胺酮。方法采用SCX 3cc（60mg）固相萃取柱萃取血中吗啡、MA、MDMA、MDA及氯胺酮,用超高效液相色谱（UPLC）-二极管阵列检测器（PDA）检测,结合保留时间和紫外光谱进行定性、定量分析,对实验各环节进行优化,并进行实际案例检测。结果吗啡、MA、MDMA、MDA、氯胺酮的固相萃取提取回收率分别为81.4%±2.51%、88.2%±2.48%、91.8%±2.03%、93.8%±1.46%、74.8%±2.27%,峰面积和质量浓度的线性关系良好（r〉0.999）,线性范围分别为0.08～100μg/mL、0.4～100μg/mL、0.2～75μg/mL、0.3～75μg/mL、0.4～100μg/mL,检出限分别为30pg、200pg、80pg、100pg、200pg。结论本文所建方法适用于血中吗啡、苯丙胺类、氯胺酮常见毒品的筛选及定量分析。     

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。     

甲胺磷在犬体内的死后分布

目的建立甲胺磷的犬灌胃染毒致死模型,观察甲胺磷在犬体内的死后分布规律。方法犬经8倍LD50（7.4mg/kg）剂量甲胺磷灌胃后,观察其中毒症状,死亡后即刻解剖,分别取心、肝、脾、肺、肾、脑、右上肢肌、右下肢肌、胸肌、胃组织、心血、胆汁、玻璃体液和尿液,GC/MS和GC法检测其中甲胺磷含量。结果犬8倍LD50甲胺磷灌胃染毒后20min内出现中毒症状（,53.3±14.1）min死亡。各组织脏器及体液中甲胺磷含量由高到低分别为胃（99.84±0.87）μg/g、脾（46.87±28.67）μg/g、肝（43.82±22.74）μg/g、肾（43.79±29.04）μg/g、心血（35.36±13.98）μg/mL、肺（35.25±18.59）μg/g、尿34.81μg/mL、胸肌（19.23±17.18）μg/g、右上肢（16.92±8.98）μg/g、心（15.09±6.11）μg/g、右下肢（12.83±7.63）μg/g、脑（10.91±4.13）μg/g、胆汁（6.75±1.45）μg/mL、玻璃体液（6.22±4.97）μg/mL。结论甲胺磷在犬体内死后分布不均,胃、脾、肝、肾、心血、肺、尿检材中含量较高,可作为疑似甲胺磷中毒毒物分析的检材。     

高效液相色谱法测定人血液、尿液中的2,4-D丁酯

目的建立检测血液、尿液中2,4-D丁酯的高效液相色谱分析方法。方法采用正己烷为样品萃取溶剂,色谱柱为Zorbax SB-Aq柱,流动相为V（甲醇）∶V（水）=60∶40。结果 2,4-D丁酯在血液和尿液中的线性范围分别为0.10～10.00μg/mL（r≥0.999 8）和0.08～8.00μg/mL（r≥0.999 5）,检测限分别为0.002 0μg/mL和0.001 8μg/mL,准确度为94.5%～104.5%,日内、日间精密度≤4.5%。结论本研究建立的血液、尿液中2,4-D丁酯的提取和HPLC检测方法,可应用于2,4-D丁酯中毒的快速检验和中毒死亡的法医学鉴定。     

人血、尿中富马酸喹硫平的气相色谱分析

目的建立人血、尿中富马酸喹硫平的气相色谱分析方法。方法用乙醚提取血、尿中的富马酸喹硫平，直接对其进行定性、定量分析。以正常人血、尿为空白样本，分别添加标准富马酸喹硫平，确定检材的前处理方法、色谱分析条件、工作曲线、线性范围、方法的精密度、回收率等，并对1例大剂量服用富马酸喹硫平中毒死者的体液浓度进行测定。结果该方法分析血、尿中富马酸喹硫平的线性范围分别为8．0～800．0μg／ml和20．0—800．0μg/ml；最低检测限分别为0．04μg／ml和0．10μg／ml（S／N≥3），日内、日间精密度均小于4％，回收率在97．08％-101．42％之间。结论该分析方法操作便捷、实用、准确度高，适用于富马酸喹硫平的临床血药浓度快速监测和法医毒物鉴定。     

GC法检测血液和尿液中甲基苯丙胺和咖啡因

目的建立同时测定血、尿中甲基苯丙胺和咖啡因含量的方法。方法应用GC／NPD技术,以4-苯基丁胺为内标,直接碱化,用氯仿提取,三氟乙酸酐衍生化,8CB熔融石英毛细管柱（30m×0．25mm×0．25μm）分析。结果生物样品中甲基苯丙胺与咖啡因在0．012—7．5μg/mL浓度范围内线性关系良好,检测限（S／N=3）依次为1．2ng／mL,0．6ng／mL（血）;1．6ng／mL,0．8ng／mL（尿）。苯丙胺在0．017—10．0μg／mL浓度范围内线性关系良好,检测限为1．6mg／mL（血）,3．2ng／mL（尿）。所有样本回收率均大于85％。结论本方法准确、灵敏,适用于血、尿中甲基苯丙胺及其代谢物苯丙胺的三氟乙酸酐衍生化物和咖啡因的同时检测,为判定滥用毒品种类、追查毒品来源以及研究生物体内甲基苯丙胺和咖啡因的交互影响提供了检测手段。     

大鼠血液、尿液中阿米替林的气相色谱快速分析

目的建专：m液及尿液中阿米替林（AMTL）的气相色谱分析方法,、方法以正常大鼠m液及尿液为空F1样奉,分别添加AMTI-标准品和内标SKF525A。实验大鼠以AMTL2倍LD50灌胃,致大鼠急性中毒后提取血液及尿液。用乙醚提取样本中AMTL,采用GC／FID法进行定量分析,并考察实验条件,结果采用该方法,血液及尿液中AMTL线性池用分别为5～150μg／mL（r=0．993）和5～150μg／mL（r=0．998）;最低检测限（S／N／〉3）均为1．0陆g／mL;口内、口间精密度均小于6％,同收率存95.5％～105．6％之间。结论该方法方操作便捷、捧确度高,适用=fAMTL临床治疗中血药浓度快速监测和法医毒物分析鉴定。     

气相色谱-串联质谱法分析尿和血中除草剂百草枯

目的建立尿和血中百草枯的离子交换固相萃取-气相色谱-串联质谱分析方法。方法尿样加内标乙基百草枯,用732阳离子交换树脂提取;血样加内标乙基百草枯,用三氯乙酸凝聚蛋白质后取上清液用732阳离子交换树脂提取。提取物用硼氢化钠在水溶液中碱性条件下还原,还原物用有机溶剂提取进行气相色谱-串联质谱法分析。结果尿和血中百草枯的提取率分别为76％和74％,检测限分别为2ng／mL和10ng／mL,尿添加百草枯100ng／mL和血添加百草枯500ng／mL水平的回收率分别为99．6±5．6％和99．3±7．6％（Mean±CV）。结论本文建立的分析方法灵敏度高,能够满足中毒致死案件检验及临床毒物检验的需要。     

中毒致死者体内芬氟拉明的GC/NPD,GC/MS法测定

建立了生物检材中芬氟拉明的定性定量分析方法。体液及脏器组织经有机溶剂提取后 ,用GC/MS法进行药物筛选、定性 ,生物检材中的芬氟拉明浓度用4 -苯丁胺作内标、GC/NPD法测定。测得芬氟拉明中毒致死者的血液、尿液、肝等组织中浓度分别为7.8μg/ml、64.2μg/ml、31.3μg/g。并对尸体解剖所见及方法可行性进行讨论     

体液中氟乙酰胺SPE-GC/MS检测

目的　利用GC/MS与固相萃取 (SPE)技术相结合 ,开发血和尿样中氟乙酰胺鼠药的GC/MS定量分析新方法 ,并用于实际案例检测。方法　选择乙酰胺为内标 ,通过比较不同固相柱的萃取效率和不同条件对回收率的影响 ,优化用于血和尿样中氟乙酰胺萃取的固相柱和提取条件 ,利用氟乙酰胺与乙酰胺质谱图的分子离子峰面积之比与氟乙酰胺浓度的定量关系 ,建立血和尿样中氟乙酰胺鼠药的GC/MS定量分析新方法。结果　用硅胶柱萃取 ,峰面积之比与氟乙酰胺浓度在 5 0～ 90 μg/ml范围呈线性关系 ,检测限为 1 0 μg/ml。血样中氟乙酰胺检测的平均回收率达 91 6% ,标准偏差小于 7 3 %。结论　此法对实际样品的测定证明可满足氟乙酰胺鼠药中毒的定性定量要求。     

Benzodiazepine findings in blood and urine by gas chromatography and immunoassay

Gas chromatography (GC) and immunoassay techniques applied to blood and urine specimens were compared for the screening of benzodiazepines in postmortem forensic toxicology. Five hundred and six such successive postmortem cases in which both urine and peripheral blood was sent for toxicological analysis by the medical examiners were selected. The urine specimens were tested by the Emit((R)) d.a.u. Benzodiazepine Assay, and in parallel, the blood and urine specimens were screened for benzodiazepine drugs and their metabolites by an established automated dual-column GC method. The lowest number of positives (153) was obtained when immunoassay was performed without enzyme hydrolysis. When urine samples were hydrolysed before immunoassay, the number of positives increased to 175. The highest number of positives (200) was obtained in urine by GC, and the screening of blood by GC yielded 185 quantitative results. Despite the urine GC screening produced the most positives, the quantitative screening of the blood by GC appears to be the most efficient approach in postmortem forensic toxicology, considering the fact that although urine findings confirm the presence of the drug, quantitative results in urine are irrelevant to acute toxicity.     

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.     

The comparison of toluene determination between headspace-solid phase microextraction and headspace methods in glue-sniffer's blood and urine samples

An accurate and simple method was developed to determine the level of toluene in urine and blood quantitatively by using the gas chromatography/mass spectrometry (GC/MS) with headspace--solid phase microextraction (HS-SPME) technique. An assembly of SPME with a replaceable extraction fiber, coated with 100 microm polydimethylsiloxane, was used. The detection limit of toluene in blood and urine with HS-SPME technique was 10 times higher than that with headspace (HS) technique. To compare the HS-SPME with HS technique for the determination of toluene in biological fluids, blood and urine samples from glue sniffers were analyzed by both methods. The level of toluene by the two techniques was highly correlated: the correlation coefficient (r2) between the two sets of values were 0.98 and 0.96 in urine and blood, respectively.     

Simultaneous analyses of cocaine, cocaethylene, and their possible metabolic and pyrolytic products

A method was developed for simultaneously analyzing cocaine (COC), benzoylecgonine (BZE), norbenzoylecgonine (BNE), norcocaine (NCOC), ecgonine (ECG), ecgonine methyl ester (EME), m-hydroxybenzoylecgonine (HBZE), anhydroecgonine methyl ester (AEME), cocaethylene (CE), norcocaethylene (NCE), and ecgonine ethyl ester (EEE) in blood, urine, and muscle. Available deuterated analogs of these analytes were used as internal standards. Proteins from blood and muscle homogenate were precipitated with cold acetonitrile. After the removal of acetonitrile by evaporation, the supernatants and urine were subjected to solid-phase extraction. The eluted analytes were converted to their hydrochloride salts and derivatized with pentafluoropropionic anhydride and 2,2,3,3,3-pentafluoro-1-propanol. The derivatized products were analyzed by a gas chromatograph (GC)/mass spectrometer by selected ion monitoring. The limit of detection (LOD) for COC, BZE, NCOC, EME, CE, NCE, and EEE was 2ng/ml, while the LODs for BNE, ECG, HBZE, and AEME were 25, 640, 50, and 13 ng/ml, respectively. This method was successfully applied in analyzing 13 case samples from aviation accident pilot fatalities and motor vehicle operators. AEME concentrations found in the 13 samples were consistent with those produced solely by the GC inlet pyrolysis of COC controls in blood. Anhydroecgonine cannot be used as a marker for the abuse of COC by smoking because it is also pyrolytically produced from COC metabolites on the GC inlet. The developed method can be effectively adopted for analyzing COC and related compounds in urine, blood, and muscle by a single extraction with increased sensitivity through formation of hydrochloride salts and using a one-step derivatization.