丁丙诺啡的检验

目的建立检验丁丙诺啡的方法。方法用气质联用仪与高效TLC法进行定性分析。结果丁丙诺啡在展开剂苯∶正己烷∶二乙胺=40∶10∶10时,Rf值为0.55;环己烷∶丙酮=1∶1时,Rf值为0.35;质谱图保留时间为19.617min。结论本方法操作简便、准确,适合办案。     

微波照射在衍生化反应中的应用

介绍了用微波照射技术快速制备吗啡、苯丙胺类的乙酰、三氟乙酰、五氟丙酰、七氟丁酰、MSTFA衍生物方法。常规加热方法制备这些衍生物需在60～70℃反应30min,而使用微波照射（~400W,仅需2～3min即可完成．二种方法所得的衍生物气相保留时间和质谱碎片相同．     

五氟丙酰衍生化-气相色谱/质谱联用法分析尿液中7-氨基硝西泮

目的用五氟丙酰衍生化-气相色谱/质谱联用法分析尿液中硝西泮的主要代谢物7-氨基硝西泮。方法尿液经乙醚萃取后,用五氟丙酰酸酐(PFPA)进行衍生化,得到7-氨基硝西泮衍生化物的总离子流色谱图和质谱图。结果根据7-氨基硝西泮衍生化物色谱的保留时间和质谱中主要特征离子的质荷比进行定性分析;用7-氨基氟硝西泮做内标,以7-氨基硝西泮和内标衍生化物定量离子的色谱峰面积比与浓度的关系进行定量分析。结论用五氟丙酰衍生化-GC/MS分析尿液中硝西泮的主要代谢物7-氨基硝西泮的方法定性、定量灵敏准确,测定结果可应用于司法鉴定。     

LC-MS/MS法快速测定头发中可卡因及其代谢物苯甲酰爱康宁

目的建立头发中可卡因(cocaine)及其代谢物苯甲酰爱康宁(benzoylecgonine)的液相色谱-串联质谱(LC-MS/MS)快速测定方法。方法去污处理后的头发中加入氘代内标(可卡因-D_3和苯甲酰爱康宁-D_8),经甲醇超声提取后用Restek Allure PFP丙基柱分离,采用多反应监测模式同时测定可卡因和苯甲酰爱康宁。结果头发中可卡因和苯甲酰爱康宁在0.02~10.00 ng/mg质量分数范围内线性关系良好,检出限均为0.01 ng/mg。结论本研究所建方法样品前处理简单、快速、选择性好,适用于头发中可卡因及代谢物苯甲酰爱康宁的检测。     

LC-MS／MS测定尿液中可卡因及其代谢物苯甲酰爱康宁

目的建立尿液中可卡因(cocaine,COC)及其代谢物苯甲酰爱康宁(benzoylecgonine,BZE)的液相色谱-串联质谱分析方法。方法尿液经固相萃取后,用AllurePFP丙基柱分离,以V(甲醇):V(20mmol/L乙酸胺和0.1%甲酸的缓冲溶液)=80∶20为流动相,采用二级质谱多反应监测模式检测COC和BZE。按10mg/kg的剂量对豚鼠腹腔注射可卡因,给药后收集7d尿液。结果尿液中COC和BZE在2.0～100ng/mL质量浓度范围内线性关系良好(r=0.9995),最低检测限(LOD)为0.5ng/mL;回收率大于90%;日内和日间精密度均小于6%;豚鼠尿液中主要检测目标物是BZE,且BZE检测时限也较COC长。结论所建方法灵敏度高,选择性好,适用于尿液中可卡因和苯甲酰爱康宁的检测。     

银环蛇中毒死亡鉴定方法的实验研究(Ⅱ)──长碳臂活化生物素─马抗银环蛇抗体的制备

作者用ｄ－生物素自制Ｎ－羟基丁二酰亚胺６－生物素化酰氨已酯（长碳臂活化生物素）。质谱分子离子峰测定分子量为４５４；红外光谱分析各官能基团与分子结构式吻合。探讨了长碳臂活化生物素与精制马抗银环蛇抗体交联的最适比例。与普通活化生物素标记、辣根过氧化物酶标记的同样抗体相比，稀释滴度分别提高４—８倍。     

LC-MS/MS法检测人血液中的利多卡因及其代谢物

目的建立人血液样品中利多卡因及其代谢物单乙基甘氨酰二甲苯胺(MEGX)和甘氨酰二甲苯胺(GX的液相色谱-串联质谱(LC-MS/MS)分析方法。方法人血液样品经乙腈沉淀蛋白后,Zorbax RRHD Plus C18柱(2.1mm×50mm,1.8μm)分离,以0.1%甲酸和乙腈为流动相进行洗脱。质谱采用电喷雾正离子化(ESI+),多反应监测扫描模式。结果血液中利多卡因、MEGX和GX在相应范围内线性良好,相关系数(r 0.9950)。在血液中检出限分别为0.1 ng/mL、0.5 ng/mL和0.2 ng/mL,方法回收率为92.7%～103.9%,准确度为92.9%～113.1%,日内、日间精密度的相对标准偏差均不超过13.0%。在1例肌肉注射利多卡因死者心血中利多卡因、MEGX和GX的质量浓度分别为1.520μg/mL、0.019μg/mL和0.266μg/mL。结论本方法灵敏度高、选择性好,适用于血液中利多卡因及其代谢物的检测,可为利多卡因临床治疗过程中的药物浓度监测和法医学鉴定提供技术支撑。     

海洛因的薄层扫描定量测定法

本文采用薄层扫描法测定海洛因的含量,以环己烷:苯:二乙胺(70:25:10)为展开剂,并用HLC法对其定量结果进行验证,两者间相对偏差不超过2％。方法简便、快速、准确。     

气质联用仪自动筛选常见毒物的应用研究

目的建立快速、灵敏的常见毒物的质谱自动筛选检测方法。方法建立常见毒物的质谱用户库，优化分离条件，优化质谱数据的自动分析参数，进行标样和样品分析。结果建立了含1306种常见毒物的质谱用户库；建立了自动筛选方法；得到了150种常见毒物的保留时间和检测限。结论建立的方法具有快速、灵敏、准确的优点，完全可替代繁杂的质谱检索手工操作。     

液相色谱质谱联用测定乌头碱在大鼠体内代谢产物

目的鉴定乌头碱在大鼠体内的主要代谢产物。方法灌胃给予雄性大鼠1.0mg/kg乌头碱后,收集24h尿液,固相萃取法提取,液相色谱-质谱法测定乌头碱及其代谢物。结果经与空白组对照发现给药后大鼠尿样中除乌头碱原体外还有4种代谢产物,并分别测得其准分子离子峰及其各级碎片离子。结论经与对照品比较及质谱断裂规律推断4个代谢产物分别为中乌头碱、16-O-去甲基乌头碱、16-O-去甲基中乌头碱、苯甲酰乌头碱。     

Body fluid levels of lysergide (LSD)

Published lysergide (LSD) levels in body fluids are summarised, together with the results of 20 cases in which we determined LSD in body fluids by radioimmunoassay. The validity of methods used for LSD analysis is discussed.     

The determination of lysergide (LSD) in urine by high-performance liquid chromatography-isotope dilution mass spectrometry (IDMS)

The use of isotope dilution mass spectrometry (IDMS) has been investigated for the forensic confirmation of lysergic acid diethylamide (LSD) in urine by LC-MS. The advantages of using a deuterated analog of LSD as an internal standard over methysergide are discussed. This study includes a comparison of the electrospray mass spectra of LSD, LSD-d3 and methysergide, and discusses the choice of suitable ions for use in selected ion monitoring (SIM) mode. An IDMS method is presented for the LC-MS confirmation of LSD in urine, with a limit of quantification (LOQ) of 0.5 ng/mL, reflecting the forensic requirement at this laboratory. Under some circumstances the LOQ can be improved to 0.1 ng/mL. This method is linear in the range tested (up to 10 ng/mL LSD in urine) and has been validated in terms of accuracy and precision.     

LSD and 9,10-dihydro-LSD Analyses in Street Drug Blotter Samples via Easy Ambient Sonic-Spray Ionization MassSpectrometry (EASI-MS)

Normally, the identification of the LSD drug is performed by forensic laboratories, using the Ehrlich spot test. However, this is a nonspecific analysis. Additionally, the Brazilian Federal Police has identified the presence of a new compound in seized blotters: 9,10-dihydro-LSD, an uncontrolled substance. In this work, easy ambient sonic-spray ionization mass spectrometry in the positive ion mode, EASI(+)-MS, was used to characterize LSD and 9,10-dihydro-LSD compositions directly from the surface of blotters. The presence of LSD in the seized blotter samples were also confirmed via high-performance liquid chromatography with ultraviolet detector. In a set of 41 blotters analyzed by EASI(+)-MS, 28 showed positive results for LSD, seven for 9,10-dihydro-LSD, and another six samples showed negative results for both LSD and 9,10-dihydro-LSD. The combination of thin layer chromatography with EASI-MS also demonstrated to be a relatively simple and powerful screening tool for forensic analysis of street drugs.     

Amphetamine, cocaine and cannabinoids use among truck drivers on the roads in the State of Sao Paulo, Brazil

Lysergic acid diethylamide (LSD) is a potent hallucinogen, active at very low dosage and its determination in body fluids in a forensic context may present some difficulties, even more so in hair. A dedicated liquid chromatography-electrospray-tandem mass spectrometry (LC-ES-MS/MS) assay in hair was used to document the case of a 24-year-old man found dead after a party. Briefly, after a decontamination step, a 50mg sample of the victim's pubic hair was cut into small pieces (<1mm length), and incubated overnight in 3mL of phosphate buffer pH 5 at room temperature. After a liquid-liquid extraction (dichloromethane/ether), the extract was analyzed using a LC-ES-MS/MS method exhibiting a limit of quantification of 0.5pg/mg for LSD. A LSD concentration of 0.66pg/mg of pubic hair was observed. However, this result remains difficult to interpret owing to the concomitant LSD presence in the victim's post mortem blood and urine, the lack of previously reported LSD concentrations in hair, and the absence of data about LSD incorporation and stability in pubic hair.     

Determination of lysergic acid diethylamide in body fluids by high-performance liquid chromatography and fluorescence detection--a more sensitive method suitable for routine use

A new method for determination of lysergic acid diethylamide (LSD) in body fluids by high-performance liquid chromatography and fluorescence detection was developed based on previously published methods. The new method is suitable for confirmation of samples tested positive by immunoassay, avoiding loss of LSD by absorption to surfaces. The reduced loss of LSD results in improved sensitivity. This is achieved by adding ethylene glycol to the samples, which cover glass surfaces. This principle can similarly be used to improve analysis of other drugs. Body fluids for analysis included urine and whole blood. An internal standard was applied for quantification of LSD. The new method offers satisfying precision data and has a detection limit of less than 0.05 ng/nL.     

Evaluation of a commercial radioimmunoassay kit for the detection of lysergide (LSD) in serum, whole blood, urine and stomach contents

The Diagnostic Products Corporation Coat-A-Count radioimmunoassay kit for LSD in urine has been evaluated for use in forensic toxicology with a variety of sample types. The cut-offs (defined as the mean response of blank samples plus three standard deviation) for LSD in serum, haemolysed whole blood, urine and stomach contents were 0.06, 0.050-0.055, 0.18 and 0.18 ng/ml, respectively. Preliminary extraction of LSD from the samples is not usually necessary. The precision of the analysis and the recoveries from spiked samples were satisfactory. The cross-reactivities of 2-oxo-LSD, lysergic acid methyl propylamide, lysergic acid monoethylamide and nor-LSD were estimated to be 11,6,2 and 1% respectively relative to LSD (100%).     

Gas chromatographic/mass spectrometric determination of lysergic acid diethylamide (LSD) in serum samples

A sensitive method for the detection and quantification of lysergic acid diethylamide (LSD) in serum samples is described. After liquid-liquid extraction the trimethylsilyl derivative of LSD is detected by gas chromatography — mass spectrometry. Experiments with spiked samples resulted in a recovery of 76%, the coefficient of variation was 9.3%. Excellent linearity was obtained over the range 0.1–10 ng ml⁻¹. Additionally experiments demonstrating the light sensitivity of LSD are presented together with casuistics.     

Analysis of LSD in human body fluids and hair samples applying ImmunElute columns

Immunoaffinity extraction units (LSD ImmunElute) are commercially available for the analysis of lysergic acid diethylamide (LSD) in urine. The ImmunElute resin contains immobilized monoclonal antibodies to LSD. We applied the ImmunElute procedure to serum and also to human hair samples. For hair analysis the samples were first extracted with methanol under sonication. The extracts were then purified using the ImmunElute resin. LSD analysis was carried out with HPLC and fluorescence detection. The immunoaffinity extraction provides highly purified extracts for chromatographic analysis. The limit of detection (signal-to-noise ratio = 3) has been determined to be < 50 pg regardless of which sample material was used. The procedure was applied to authentic hair samples from drug abusers (n = 11). One of these samples tested positive with an amount of 110 pg LSD in 112 mg extracted hair corresponding to a concentration of 1 pg/mg.     

Stability studies of ALD-52 and its homologue 1P-LSD

With the emergence of new psychoactive substances (NPSs) over the years, the substances detected on stamps (also known as blotter papers) have also evolved from the traditional drug—lysergic acid diethylamide (LSD) to the multiple variants of lysergamides such as ALD-52 and 1P-LSD. The analysis of such blotter papers is usually done by solvent extraction followed by identification using gas chromatography–mass spectrometry (GC-MS). This study has shown that hydrolysis to form LSD was observed in GC-MS analysis when ALD-52 was extracted with methanol. The extraction of ALD-52 using other solvents such as acetonitrile, ethanol, isopropyl alcohol, ethyl acetate, and acetone, followed by GC-MS analysis, was investigated. It is shown that alcoholic solvents such as methanol and ethanol will result in the conversion of ALD-52 to LSD during GC-MS analysis, whereas the sterically hindered isopropyl alcohol will prevent this conversion. Investigation also shows that the hydrolysis of ALD-52 to LSD occurs at the GC injector port. It was also observed that the degree of hydrolysis was more pronounced at a lower concentration (0.1 mg/mL). The study was extended to a close analog—1P-LSD, and the results showed that 1P-LSD similarly hydrolyzes to LSD. However, 1P-LSD was observed to be more stable than ALD-52 due to steric hindrance because of the propanoyl group.