气相色谱法同时测定大麻、海洛因和鸦片中的8种组分

研究了可待因、吗啡、罂粟碱、那可汀、大麻酚、大麻二酚、四氢大麻酚和二乙酰吗啡在大口径毛细管柱上的色谱行为。采用程序升温，直接进样，在HP-1色谱柱上，使所测8种组分及内标物均获得良好的分离。据此建立了大口径毛细管气相色谱法同时对大麻、鸦片和海洛因毒品中多组分的快速测定方法。经样品测定，其平均回收率为95％-102．4％；最低检测限为0．10-0．50mg／L；相对标准偏差为0．9％-2．6％。     

高效液相色谱检测大麻中Δ9-四氢大麻酚的分析方法研究

建立了大麻毒品中主要有效成分Δ9-四氢大麻酚的液相色谱分析方法.选择甲醇作为大麻植物或大麻树脂的提取溶剂.采用岛津ODS-SP型(150 mm×4.6 mm,5μm)色谱柱作为定量方法的标准柱,紫外检测器主定量波长为210 nm,辅定量波长为195 nm或220 nm.以水-乙腈为流动相进行梯度洗脱,流速1mL/min,柱温40℃,进样量10 μL.在优化条件下,△9-四氢大麻酚在0.5～ 100.0 mg/L范围内线性良好,外标法及内标法的相关系数(r2)均大于0.99999.方法的检出限(S/N≥3.3)和定量下限(S/N≥ 10)分别为0.12 mg/L和0.40 mg/L.用该方法检测某大麻树脂样本,△9-四氢大麻酚含量的不确定度评定结果为5.32％±0.17％,k=2.实验结果表明,该方法快速、灵敏、准确、可靠,适用于大麻植物及树脂的定量测定.     

超高效液相色谱-串联质谱法同时测定食用油中痕量的δ-9-四氢大麻酚、大麻酚和大麻二酚

建立了超高效液相色谱-串联质谱(UPLC-MS/MS)同时测定食用油中δ-9-四氢大麻酚(THC)、大麻酚(CBN)和大麻二酚(CBD)的方法。目标分析物经甲醇提取、中性氧化铝固相萃取柱净化后,采用UPLC-MS/MS分离和检测。实验以氘代四氢大麻酚(THC-D3)为内标物,采用同位素内标法定量。在3个添加水平下,目标物的平均回收率为68.0%～101.6%,相对标准偏差为7.0%～20.1%。方法检出限为0.06～0.17μg/kg,定量限为0.20～0.52μg/kg。该方法能够满足食用油中痕量四氢大麻酚、大麻酚和大麻二酚检测的需要。     

超高效液相色谱-串联质谱法同时测定食用油中痕量的δ-9-四氢大麻酚、大麻酚和大麻二酚

建立了超高效液相色谱-串联质谱(UPLC-MS/MS)同时测定食用油中δ-9-四氢大麻酚(THC)、大麻酚(CBN)和大麻二酚(CBD)的方法。目标分析物经甲醇提取、中性氧化铝固相萃取柱净化后,采用UPLC-MS/MS分离和检测。实验以氘代四氢大麻酚(THC-D3)为内标物,采用同位素内标法定量。在3个添加水平下,目标物的平均回收率为68.0%～101.6%,相对标准偏差为7.0%～20.1%。方法检出限为0.06～0.17 μg/kg,定量限为0.20～0.52 μg/kg。该方法能够满足食用油中痕量四氢大麻酚、大麻酚和大麻二酚检测的需要。     

单柱离子色谱法同时测定磷酸中痕量钠（Ⅰ）和铁（Ⅲ）

以酒石酸－乙二胺为淋洗液的单柱离子色谱法同时测定磷酸中痕量钠（Ⅰ）和铁（Ⅲ）。淋洗液最佳浓度为４．０ｍｍｏｌ．Ｌ￣（－１）、酒石酸／１．０ｍ　ｍｏｌ·Ｌ￣（－１）乙二胺。最低检测限为Ｎａ￣＋０．０５μｇ／ｍＬ、　Ｆｅ３＋　０．４５μｇ／ｍＬ。电导检测灵敏度为２．０μｇ／ｃｍ。线性范围Ｎａ￣＋、Ｆｅ３＋０．２～１．５×１０３μｇ／ｍＬ、２．５～１．０×１０３μｇ／ｍＬ。相对平均偏差Ｎａ￣＋为２．０３％、Ｆｅ３＋为０．８３％。平均回收率Ｎａ￣＋为９８．２６％、Ｆｅ３＋为９７．６２％。本法简便、快速、准确、选择性好。     

增强型脂质去除净化剂结合超高效液相色谱-串联质谱法测定食品中8种大麻素类化合物

研究在优化前处理条件及色谱分离的基础上,建立了同时测定巧克力、软糖、糕点、饼干、饮料、白酒等6种典型食品基质中8种大麻素类化合物的超高效液相色谱-串联质谱(UPLC-MS/MS)的测定方法。前处理方法中考察了不同的净化方式,采用增强型脂质去除净化剂(EMR-Lipid)解决了巧克力中复杂油脂及软糖中胶质难以去除的问题;同时净化溶液在氮吹前加入10%丙三醇甲醇溶液,解决了目前文献方法中直接氮吹对回收率影响很大的关键问题。样品以乙腈为提取溶剂,EMR-Lipid为净化剂进行净化,无水硫酸钠除水后,乙腈层加入10%丙三醇甲醇溶液100μL,氮吹至近干;采用Waters ACQUITY UPLC BEH Shield RP18色谱柱进行分离,电喷雾负离子扫描,多反应监测(MRM)模式检测,基质匹配外标法定量。方法学研究表明,四氢大麻酚、次大麻二酚、四氢大麻素、大麻萜酚在2～200 ng/mL范围内线性关系良好;大麻酚、大麻二酚、大麻二酚酸、四氢大麻酚酸A在0.4～40 ng/mL范围内线性关系良好,相关系数(r)均大于0.995;检出限和定量限分别为0.8～4μg/kg和2～10μg/kg。在...     

高效毛细管电泳－安培检测法测定牙膏中丙三醇和山梨醇

用高效毛细管电泳－安培检测装置，以２００μｍ铜圆盘电极为工作电极，在碱性介质中，建立了分离测定丙三醇和山梨醇的最佳实验条件。结果表明：平均理论塔板数为２．４×１０５／ｍ，丙三醇和山梨醇的浓度检测限分别为３００μｇ／Ｌ和２００μｇ／Ｌ，线性范围接近３个数量级。在５．００～５０．０ｍｇ／Ｌ内，丙三醇和山梨醇的相关系数分别为０．９９９７和０．９９９５。样品测定结果与用高效液相色谱法测定的结果基本一致，回收率在９２％～１０４％之间     

大麻中3种酚类成分测定专用固相萃取柱的设计与应用

大麻中的主要成分大麻二酚(CBD)、大麻酚(CBN)和 Δ9-四氢大麻酚(Δ9-THC)的含量决定了其性质和应用.在液相色谱分析中,由于大麻提取液中含有较多杂质,需要净化.该文基于大麻中CBD、CBN和 Δ9-THC的结构特征及样品基质组成,根据中性氧化铝、硅酸镁和石墨化炭黑的不同表面特征,考察了这3种吸附剂对大麻提取...     

离子选择电极—流动注射分析法动力学测定葡萄糖存在下的果糖

本文将离子电极与流动注射分析相结合，利用３０℃下，在强碱性介质中，果糖和葡萄糖与２，４－二硝基酚钠反应速度明显差异，动力学测定了葡萄糖存在下果糖的含量。自制了２，４－二硝基酚电极作为动力学电位测定用的工作电极。本法测定果糖的范围为０．０２～１．００ｍｏｌ／Ｌ，其ＲＳＤ为４．０％～４．９％，ＲＥ为１．０～５．０％；当Ｃ葡／Ｃ果≤３倍时，葡萄糖的干扰不超过５％；本法也曾成功地用于果葡萄浆测定，其ＲＳＤ     

几种挥发性有机酚的离子淌度谱研究

篱子淌度谱仪在负高压方式下测得苯酚、２－氯代酚、２，４－二氯代酚及五氯代酚的折合淌度值分别为２．１２、２．０１、１．９３、１．７４ｃｍ＾２Ｖ＾－１ｓ＾－１，检测限分别为１．０、０．１、０．５、０．５μｇ／Ｌ，２－氯代酚、２，４－二氯代酚的二聚体折合沿度值分别为１．６０、１．４７ｃｍ＾２Ｖ＾－１Ｓ＾－１，并对苯酚、进行了分析测定，并讨论了淌度值与分子量，佞子形状之间的关系。     

基于超高效液相色谱-质谱联用技术对大麻植物中3种成分及化学表型分析

建立了超高效液相色谱-质谱联用(UPLC/PDA-QDa)同时对大麻植物中Δ9-四氢大麻酚(Δ9-THC)、大麻酚(CBN)和大麻二酚(CBD)进行定性与定量分析的方法.缴获的大麻植物用甲醇超声萃取, 采用甲醇(含0.1%甲酸)和超纯水为流动相, 等度洗脱, 流速为0.2 mL/min, 经Waters UPLC BEH C18柱(50 mm×2.1 mm, 1.7 μm)分离, 利用光电二极管阵列检测器(PDA)在220 nm波长下检测, 并通过质谱检测器(QDa)对目标洗脱峰进行追踪确证.在0.5~20 μg/mL浓度范围内, 3种大麻酚类化合物的质量浓度与峰面积呈良好的线性关系, R≥0.999;低、中、高添加水平的平均回收率为82%~102%, 相对标准偏差(RSD)在0.4%~4.1%之间.本方法稳定、简便、灵敏, 能够满足检测需求.根据Δ9-THC、(Δ9-THC+CBN)/CBD、Δ9-THC/CBD或CBN/CBD表型指数, 区分不同产地大麻的化学表型, 为大麻植物的检测分析和质量控制提供了有效手段.     

Oral fluid cannabinoid concentrations following controlled smoked cannabis in chronic frequent and occasional smokers

Oral fluid (OF) is an alternative biological matrix for monitoring cannabis intake in drug testing, and drugged driving (DUID) programs, but OF cannabinoid test interpretation is challenging. Controlled cannabinoid administration studies provide a scientific database for interpreting cannabinoid OF tests. We compared differences in OF cannabinoid concentrations from 19 h before to 30 h after smoking a 6.8 % THC cigarette in chronic frequent and occasional cannabis smokers. OF was collected with the Statsure Saliva Sampler? OF device. 2D-GC-MS was used to quantify cannabinoids in 357 OF specimens; 65 had inadequate OF volume within 3 h after smoking. All OF specimens were THC-positive for up to 13.5 h after smoking, without significant differences between frequent and occasional smokers over 30 h. Cannabidiol (CBD) and cannabinol (CBN) had short median last detection times (2.5–4 h for CBD and 6–8 h for CBN) in both groups. THCCOOH was detected in 25 and 212 occasional and frequent smokers’ OF samples, respectively. THCCOOH provided longer detection windows than THC in all frequent smokers. As THCCOOH is not present in cannabis smoke, its presence in OF minimizes the potential for false positive results from passive environmental smoke exposure, and can identify oral THC ingestion, while OF THC cannot. THC?≥?1 μg/L, in addition to CBD?≥?1 μg/L or CBN?≥?1 μg/L suggested recent cannabis intake (≤13.5 h), important for DUID cases, whereas THC?≥?1 μg/L or THC?≥?2 μg/L cutoffs had longer detection windows (≥30 h), important for workplace testing. THCCOOH windows of detection for chronic, frequent cannabis smokers extended beyond 30 h, while they were shorter (0–24 h) for occasional cannabis smokers.     

Determination of cannabinoids in cannabis products using liquid chromatography-ion trap mass spectrometry

A method was developed and validated for the simultaneous determination of five cannabinoids, viz. cannabidiol (CBD), cannabidiol acid (CBD-COOH), cannabinol (CBN), delta9-tetrahydrocannabinol (THC), and 3'-carboxy-delta9-all-trans-tetrahydrocannabinol (THC-COOH) in cannabis products. The cannabinoids were extracted from the grinded cannabis samples with a mixture of methanol-chloroform and analysed using liquid chromatography with ion-trap-mass-spectrometry (LC-IT-MSn). For quantification the two most abundant diagnostic MS-MS ions of the analyte in the sample and external standard were monitored. For confirmation purposes the EU criteria as described in Commission Decision 2002/657/EC were followed. Fully satisfactory results were obtained, that is, unequivocal confirmation according to the most stringent EU criteria was possible. The limits of quantification were 0.1 g/kg for CBD, 0.04 g/kg for CBD-COOH, 0.03 g/kg for CBN, 0.28 g/kg for THC and 9.9 g/kg for THC-COOH. The repeatabilities, defined by R.S.D., were 2% for CBN, THC and THC-COOH at the concentration levels of respectively 0.023, 3.3 and 113 g/kg and 5% for CBD-COOH at the level of 0.34 g/kg (n = 6).     

Simultaneous quantification of cannabinoids and metabolites in oral fluid by two-dimensional gas chromatography mass spectrometry

Development and validation of a method for simultaneous identification and quantification of Δ9-tetrahydrocannabinol (THC), cannabidiol (CBD), cannabinol (CBN), and metabolites 11-hydroxy-THC (11-OH-THC) and 11-nor-9-carboxy-THC (THCCOOH) in oral fluid. Simultaneous analysis was problematic due to different physicochemical characteristics and concentration ranges. Neutral analytes, such as THC and CBD, are present in ng/mL, rather than pg/mL concentrations, as observed for the acidic THCCOOH biomarker in oral fluid. THCCOOH is not present in cannabis smoke, definitively differentiating cannabis use from passive smoke exposure. THC, 11-OH-THC, THCCOOH, CBD, and CBN quantification was achieved in a single oral fluid specimen collected with the Quantisal™ device. One mL oral fluid/buffer solution (0.25 mL oral fluid and 0.75 mL buffer) was applied to conditioned CEREX^® Polycrom™ THC solid-phase extraction (SPE) columns. After washing, THC, 11-OH-THC, CBD, and CBN were eluted with hexane/acetone/ethyl acetate (60:30:20, v/v/v), derivatized with N,O-bis-(trimethylsilyl)trifluoroacetamide and quantified by two-dimensional gas chromatography electron ionization mass spectrometry (2D-GCMS) with cold trapping. Acidic THCCOOH was separately eluted with hexane/ethyl acetate/acetic acid (75:25:2.5, v/v/v), derivatized with trifluoroacetic anhydride and hexafluoroisopropanol, and quantified by the more sensitive 2D-GCMS–electron capture negative chemical ionization (NCI-MS). Linearity was 0.5–50 ng/mL for THC, 11-OH-THC, CBD and 1–50 ng/mL for CBN. The linear dynamic range for THCCOOH was 7.5–500 pg/mL. Intra- and inter-assay imprecision as percent RSD at three concentrations across the linear dynamic range were 0.3–6.6%. Analytical recovery was within 13.8% of target. This new SPE 2D-GCMS assay achieved efficient quantification of five cannabinoids in oral fluid, including pg/mL concentrations of THCCOOH by combining differential elution, 2D-GCMS with electron ionization and negative chemical ionization. This method will be applied to quantification of cannabinoids in oral fluid specimens from individuals participating in controlled cannabis and Sativex^® (50% THC and 50% CBD) administration studies, and during cannabis withdrawal.     

In Situ Decarboxylation-Pressurized Hot Water Extraction for Selective Extraction of Cannabinoids from Cannabis sativa. Chemometric Approach

Isolation of the therapeutic cannabinoid compounds from Cannabis Sativa L. (C. Sativa) is important for the development of cannabis-based pharmaceuticals for cancer treatment, among other ailments. The main pharmacological cannabinoids are THC and CBD. However, THC also induces undesirable psychoactive effects. The decarboxylation process converts the naturally occurring acidic forms of cannabinoids, such as cannabidiolic acid (CBDA) and tetrahydrocannabinolic acid (THCA), to their more active neutral forms, known as cannabidiol (CBD) and tetrahydrocannabinol (THC). The purpose of this study was to selectively extract cannabinoids using a novel in situ decarboxylation pressurized hot water extraction (PHWE) system. The decarboxylation step was evaluated at different temperature (80–150 °C) and time (5–60 min) settings to obtain the optimal conditions for the decarboxylation-PHWE system using response surface methodology (RSM). The system was optimized to produce cannabis extracts with high CBD content, while suppressing the THC and CBN content. The identification and quantification of cannabinoid compounds were determined using UHPLC-MS/MS with external calibration. As a result, the RSM has shown good predictive capability with a p-value < 0.05, and the chosen parameters revealed to have a significant effect on the CBD, CBN and THC content. The optimal decarboxylation conditions for an extract richer in CBD than THC were set at 149.9 °C and 42 min as decarboxylation temperature and decarboxylation time, respectively. The extraction recoveries ranged between 96.56 and 103.42%, 95.22 and 99.95%, 99.62 and 99.81% for CBD, CBN and THC, respectively.     

Development and validation of an LC‐MS/MS method for quantification of Δ9‐tetrahydrocannabinolic acid A (THCA‐A), THC,CBN and CBD in hair

For analysis of hair samples derived from a pilot study (‘in vivo’ contamination of hair by sidestream marijuana smoke), an LC‐MS/MS method was developed and validated for the simultaneous quantification of Δ9‐tetrahydrocannabinolic acid A (THCA‐A), Δ9‐tetrahydrocannabinol (THC), cannabinol (CBN) and cannabidiol (CBD). Hair samples were extracted in methanol for 4 h under occasional shaking at room temperature, after adding THC‐D₃, CBN‐D₃, CBD‐D₃ and THCA‐A‐D₃ as an in‐house synthesized internal standard. The analytes were separated by gradient elution on a Luna C18 column using 0.1% HCOOH and ACN + 0.1% HCOOH. Data acquisition was performed on a QTrap 4000 in electrospray ionization‐multi reaction monitoring mode. Validation was carried out according to the guidelines of the German Society of Toxicological and Forensic Chemistry (GTFCh). Limit of detection and lower limit of quantification were 2.5 pg/mg for THCA‐A and 20 pg/mg for THC, CBN and CBD. A linear calibration model was applicable for all analytes over a range of 2.5 pg/mg or 20 pg/mg to 1000 pg/mg, using a weighting factor 1/x. Selectivity was shown for 12 blank hair samples from different sources. Accuracy and precision data were within the required limits for all analytes (bias between ?0.2% and 6.4%, RSD between 3.7% and 11.5%). The dried hair extracts were stable over a time period of one to five days in the dark at room temperature. Processed sample stability (maximum decrease of analyte peak area below 25%) was considerably enhanced by adding 0.25% lecithin (w/v) in ACN + 0.1% HCOOH for reconstitution. Extraction efficiency for CBD was generally very low using methanol extraction. Hence, for effective extraction of CBD alkaline hydrolysis is recommended. Copyright © 2013 John Wiley & Sons, Ltd.     

Direct quantification of cannabinoids and cannabinoid glucuronides in whole blood by liquid chromatography–tandem mass spectrometry

The first method for quantifying cannabinoids and cannabinoid glucuronides in whole blood by liquid chromatography–tandem mass spectrometry (LC–MS/MS) was developed and validated. Solid-phase extraction followed protein precipitation with acetonitrile. High-performance liquid chromatography separation was achieved in 16 min via gradient elution. Electrospray ionization was utilized for cannabinoid detection; both positive (Δ⁹-tetrahydrocannabinol [THC] and cannabinol [CBN]) and negative (11-hydroxy-THC [11-OH-THC], 11-nor-9-carboxy-THC [THCCOOH], cannabidiol [CBD], THC-glucuronide, and THCCOOH-glucuronide) polarity were employed with multiple reaction monitoring. Calibration by linear regression analysis utilized deuterium-labeled internal standards and a 1/x ² weighting factor, yielding R ² values >0.997 for all analytes. Linearity ranged from 0.5 to 50 μg/L (THC-glucuronide), 1.0–100 μg/L (THC, 11-OH-THC, THCCOOH, CBD, and CBN), and 5.0–250 μg/L (THCCOOH-glucuronide). Imprecision was <10.5% CV, recovery was >50.5%, and bias within ±13.1% of target for all analytes at three concentrations across the linear range. No carryover and endogenous or exogenous interferences were observed. This new analytical method should be useful for quantifying cannabinoids in whole blood and further investigating cannabinoid glucuronides as markers of recent cannabis intake.     

高效毛细管电泳法测定银翘解毒片中的氯原酸、甘草酸和甘草次酸

建立了同时测定银翘解每片中氯原酸、甘草酸和甘草次酸的高效毛细管电泳法,电解缓冲液为20mmol／L磷酸二氢钠和5mmol／L硼砂的混合溶液（pH7.0）。方法简便快速,具有良好的精密度、回收率和线性关系,并测定了很翘解毒片中3组分的含量。