171例滥用海洛因者的尿样分析

通过 GC/MS分析方法,对 171例滥用海洛因者的尿样进行了分析、统计,结果显示：在所检样品中检出吗啡的占 74.2％,检出海洛因的占 17.6％,检出 O6－单乙酰吗啡的占 52.1％,检出可待因的占 86.5％。因此,从统计学上说,在滥用海洛因者的尿样中检出海洛因是完全可能的。     

土制海洛因的薄层色谱扫描快速检验

建立土制海洛因的快速定性和定量检测方法。土制海洛因甲醇溶解,点于GF(254)薄层板上,正庚烷：氯仿：乙酸乙酯：乙醇：氨水（5：2：2：1．5：0．2）非饱和上行展开2次。薄层色谱扫描,Rf值结合斑点光谱扫描定性,色谱扫描定量。结果土制海洛因中主要成分海洛因、单乙酰吗啡、乙酰可待因、吗啡、可待因、蒂巴因、罂粟碱和那可汀分离完全,薄层扫描线性范围为0．2～2或4μg／斑点,最小检出量为0．1μg或0．2μg／斑点。本法可用于土制海洛因和海洛因的定性和定量检测。     

酶水解后同时分析海洛因、吗啡、可待因

本文以家兔为模型，用酶水解、丙酸酐衍生化处理吸毒后的尿样，用ＧＣ／ＭＳ同时分析海洛因、吗啡、可待因。     

体内海洛因代谢产物的分析研究

本文介绍了从海洛因成瘾者尿中提取净化和定性定量分析海洛因主要代谢产物单乙酰吗啡和吗啡的方法．阳性尿以乙基吗啡为内标．水解后液－液提取或液－固提取，经衍生化后采用ＧＣ／ＭＳ，ＧＣ／ＦＩＤ，ＧＣ／ＮＰＤ法分析，方法简便、准确、灵敏、重现性好．应用本法对八十余例吸毒成瘾者尿样进行测定，取得了令人满意的结果．     

三种检测尿中吗啡方法的比较分析

对２４７个尿样分别用Ｖ－Ⅱ、ＡＣ、ＴＬＣ三种方法分析，结果与ＧＣ／ＭＳ的结果对照，Ｖ－Ⅱ法的检测灵敏度最高，ＴＬＣ的检测灵敏度最低。Ｖ－Ⅱ法有假阳性５个（２．７％），ＡＣ有假阳性３个（３．７％），ＴＬＣ无假阳性结果。     

成瘾者头发样品中滥用药物的GC/MS鉴定

药物滥用影响社会生活，威胁人民健康，是一个严重的社会问题。确定药物滥用的技术方法，有TLC、GC、HPLC、GC－MS及免疫学方法等；样品有血、尿、胃内容物、脏器、唾液等，头发也是经常遇到的检材。它具有采样简单、携带方便、易长期保存等优点，在法医鉴定中具有更重要的意义。采用GC－MS方法对成嫣者头发样品中的滥用药物进行分析鉴定，可检出吗啡、可待因、6一单乙酸基吗啡、乙酸可待因与海洛因。该法样品处理方法简单（甲醇一步超声提取），样品用量少（20毫克即可），检测结果准确可靠，现报告如下。材料与方法一、仪器与试剂1…     

内标法固相提取-GC/MS检测海洛因吸食者尿液中代谢物

本文建立了以SKF-525A作内标、GDX－301作固相提取剂、用GC／MS方法测定海洛因吸食者尿液中代谢物浓度的方法。系统考查了吗啡、单乙酰吗啡的提取回收率、线性关系等指标。所建立的方法对吗啡和单乙酰吗啡的回收率均大于80％;最小检测浓度小于0.1μg／ml;用代谢物特征离子与内标物特征离子峰高比法测定吗啡与单乙酰吗啡的浓度,在每ml尿添加0．25μg～250μg范围内,二者均有良好的提取线性关系。并对几例海洛因滥用者的尿液进行了检测。     

头发中检验海洛因代谢物应用于吸毒时间的推断

运用气／质联用-选择离子（GC／MS－SIM）技术对吸食或注射海洛因嫌疑人的头发进行分段分析，根据各段头发中是否检出6-单乙酰吗啡和吗啡，并结合头发的生长速度对吸毒时间作出大致推断。该方法专一性较好，检出下限0．5ng／mg，能够推断出剪取吸毒嫌疑人头发前几个月或某一个时期内是否经常性服用海洛因。     

萃取方式对海洛因滥用者毛发中代谢物分析的影晌

目的比较液相萃取和同相萃取对毛发中海洛因毒品代谢物分析的影响。方法对海洛因吸食者毛发和空白添加标准品毛发经甲醇超声后的提取液分别进行液相萃取、同相萃取,然后进行衍生化和GC／MS—SIM检测。结果利用同相萃取法对添加6-单乙酰吗啡的毛发进行萃取和测试,6-单乙酰吗啡的回收率为32．O％,相对标准偏差（RSD）为2．4％;而液相萃取回收率为52．6％,相对标准偏差（RSD）为4．6％。结论固相萃取较之液液萃取,有更好的重复性,更少的杂质干扰和有机溶剂消耗等优势,但甲醇超声液需要挥干后才能进行同相萃取,而且6-单乙酰吗啡的水解率高。     

GC/NPD,GC/FID分析生物品中的氟乙酰胺

报道了用ＧＣ／ＮＰＤ、ＧＣ／ＦＩＤ分析生物试样中的氟乙酰胺的方法,在１ｇ肝组织中加入５．０μｇ氟乙酰胺,回收率为８５．１％,ＲＳＤ为５．３９（ｎ＝７）;１ｍｌ血中加５μｇ,回收率为８５．１５％,ＲＳＤ为７．１１％;在１ｇ胃组织中加入１０μｇ,回收率为８１．６％,ＲＳＤ为１０．１％（ｎ＝７）。研究的方法经实验和中毒案件的应用,效果较好。     

Hair and urine analysis: relative distribution of drugs and their metabolites

This work studies the distribution of cocaine and heroin metabolites in hair and urine of living polidrug abusers. Cocaine, benzoylecgonine (BEG), ecgonine methyl ester (EME), morphine, codeine and 6-monoacetylmorphine (6-MAM) were simultaneously extracted and analyzed by GC/MS in SIM mode. The results obtained show a different distribution of heroin and cocaine metabolites in urine and hair. In urine, we generally find BEG and EME for cocaine abuse, and morphine for heroin abuse. In hair, we detect cocaine and MAM as major metabolites for cocaine and heroin abuse, respectively.     

Gas chromatographic/mass spectrometric analysis of morphine and codeine in human urine of poppy seed eaters

In this study, poppy seeds were examined for a natural constituent that might serve as a maker for the seeds' ingestion as opposed to opiate abuse. Thebaine was selected as possible marker, since it was found to be a component of all poppy seeds examined and was not a natural component of different heroin samples. During the course of this investigation, a new extraction and cleanup procedure was developed for the gas chromatographic/nitrogen phosphorus detection (GC/NPD) and gas chromatographic/mass spectrometric (GC/MS) analysis of morphine and codeine in urine. A linear response, over a concentration range of 25 to 600 ng/mL, was obtained for codeine and morphine (r = 0.9982 and 0.9947, respectively). The minimum detectable level (LOD) and limit of quantitation (LOQ) for morphine were 10 and 30 ng/mL, respectively; whereas LOD and LOQ for codeine were 2 and 8 ng/mL, respectively. The coefficients of variance (CV, n = 6) for morphine and codeine analyses at the 100-ng/mL level were 13.3 and 4.6%, respectively. This procedure was used for the analysis of urine samples from five poppy seed eaters who each ingested 200 g of poppy seed cake. Results indicated that significant amounts of morphine and codeine are excreted in urine and that in all subjects, at least at one point in time, the apparent morphine concentration as determined by radioimmunoassay (RIA) analysis exceeded the cutoff value (300 ng/mL) established for screening. Thebaine was not detected in urine specimens collected following poppy seeds ingestion and thus could not be used as a marker.     

High prevalence of 6-acetylmorphine in morphine-positive oral fluid specimens

Identification of 6-acetylmorphine, a specific metabolite of heroin, is considered to be definitive evidence of heroin use. Although 6-acetylmorphine has been identified in oral fluid following controlled heroin administration, no prevalence data is available for oral fluid specimens collected in the workplace. We evaluated the prevalence of positive test results for 6-acetylmorphine in 77,218 oral fluid specimens collected over a 10-month period (January-October 2001) from private workplace testing programs. Specimens were analyzed by Intercept immunoassay (cutoff concentration=30 ng/ml) and confirmed by GC-MS-MS (cutoff concentrations=30 ng/ml for morphine and codeine, and 3 ng/ml for 6-acetylmorphine). Only morphine-positive oral fluid specimens were tested by GC-MS-MS for 6-acetylmorphine. A total of 48 confirmed positive morphine results were identified. An additional 107 specimens were confirmed for codeine only. Of the 48 morphine-positive specimens, 32 (66.7%) specimens were positive for 6-acetylmorphine. Mean concentrations (+/-S.E.M.) of morphine, 6-acetylmorphine and codeine in the 32 specimens were 755+/-201, 416+/-168 and 196+/-36 ng/ml, respectively. Concentrations of 6-acetylmorphine in oral fluid ranged from 3 to 4095 ng/ml. The mean ratio (+/-S.E.M.) of 6-acetylmorphine/morphine was 0.33+/-0.06. It is suggested that, based on controlled dose studies of heroin administration, ratios >1 of 6-acetylmorphine/morphine in oral fluid are consistent with heroin use within the last hour before specimen collection. The confirmation of 6-acetylmorphine in 66.7% of morphine-positive oral fluid specimens indicates that oral fluid testing for opioids may offer advantages over urine in workplace drug testing programs and in testing drugged drivers for recent heroin use.     

The detection of acetylcodeine and 6-acetylmorphine in opiate positive urines

Acetylcodeine (AC), an impurity of illicit heroin synthesis, was investigated as a urinary biomarker for detection of illicit heroin use. One hundred criminal justice urine specimens that had been confirmed positive by GC/MS for morphine at concentrations >5000 ng/ml were analyzed for AC, 6-acetylmorphine (6AM), codeine, norcodeine and morphine. The GC/MS analysis was performed by solid phase extraction and derivatization with propionic anhydride. Total codeine and morphine concentrations were determined by acid hydrolysis and liquid/liquid extraction. AC was detected in 37 samples at concentrations ranging from 2 to 290 ng/ml (median, 11 ng/ml). 6AM was also present in these samples at concentrations ranging from 49 to 12 600 ng/ml (median, 740 ng/ml). Of the 63 specimens negative for AC, 36 were positive for 6AM at concentrations ranging from 12 to 4600 ng/ml (median, 124 ng/ml). When detected, the AC concentrations were an average of 2.2% (0.25 to 10.2%) of the 6AM concentrations. There was a positive relationship between AC concentrations and 6AM concentrations (r=0.878). Due to its very low concentration in urine, AC was found to be a much less reliable biomarker for illicit heroin use than 6AM in workplace or criminal justice urine screening programs. However, AC detection could play an important role in determining if addicts in heroin maintenance programs are supplementing their supervised diacetylmorphine doses with illicit heroin.     

A rapid GC-MS method for the determination of dihydrocodeine,codeine, norcodeine,morphine, normorphine and 6-MAM in urine

The presence of the heroin metabolite 6-monoacetylmorphine (6-MAM) in urine is used to definitively identify recent heroin abuse. A rapid and sensitive GC-MS method for the simultaneous analysis of codeine, norcodeine, morphine, normorphine and 6-MAM in urine was developed and successfully applied to the analysis of 321 'heroin-positive' urine specimens from individual subjects (identified by the presence of 6-MAM), to provide quantitative urinary opiate excretion data for heroin abusers.The cohort analysed was composed of 238 males (age range 16-53 years) and 83 females (age range 16-50 years). The concentrations of free 6-MAM, morphine and codeine determined in these 321 specimens ranged between 103-246,312, 129-193,600 and 103-519,000 microg/l, respectively. Free norcodeine and normorphine concentrations were found to range between 143-50,200 and 205-149,700 microg/l, respectively. A statistically significant relationship was determined between the subject age and the 6-MAM concentration, possibly indicating opiate tolerance in these individuals.     

Morphine to codeine concentration ratio in blood and urine as a marker of illicit heroin use in forensic autopsy samples

A morphine to codeine ratio greater than unity (M/C>1) has been suggested as an indicator of heroin use in living individuals. The aim of this study was to examine the morphine to codeine ratio in a large population (N=2438) of forensically examined autopsy cases positive for 6-monoacetylmorphine (6-MAM) and/or morphine in blood and/or urine. Blood and urine concentrations of 6-MAM, morphine and codeine were examined using GC-MS and LC-MS/MS methods. In 6-MAM positive samples, the M/C ratio was greater than unity in 98% (N=917) of the blood samples and 96% (N=665) of the urine samples. Stratification of 6-MAM negative cases by M/C above or below unity revealed similarities in morphine and codeine concentrations in cases where M/C>1 and 6-MAM positive cases. Median blood and urine morphine concentrations were 8-10 times greater than codeine for both groups. Similarly to 6-MAM positive cases, 25-44 year-old men prevailed in the M/C>1 group. In comparison to cases where M/C ≤ 1, the M/C ratio was a hundred times higher in both 6-MAM positive and M/C>1 cases. The range of morphine concentration between the lowest and the highest quintile of codeine in M/C>1 cases was similar to that in 6-MAM positive cases. This range was much higher than for M/C ≤ 1 cases. Moreover, linear regression analyses, adjusted for age and gender, revealed a strong positive association between morphine and codeine in 6-MAM positive and M/C>1 cases. The M/C ratio appeared to be a good marker of heroin use in post-mortem cases. Both blood and urine M/C>1 can be used to separate heroin users from other cases positive for morphine and codeine.     

吸毒案件中的尿吗啡检测

目的　研究吸毒人员停止使用毒品海洛因后 ,尿吗啡含量自然递减的一般规律。方法　对确证的 1 82名吸毒 (海洛因 )人员在停止使用毒品后连续 9天采集尿样 ,用放射免疫分析法检测尿吗啡含量。结果　 1 82名吸毒 (海洛因 )人员在停止吸毒后第 8天 ,尿吗啡平均含量降至 30ng/ml。 结论　在办案中 ,吸毒 (海洛因 )人员的尿样检测 ,建议最好在末次使用海洛因 8天之内     

Concentrations of unconjugated morphine, codeine and 6-acetylmorphine in urine specimens from suspected drugged drivers

Concentrations of unconjugated morphine, codeine and 6-acetylmorphine (6-AM), the specific metabolite of heroin, were determined in urine specimens from 339 individuals apprehended for driving under the influence of drugs (DUID) in Sweden. After an initial screening analysis by immunoassay for 5-classes of abused drugs (opiates, cannabinoids, amphetamine analogs, cocaine metabolite and benzodiazepines), all positive specimens were verified by more specific methods. Opiates and other illicit drugs were analyzed by isotope-dilution gas chromatography-mass spectrometry (GC-MS). The limits of quantitation for morphine, codeine and 6-AM in urine were 20 ng/mL. Calibration plots included an upper concentration limit of 1000 ng/mL for each opiate. We identified the heroin metabolite 6-AM in 212 urine specimens (62%) at concentrations ranging from 20 ng/mL to > 1000 ng/mL. The concentration of 6-AM exceeded 1000 ng/mL in 79 cases (37%) and 31 cases (15%) were between 20 and 99 ng/mL. When 6-AM was present in urine the concentration of morphine was above 1000 ng/mL in 196 cases (92%). The concentrations of codeine in these same urine specimens were more evenly distributed with 35% being above 1000 ng/mL and 21% below 100 ng/mL. These results give a clear picture of the concentrations of unconjugated morphine, codeine and 6-acetylmorphine that can be expected in opiate-positive urine specimens from individuals apprehended for DUID after taking heroin.     

固相萃取／LC-MS／MS测定尿液中吗啡类药物

目的 建立尿液中吗啡类药物的固相萃取／LC—MS／MS方法。方法采用OASIS MCX3cc（60mg）固相萃取柱进行提取,应用LC—MS／MS方法进行检测,运用保留时间和MRM方式对尿液中吗啡类药物及其代谢物进行定性定量分析。结果磷酸盐缓冲液pH4．0时,海洛因、6-MAM、可待因、吗啡、M3G的固相萃取回收率分别达64．33％-70．21％,96．95％～117．57％,83．60％～123．63％,68．82％～91．03％,94．64％～107．33％;最低检测限（LOD）分别为5、10、5、5、2pg,线性范围0．005～10μg／mL;相关系数分别为0．9998、0．9958、0．9992、0．9994、0．9997。结论本文所建方法,适用于尿液中吗啡类药物的分析。     

生物检材中吗啡类生物碱的LC-MS／MS分析

目的针对滥用药物分析鉴定实践中亟待解决的问题,开展LC-MS/MS分析生物检材中吗啡类生物碱的应用研究。方法满足不同的鉴定需要,分别建立血液、尿液、唾液和头发等生物检材的样品前处理方法,确定同时分析海洛因、单乙酰吗啡、吗啡、可待因、乙酰可待因、二氢可待因酮和氢吗啡酮等吗啡类生物碱的LC-MS/MS方法。将方法应用于实际案例。结果所建立的方法对吗啡类生物碱分离良好。尿液稀释法、尿液提取法和头发中吗啡的最低检测限(LOD)分别为10ng/mL、0.01ng/mL和0.01ng/mg。结论所建立的方法简便、快速、特异性强、灵敏度高。目标物中加入二氢可待因酮和氢吗啡酮扩大了方法的实用范围。