新精神活性物质——芬纳西泮的检验

目的对缴获的嫌疑药片进行定性定量检验。方法采用GC/MS确证、GC/FID内标法定量检验。结果三起不同案件的嫌疑药片,均检出芬纳西泮,含量为0.5%~1.1%。结论不同时间、不同地区缴获的三起数量较大、外观基本相同的嫌疑药片活性成分均为芬纳西泮的检验结果应引起我国禁毒执法部门的高度重视。     

GC法和GC/MS法在地区毒品情报分析中的应用

目的探讨气相色谱法(GC)和气相色谱/质谱联用法(GC/MS)在地区毒品情报分析中的应用,并用于实际样品分析。方法采用GC/MS法定性分析毒品样品中的主成分、痕量杂质、掺假剂和稀释剂,并选择GC/FID法和内标标准曲线法定量分析上述各组分,通过定性和定量数据的统计和分析,推断该地区的毒品状况。结果用GC/MS定性分析、GC/FID定量分析,和数据的统计比对,获得了某省某年27起海洛因毒品大案样品主成分、痕量杂质、掺假剂和稀释剂组成及含量的特征,发现该省缴获的大宗海洛因毒品主要以掺假和稀释后的产品出现,且咖啡因和扑热息痛为两种主要的掺假剂和稀释剂。结论GC/MS和GC/FID法在地区毒品情报分析和打击毒品犯罪中可以发挥重要作用。     

超声辅助固相萃取-HPLC法测定不同地区缴获鸦片样品中生物碱

目的本文建立了超声辅助固相萃取-HPLC法定量测定缴获鸦片样品中吗啡、可待因、蒂巴因、罂粟碱、那可汀5种生物碱并同时检出6种未知化合物的方法。采用主成分分析法区分不同地区缴获的鸦片样品。方法采用超声辅助固相萃取法提取生物碱,XDB-C18（5μm×4.6mm×250mm）色谱柱,流动相为10mM的1-庚烷磺酸钠（pH 3.2）和乙腈,梯度洗脱,紫外检测器检测。结果该方法的定量限为0.58~2.78 mg/kg。添加水平在0.2～1.5mg/mL范围内,平均加标回收率为81.0%～99.2%,相对标准偏差为1.6%～5.0%。结论本方法重现性好、定量准确,满足定量检测鸦片中生物碱含量并对不同产地鸦片进行分类的需要。     

盐酸氟胺酮的结构确证和核磁共振定量分析

对氟胺酮缴获物进行结构确证和含量测定。利用元素分析、紫外吸收光谱(UV)、红外吸收光谱(IR)、高分辨质谱(QTOF/MS)、核磁共振谱(¹H NMR、¹³C NMR、DEPT、¹H-¹H COSY、¹H-¹³C HMBC、¹H-¹³C HSQC)等手段进行定性分析；建立定量核磁共振氢谱法(¹H-qNMR)进行定量分析，以富马酸为内标，以0.5mL氘代二甲亚砜和0.1 mL重水混合溶液为溶剂，激发脉冲角度为30°，测定温度为303 K，脉冲延迟时间为30 s，采样次数为16次。实验确证了缴获物为盐酸氟胺酮，并成功建立了定量核磁共振法，此方法专属性良好；稳定性可达56 h；耐用性符合要求；盐酸氟胺酮与内标富马酸的质子摩尔比在0.453 0～2.151 2范围内线性关系良好，R²为1.000；缴获物中盐酸氟胺酮的含量测定结果为99.86%。定量核磁共振法操作简单、快速，在无...     

3,4-亚甲二氧基甲卡西酮的鉴定

目的 建立基于傅里叶变换红外光谱(FTIR)、气相色谱-质谱(GC-MS)结合高分辨质谱技术联合鉴定未知样品的方法.方法 未知样品采用红外专用取样器直接检测;甲醇溶解后采用GC-MS和组合型高分辨质谱检测,以MDMA为内标物.结果 未知样品获得的红外光谱特征吸收峰为1679(C=O键),1603,1502,1453,1423,1259,1121,1090,1035,930,887,838,768,742和717cm-1,质谱特征碎片峰(m/z)为58.1,91.0,120.9,149.0和207.0,测得的精确质量数[M+H]+为208.0966.经信息分析未知样品鉴定为3,4-亚甲二氧基甲卡西酮,该物质属于新型化学合成卡西酮类精神活性物质,已经列入部分欧盟国家的管制药物目录.结论 本方法可用于3,4-亚甲二氧基甲卡西酮的鉴定.     

同位素比值质谱法鉴别海洛因来源——1.海洛因水解制备吗啡的研究

同位素比值质谱法(IRMS)是目前鉴别缴获的海洛因来源的三种主要方法之一。用该法研究海洛因的来源应分别考虑吗啡来源地和乙酰化试剂来源二方面的因素。本文以缴获的海洛因毒品制备吗啡的方法着手,从酸性和碱性两条路线考察了海洛因水解制备吗啡的方法。研究水解的实验条件,达到了码啡90%以上的产率和95%以上的纯度。首次提出了最佳的反应参数组合,它们分别为:反应温度100℃,反应时间30min,海洛因样品(包括海洛因盐酸盐和游离碱)与盐酸的摩尔比1:3.0;反应温度100℃,时间45min,海洛因盐酸盐与KOH的摩尔比1:4.4,海洛因游离碱与KOH的摩尔比1:3.4。本文还考察了吗啡气相色谱(GC)定量的工作曲线,并对吗啡的TMS衍生物的GC、GC/MS测定结果进行了比较。     

生物样品中去痛片4种成分及其8种代谢物的GC-MS/MS法检测

目的建立固相支撑液液萃取(supported liquid-liquid extraction,SLE),GC-MS/MS法同时测定生物样品中去痛片4种成分及其8种代谢物的方法,为去痛片相关案件的法医学鉴定提供依据。方法采用SLE萃取,GC-MS/MS检测,MRM记录方式,利用保留时间和离子对比例定性,内标法和工作曲线法定量,建立血液和组织中去痛片及其代谢物的GC-MS/MS检测方法。结果经SLE萃取,GC-MS/MS法同时检测大鼠血和组织中去痛片及其代谢物,萃取率为37.57%~95.87%,检测线性范围为0.12μg/m L~16.00μg/m L,相关系数(r)为0.989 6~0.999 7,LOD为0.23ng/m L~14.48ng/m L,检测准确度为79.63%~122.90%,日内和日间精密度分别为0.99%~7.43%和2.19%~10.6%。结论 SLE萃取、GC-MS/MS法可检测生物样品中去痛片成分及其代谢物,具有快速、简便、准确度和精密度高的特点,可应用于去痛片相关案件的法医学鉴定。     

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。     

GC-MS/MS法检测生物样品中硫丹含量

目的建立生物样品中硫丹(α硫丹和β硫丹)的气相色谱-串联质谱(GC-MS/MS)检测方法,观察硫丹在水生动物体内的分布,为相关案件的法医学鉴定提供实验依据。方法血液和肌肉样品采用乙腈沉淀蛋白,GC-MS/MS法检测,多反应监测模式扫描,以保留时间和离子比例定性,外标工作曲线法定量。结果血液样品中α硫丹和β硫丹在0.062 5~10μg/mL范围内线性关系良好,相关系数(r)均大于0.99,检出限分别为1 ng/mL和2 ng/mL,定量限分别为4 ng/mL和8 ng/mL。肌肉样品中α硫丹和β硫丹在0.062 5~10μg/g范围内线性关系良好,相关系数(r)均大于0.98,检出限分别为1 ng/g和4 ng/g,定量限分别为4 ng/g和16 ng/g。血液和肌肉样品中α硫丹和β硫丹的准确度为90.76%~108.91%,日内精密度(RSD)为2.35%~8.71%,日间精密度(RSD)为5.44%~10.29%。中毒案件中,在鱼和螃蟹体内各部位均检出硫丹,且不同部位间含量差异均具有统计学意义。结论本研究建立的硫丹GC-MS/MS检测方法快捷、准确、灵敏,适用于微量生物检材中硫丹的检测。硫丹在鱼和螃蟹体内分布不均匀,为硫丹相关法医学鉴定案件中毒物分析检材的采集和分析提供了依据。     

QuEChERS-LC/MS快速检测兽用麻药“舒泰”

目的本文对兽药"舒泰"中有效成分进行了结构确证,并建立了生物检材中替来他明和唑拉西泮的快速检验方法。方法在血液和尿液的生物检材中,通过加标实验,经QuEChERS萃取后,进行LC/MS对替来他明和唑拉西泮的定性定量检测分析。结果在血液和尿液的生物样品的加标实验中,替来他明的RSD%在0.5%~3.5%,唑拉西泮的RSD在0.5%~1.1%;替来他明的回收率在75.8%~100.3%,唑拉西泮的回收率在68.8%~76.6%,其中血液中替来他明的方法检出限为0.16ng/mL,尿液中为0.20ng/mL,唑拉西泮在血液中的方法检出限0.17ng/mL,尿液中为0.22ng/mL。结论建立的QuEChERS萃取方法,操作流程简便,方法重现性好,只需100μL取样量,更适合于痕量生物检材中替来他明和唑拉西泮的检验分析。     

Identification of Different Forms of Cocaine and Substances Used in Adulteration Using Near‐infrared Raman Spectroscopy and Infrared Absorption Spectroscopy

Identification of cocaine and subsequent quantification immediately after seizure are problems for the police in developing countries such as Brazil. This work proposes a comparison between the Raman and FT‐IR techniques as methods to identify cocaine, the adulterants used to increase volume, and possible degradation products in samples seized by the police. Near‐infrared Raman spectra (785 nm excitation, 10 sec exposure time) and FT‐IR‐ATR spectra were obtained from different samples of street cocaine and some substances commonly used as adulterants. Freebase powder, hydrochloride powder, and crack rock can be distinguished by both Raman and FT‐IR spectroscopies, revealing differences in their chemical structure. Most of the samples showed characteristic peaks of degradation products such as benzoylecgonine and benzoic acid, and some presented evidence of adulteration with aluminum sulfate and sodium carbonate. Raman spectroscopy is better than FT‐IR for identifying benzoic acid and inorganic adulterants in cocaine.     

Near Infrared Spectroscopy Detection and Quantification of Herbal Medicines Adulterated with Sibutramine

There is an increasing demand for herbal medicines in weight loss treatment. Some synthetic chemicals, such as sibutramine (SB), have been detected as adulterants in herbal formulations. In this study, two strategies using near infrared (NIR) spectroscopy have been developed to evaluate potential adulteration of herbal medicines with SB: a qualitative screening approach and a quantitative methodology based on multivariate calibration. Samples were composed by products commercialized as herbal medicines, as well as by laboratory adulterated samples. Spectra were obtained in the range of 14,000–4000 per cm. Using PLS‐DA, a correct classification of 100% was achieved for the external validation set. In the quantitative approach, the root mean squares error of prediction (RMSEP), for both PLS and MLR models, was 0.2%w/w. The results prove the potential of NIR spectroscopy and multivariate calibration in quantifying sibutramine in adulterated herbal medicines samples.     

基于化学计量法的FTIR鉴别心源性猝死

目的联合应用傅里叶变换红外光谱技术及化学计量法对心源性猝死的大鼠进行鉴别分析。方法注射药物或空气分别诱导大鼠的心源性猝死及空气栓塞死亡模型。应用Nicolet i Z10 FTIR光谱仪采集血清样本的红外光谱,联合OMNIC及Unscrambler软件,基于光谱不同分子吸收区间建立偏最小二乘回归模型。结果基于指纹区(1 200~900cm-1)建立PLS模型,均方根误差和决定系数分别是0.068 3、0.981 3,预测均方根偏差和预测决定系数分别是0.104 8、0.956 1;基于蛋白质酰胺区间(1 720~1 480cm-1)建立PLS模型,RMSE和R2分别是0.058 6,0.986 2,RMSEP和预测R~2分别是0.079 4、0.974 7。综合分析两种模型,蛋白质酰胺区间的RMSEP更小,且预测R2更大,提示其预测效果略好于指纹区间。结论联合FTIR及化学计量法,基于蛋白质及指纹区的分子特征均可有效鉴别大鼠的心源性猝死,其中两种不同死因引起的蛋白质差异更为显著。     

Comparison and classification of methamphetamine seized in Japan and Thailand using gas chromatography with liquid-liquid extraction and solid-phase microextraction

Methamphetamine (MA) is one of the most frequently abused drugs worldwide. The aim of this study is to improve the analytical method for profiling MA impurity in order to compare and classify MA crystals seized in different countries and to investigate the relationships between seizures. To compare MA samples seized in Japan and Thailand, the following analytical method was adopted. A 50mg sample of MA.HCl was dissolved in 1ml of buffer solution (four parts 0.1M phosphate buffer, pH 7.0, and one part 10% Na(2)CO(3)), impurities were extracted with 0.5ml of ethyl acetate containing four internal standards (n-decane, n-pentadecane, n-eicosane and n-octacosane) and analyzed by gas chromatography with a flame ionization detector on a DB-5 capillary column (0.32mm i.d.x30m, film thickness 1.0mum). Fourteen characteristic peaks on chromatograms were selected for the comparison and classification of samples, and the data were evaluated by the Euclidean distance of the relative peak areas after logarithmic transformation. Sixty-nine samples seized in Japan and 42 seized in Thailand were analyzed. The samples were classified into four groups roughly by cluster analysis. In addition, when it was difficult to compare samples that had fewer impurities on chromatograms obtained from liquid-liquid extraction (LLE), solid-phase microextraction (SPME) was effective. Because many characteristic peaks were detected using SPME, SPME made it easy to compare samples of high purity. The combination of LLE and SPME was useful for impurity profiling of MA samples seized in different countries.     

Quantification of the amphetamine content in seized street samples by Raman spectroscopy

A Raman spectroscopy method for determining the drug content of street samples of amphetamine was developed by dissolving samples in an acidic solution containing an internal standard (sodium dihydrogen phosphate). The Raman spectra of the samples were measured with a CDD-Raman spectrometer. Two Raman quantification methods were used: (1) relative peak heights of characteristic signals of the amphetamine and the internal standard; and (2) multivariate calibration by partial least squares (PLS) based on second derivative of the spectra. For the determination of the peak height ratio, the spectra were baseline corrected and the peak height ratio (h(amphetamine at 994 cm(-1) )/h(internal standard at 880 cm(-1) )) was calculated. For the PLS analysis, the wave number interval of 1300-630 cm(-1) (348 data points) was chosen. No manual baseline correction was performed, but the spectra were differentiated twice to obtain their second derivatives, which were further analyzed. The Raman results were well in line with validated reference LC results when the Raman samples were analyzed within 2 h after dissolution. The present results clearly show that Raman spectroscopy is a good tool for rapid (acquisition time 1 min) and accurate quantitative analysis of street samples that contain illicit drugs and unknown adulterants and impurities.     

傅立叶变换红外光谱法检验口红的研究

目的建立一种灵敏、准确、无损的口红检验方法。方法利用傅立叶变换红外光谱仪,采用SmartPerformer采样器,对202个不同产地、不同品牌和同一品牌不同牌号的口红样品进行分析检验。结果依据红外光谱图中吸收峰的不同,可以将口红样品加以区分。结论该检验方法不破坏检材,重现性好,可用于鉴定案件现场中提取到的口红物证。     

Examination of lubricating oils by infrared spectroscopy

Approximately 60 oil samples obtained from the chassis of various motor cars have been examined by infrared spectroscopy. The samples were oils from the engine, gearbox and back-axle. Differences in absorbance of some absorption bands in the infrared spectra (IR) of oil samples were observed. An optimal set of absorption bands was chosen, which was used for quantitative comparison of slightly differing spectra. The significance of differences was tested using Hotelling's T²-test.     

Component analysis of illicit heroin samples with GC/MS and its application in source identification

A novel method based on GC/MS and GC for component analyses of seized illicit heroin was established by using SKF525A as an internal standard. The main components in illicit heroin products such as heroin, O3-acetylmorphine, monoacetylcodeine, and O6-acetylmorphine were determined quantitatively and the organic adulterants such as paracetamol, acetaminophen caffeine and theophylline were detected qualitatively using the developed method. With these obtained data, 500 seized illicit heroin samples were divided into nine groups. The decomposition pattern of heroin was studied. The dependencies of both the decomposition pattern and the content ratios of monoacetylcodeine to heroin and monoacetylcodeine to O6-acetylmorphine on the source of the seized illicit heroin were observed. This information was used to develop a novel method for its source identification. The examination results were in agreement with the practical cases, thus providing significant information for detection of criminal cases involving illicit heroin.     

Secondary ion mass spectrometric characterization of nail polishes and paint surfaces

A variety of paint and fingernail polish samples, which were visually similar, but had different chemical compositions and formulations, was analyzed using quadrupole static secondary ion mass spectrometry (SIMS). Coating distinction was easily achieved in many cases because of the presence of dominant ions derived from the components of the coating, which could be observed in the SIMS spectra. In other instances, coating distinction was difficult within a product line because of spectral complexity; for this reason and because of the large numbers of spectra generated in this study, multivariate statistical techniques were employed, which allowed the meaningful classification and comparison of spectra. Partial Least Squares (PLS) and Principal Component Analysis (PCA) were applied to quadrupole SIMS data. PCA showed distinct spectral differences between most spectral groups, and also emphasized the reproducibility of the SIMS spectra. When using PLS analysis, reasonably accurate coating identification was achieved with the data. Overall, the PLS model is more than 90% effective in identifying the spectrum of a particular coating, and nearly 100% effective at telling which coating components represented in the PLS models are not present in a spectrum. The level of spectral variation caused by sample bombardment in the SIMS analysis was investigated using Fourier transform infrared spectroscopy (FT-IR) and quadrupole static SIMS. Changes in the FT-IR spectra were observed and were most likely a result of a number of factors involving the static SIMS analysis. However, the bulk of the sample is unaltered and may be used for further testing.