The application of chromatographic and spectroscopic techniques for the analysis of certain antiinflammatory agents

Optimal conditions for the separation of diclofenac and ketorolac in the presence of other pharmaceutical products and narcotic substances are described with the help of gas and high performance liquid chromatography. The detection limits for individual compounds were established and the characteristic ions were identified. The possibility of application of IR- and UV-spectroscopy for the analysis of selected narcotic and non-narcotic analgesics was evaluated.     

氟乙酸五氟苄基酯的气相色谱分析

目的 对氟乙酸根阴离子的衍生物-氟乙酸五氟苄基酯(PFB-MFA)进行了气相色谱分析，以满足氟乙酰胺类鼠药化验工作的需要。方法 使用GC／ECD、GC／MS Scan、GC／MS SIM对该化合物的标准溶液进行了分析，得到了各种分析方法的校正曲线及检测限。结果 三种方法测定PFB-MFA的线性范围分别为GC／ECD 0.01～0.1ng／μl、GC／MS SCAN 1～100ng／μl、GC／MS SIM 5×10~(-3)～1ng／μl。三种方法对氟乙酸根阴离子的检测限分别为：GC／ECD1.31×10~(-4)ng／μl、GC／MS SCAN 0.13ng／μl、GC／MS SIM 1.76×10~(-4)ng／μl。结论 氟乙酸根阴离子的衍生物氟乙酸五氟苄基酯在GC／ECD及GC／MS上具有一定的线性范围，有非常高的灵敏度，可用于法庭科学的定性定量分析。     

Thin layer chromatography for the analysis of certain anti-inflammatory medicines

This work was devoted to the elucidation of conditions for isolation of ketorolac and diclofenac from biological fluids. A method is proposed for the extraction of these compounds from solutions with organic solvents at different pH values. Other methods permit to optimize identification of analytes by thin layer chromatography while the densitometric technique may be used for qualitative and quantitative analysis of their composition in biological fluids.     

生物检材中甲基苯丙胺及苯丙胺的分析研究进展

对近几年国内外22篇有关生物检材中甲基苯丙胺及苯丙胺测定的文献进行了综述。介绍了血、尿、毛发等生物检材的收集与预处理方法,比较了生物检材中甲基苯丙胺及苯丙胺的液-液萃取(LLE)、固相萃取(SPE)、固相微萃取(SPME)和顶空固相微萃取(HS-SPME)等提取方法,以及内标的选取、不同的衍生化方法和包括免疫、GC/MS、GC/NPD、GC/ECD、GC/FID、HPLC、HPCE在内的各种检测方法。最后,对分析结果的评定进行了讨论。     

Analysis of amphetamines by supercritical fluid chromatography,high-performance liquid chromatography,gas chromatography and capillary zone electrophoresis; a preliminary comparison

A supercritical fluid chromatographic method with UV detection (SFC–UV) for the quantitative separation of phenylisothiocyanate (PITC)-derivatised amphetamines is described and compared to high-performance liquid chromatography–diode array detection (HPLC–DAD), gas chromatography–flame ionisation detection (GC–FID) and capillary zone electrophoresis–diode array detection (CZE–DAD) analyses of amphetamine and related compounds. Difficulties in the analysis of common amphetamines by SFC are discussed. Of the methods described in this paper, the SFC method offered the greatest sensitivity at 0.01–0.02 μg of drug on column. Suggestions are made for the use of combinations of these techniques for the identification of amphetamines when gas chromatography–mass spectrometry is not available.     

尿样中苯骈二氮杂Zhu类药物筛选分析研究

目的建立尿样中苯骈二氮杂类药物两种筛选分析方法.方法用GC/ECD、GC/MS直接测定苯骈二氮杂类药物原体和GC/ECD、GC/MS测定1,4-苯骈二氮杂类药物的酸水解产物苯甲酮同系物.结果GC/ECD直接测定苯骈二氮杂类药物方法,大部分药物的回收率为60%～90%,线性范围为20～200ng/ml尿,线性相关系数大于0.99,最低检出限达0.5ng/ml～10ng/ml.结论所建两种方法各有其特点又可相互补充,已成功地应用于司法鉴定实践.     

Detection of the cholinesterase inhibitor tacrine and its main metabolites

Tacrine, a cholinesterase inhibitor for symptomatic treatment of minor to moderate dementia, and its primary metabolites 1-hydroxy-tacrine and 4-hydroxy-tacrine were studied by means of thin-layer chromatography, UV spectroscopy and gas-chromatography/mass spectroscopy. The analytical data (corrected hRf values, UV spectra in solution as well as reflectance spectra, high-pressure liquid chromatography data, GC retention indices and EI mass spectra) including various derivatization methods are described.     

兔体内三唑仑及其代谢物的检测

目的不同方法检测三唑仑及代谢物α-羟基三唑仑，为其及时、准确的检测提供科学证据和最优方法。方法用GC／NPD、GC／MS、MS／MS、GC／ECD对兔体内三唑仑及代谢物α-羟基三唑仑进行检测。结果GC／ECD法最易检测出三唑仑及其代谢物。结论兔胃及内容物、尿液中容易检测到三唑仑及其代谢物；运用酶水解后，检测率最高；GC／ECD检测三唑仑及其代谢物的灵敏度最高。     

The Characterization of 3,4-Dimethylmethcathinone (3,4-DMMC)

Analogs and derivatives of traditional illicit drugs are ever increasing in variety and creativity. Staying abreast of the new developments is a constant challenge for every forensic laboratory. Recently, a seizure from Australian Customs Service presented our laboratory with the designer cathinone 3,4-dimethylmethcathinone (3,4-DMMC). Gas chromatography/mass spectrometry (GC/MS), liquid chromatography/mass spectrometry (LC/MS), nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy, and ultraviolet (UV) spectrophotometry were employed to analyze the spectroscopic characteristics of this cathinone. As an analog, 3,4-DMMC exhibits similar if not identical IR and UV profiles to mephedrone (4-MMC) and methcathinone; however, the retention time from GC is unique as expected, and the electron impact fragmentation pattern is consistent with the fragmentation pattern of other cathinones. The chemical shifts of the carbons and hydrogens were assigned by both one- and two-dimensional NMR techniques, while the molecular weight was confirmed by LC/MS.     

Problems in using high performance liquid chromatography for drug analysis

Some problems encountered in using high performance liquid chromatography (HPLC) for drug analysis are discussed. These include high procurement and operational costs, lengthy training required, excessive downtimes , lower precision in HPLC versus gas chromatography (GC) and lack of a universal sensitive detector. Some solutions to these difficulties are presented.     

A preliminary study of the analysis of explosives using packed-column supercritical fluid chromatography with atmospheric pressure chemical ionisation mass spectrometric detection

A packed-column supercritical fluid chromatographic (SFC) separation of explosive compounds hyphenated to atmospheric pressure chemical ionisation (APCI) mass spectrometric (MS) detection has been developed. Nitroaromatics, nitramines and nitrate esters can be resolved and identified, with theoretical limits of detection of approximately 100 ng on column. This represents a development over previously described gas chromatography–thermal energy analysis (GC–TEA), gas chromatography– electron capture detection (GC–ECD) and SFC methods for the analysis of explosives due to the molecular identification afforded by the mass spectrometry. Explosives in the combinations expected in commercially available mixtures can be separated and identified. A successful application to a laboratory trial simulating casework is described.     

甲卡西酮概述及其分析方法

甲卡西酮吸食后具有精神刺激剂作用,有时候作为娱乐药物,具有成瘾性,长期高剂量使用可能导致急性神经紊乱。甲卡西酮R位的碳氧双键具有极性,因此像安非他明一样可以通过血脑屏障。它是潜在的中枢神经系统刺激剂和多巴胺再吸收抑制剂。甲卡西酮在美国是I类精神管制药物,任何情况下都是非法使用。本文还综述了甲卡西酮的检验分析方法,包括物理分析方法和仪器分析方法。仪器分析方法主要是气相色谱／质谱法（GC／MS）、高效液相色谱法（HPLC）,此外还有紫外光谱法（uV）,红外光谱法（IR）,核磁共振光谱法（NMR）以及毛细管电泳（CE）等方法。     

尿中氯胺酮及其代谢物检测的研究

目的建立氯胺酮滥用者尿中氯胺酮及其代谢物检测方法。方法尿液用有机溶剂液-液萃取,气相色谱/氮磷检测器、电子捕获检测器、氢火焰检测器和气-质联用仪测定。结果确认了尿液中氯胺酮的主要代谢物,尿液中氯胺酮及去甲氯胺酮的最小检测限均为2ng/mL,脱氢去甲氯胺酮的最小检测限为5ng/mL。结论所建方法快速、灵敏、准确,能够满足氯胺酮滥用者尿液检测的需要。     

Comparative analysis of gamma-hydroxybutyrate and gamma-hydroxyvalerate using GC/MS and HPLC

This paper describes two analytical techniques used to separate and quantify gamma-hydroxybutyrate (GHB) and gamma-hydroxyvalerate (GHV). The first technique was a N,O-bis(trimethylsilyl)triflouro-acetimide-trimethylchlorosilane derivatization, followed by gas chromatography/mass spectrometry analysis using an HP-5 capillary column at a rate of 1.0 mL/min with a run time of 9.25 min. This technique was found to be sensitive (LOD 1 pg on column) and gave a low average error (5%) in a beverage study. When supplemented by a surrogate spike, the method yielded 97% analyte recovery from beverages. The second technique was high-performance liquid chromatography/UV (HPLC/UV) using a C-18 column with a (20:80% v/v) methanol:dibasic phosphoric buffer (10 mM, pH 3) at a rate of 1.00 mL/min with a run time of 7.5 min. UV detection occurred at 254 nm. This method was found to be less sensitive (LOD 0.05 microg on column) for direct analysis of aqueous samples. To remove interferences seen in the beverage study, a liquid-liquid extraction before HPLC analysis was tested. However, a decreased sensitivity (LOD 100 microg on column) and irreproducible peak profiles resulted.     

Postmortem determination of the biological distribution of sufentanil and midazolam after an acute intoxication

A case is presented of a death caused by self-injection of sufentanil and midazolam. Biological fluids and tissues were analyzed for midazolam by high performance liquid chromatography (HPLC) and gas chromatography/mass spectrometry (GC/MS) and for sufentanil by GC/MS. Midazolam was extracted from basified fluids or tissues homogenated with n-butyl chloride and analyzed by HPLC by using a phosphate buffer: acetonitrile (60:40) mobile phase on a mu-Bondapak C18 column at 240 nm. Sufentanil was extracted from basified fluids and tissue homogenates with hexane:ethanol (19:1). GC/MS methodology for both compounds consisted of chromatographic separation on a 15-m by 0.25-mm inside diameter (ID) DB-5 (1.0-micron-thick film) bonded phase fused silica capillary column with helium carrier (29 cm/s) splitless injection at 260 degrees C; column 200 degrees C (0.8 min) 10 degrees C/min to 270 degrees C; and electron ionization and multiple ion detection for midazolam (m/z 310), methaqualone (IS, m/z 235), sufentanil (m/z 289), and fentanyl (IS, m/z 245). Sufentanil concentrations were: blood 1.1 ng/mL, urine 1.3 ng/mL, vitreous humor 1.2 ng/mL, liver 1.75 ng/g, and kidney 5.5 ng/g. Midazolam concentrations were: blood 50 ng/mL, urine 300 ng/mL, liver 930 ng/g, and kidney 290 ng/g. Cause of death was attributed to an acute sufentanil/midazolam intoxication and manner of death a suicide.     

Chromatographic and spectroscopic profiles of Cannabis of different origins: Part I

High-resolution capillary gas chromatography with flame ionization detection and mass spectrometry (GC and GC/MS) and high-performance liquid chromatography (HPLC) were used to establish complex chemical profiles (chemical signatures) of Cannabis samples of known origin. Over 100 compounds could be differentiated, including noncannabinoids (terpenes, alkanes) as well as minor and major cannabinoids and their acids. A characteristic peak pattern was found within a limited number of specimens of identical origin. Correlation studies on the basis of peak area ratios [A(x)/A(i.s.)] showed the feasibility of tracing Cannabis chemically to its country of origin. Several forensic science applications for the chromatographic and spectroscopic profiles of confiscated Cannabis samples are discussed, such as detection of additives (phencyclidine), differentiation of chemotypes, and monitoring of tetrahydrocannabinol (THC) potency.     

Racemization of aspartic acid from human dentin in the estimation of chronological age

The estimation of chronological age in cadavers, human remains and in living human beings by various methods is discussed. These methods, which are based on the age dependent non-enzymatic changes of l-form amino acids to d-form amino acids, mainly aspartic acid, are among the most reliable and accurate methods to date. Most of these methods use gas chromatography (GC). In this review, results of aspartic acid racemization in dentin at different targets are discussed. In addition, pre-considerations and guidelines are given for the selection of dentin from teeth. A pilot project was run to evaluate the efficiency of high performance liquid chromatography (HPLC) coupled with fluorescence detection. New buffer conditions were found to obtain stable derivatives of aspartic acid enantiomers for the estimation of racemization.     

Comparative analysis of illicit heroin samples

The comparative analysis of street heroin samples is still an object of scientific discussion. A combination of a wide range of analytical techniques is necessary to obtain a valid amount of information about the sample composition, and it is impossible to define an unique analytical approach. We suggest a complete analytical sequence based on analysis of volatile compounds, opiates, diluents, adulterants and metals, by head space gas chromatography (HS/GC), gas chromatography mass spectrometry (GC/MS), thin layer chromatography (TLC), high pressure liquid chromatography (HPLC) and atomic absorption (AA) using a sample amount as low as 50-100 mg. The outlined procedure can be successfully applied to routine work, thus obtaining suitable information about a sample's chemical composition. This helps to attribute or exclude common sources of separate specimens. Results obtained on 33 street heroin samples confiscated in the metropolitan area of Rome are listed.     

Detection of delta 9-THC in saliva by capillary GC/ECD after marihuana smoking

A method is described for the determination of delta 9-tetrahydrocannabinol (delta 9-THC) in the saliva by the use of a combination of moving-precolumn injector and glass capillary gas chromatograph with electron capture detector (GC/ECD). There were no interfering peaks due to impurities around the peak of pentafluoropropyl derivative of delta 9-THC (delta 9-THC-PFP). This GC/ECD method was linear over the range of 5-200 ng/ml of delta 9-THC-PFP. The lower detection limit was approximately 1 ng/ml. delta 9-THC content in the saliva after experimental marihuana smoking was measured by this method. It was demonstrated that for at least 4 h after smoking the level of delta 9-THC was sufficient for detection.     

用五氟苄基溴对五氯酚进行衍生化的方法

目的五氟苄基溴(PFBBr)衍生化试剂对五氯酚进行衍生化研究。方法运用GC/MS、GC/ECD印证分析衍生化产物。结果改变了五氯酚的挥发性,提高检测灵敏度,在本文控制的实验条件下,五氯酚-PFBBr衍生物的检测限可达1pg。结论为检测微量五氯酚提供了一种有效手段。