Detection of methadone in human hair by gas chromatography/mass spectrometry

Summary Determination of methadone in human hair by gas chromatography/mass spectrometry was described. Helium as carrier gas, a 30-m bonded phasefused silica DB-1 capillary column and splitless injection at 230°C temperature were used. The concentrations of methadone and its metabolites were measured in addition by radioimmunoassay (RIA). Both methods GC/MS and RIA showed the presence of methadone in human hair.     

Determination of cocaine in human hair by gas chromatography/mass spectrometry

Summary A qualitative method for the determination of cocaine alone without its metabolites in human hair by gas chromatography/mass spectrometry (GC/MS) was developed. The assay used helium as carrier gas, a 30-m bonded phase fused silica OV-1 capillary column, and solid injection at 290°C evaporator temperature.The cocaine concentrations in hair were determined also by radio-immunoassay (RIA). The values obtained are the sum of cocaine and its metabolites.Both GC/MS and RIA meet the requirements for the determination of drug abuse by two different methods in forensic science.     

Identification of a dextropropoxyphene metabolite by gas chromatography—mass spectrometry

Summary Gas chromatography in combination with high and low resolution mass spectrometry has been used for identification of metabolites of dextropropoxyphene isolated from liver extract.

---

Zusammenfassung Für die Identifikation der Metaboliten von Dextropropoxyphen aus Leberextrakten wurde eine Kombination der Gaschromatographie mit der hoch und niedrig auflösenden Massenspektrometrie angewandt.

     

The confirmation of 9-carboxy-THC in urine by gas chromatography/mass spectrometry

A mass spectral method for the identification of the urine metabolite of THC, 11-nor-delta-9-tetrahydrocannabinol-9-carboxylic acid, has been developed. The metabolite is extracted from the urine, derivatized to the methyl ester, methyl ether, and analyzed on a gas chromatograph/mass spectrometer. Identification of the metabolite is based on the retention time of the derivatized compound and its electron impact (EI) or chemical ionization (CI) mass spectrum. The EI spectrum shows three characteristic ions at masses 313, 357, and 372 (the molecular ion). When methane is used as the reactant gas, the CI spectrum shows an ion at 341 and an M + 1 ion at mass 373.     

Simultaneous determination of tryptamine analogues in designer drugs using gas chromatography–mass spectrometry and liquid chromatography–tandem mass spectrometry

In recent years, a large number of tryptamine-based designer drugs have been encountered in forensic samples. We have developed simultaneous analytical methods for 14 tryptamine analogues using gas chromatography–mass spectrometry (GC–MS) and liquid chromatography–tandem mass spectrometry (LC–MS–MS). Trimethylsilyl (TMS) derivatives of the analytes were separated on a DB-1ms column within 15 min. The structural isomers could be differentiated by electron ionization GC–MS. LC–MS–MS with a C₁₈ column could separate structural isomers of tryptamines except for a combination of 5-methoxy-N,N-diethyltryptamine and 5-methoxy-N-methyl-N-isopropyltryptamine. Higher collision energy gave different product ion spectra between the structural isomers. The results indicate that GC–MS is the first choice for identification of tryptamines, preferably after TMS derivatization, and LC–MS–MS can be used as a complementary approach for the unequivocal differentiation of tryptamine isomers.     

Forensic toxicologic analysis of methamphetamine and amphetamine in body materials by gas chromatography/mass spectrometry

Summary Qualitative and quantitative analysis of methamphetamine and amphetamine in biologic materials was carried out by gas chromatography/mass spectrometry. A deuterium-labeled methamphetamine was employed as an internal standard with a detection limit of 50 pg and absolute stability and reproducibility. Blood was found to be the best material for estimation of the toxicity of the stimulant drug. It can be replaced by muscle which contains methamphetamine concentrations close to those of blood. The authors' classification of the toxic blood levels of methamphetamine from therapeutic to fatal doses was confirmed by additional data obtained from new case studies.Supported by a grant-in-aid for scientific research in 1983/1984 from the Japanese Ministry of Education     

Simultaneous quantitative analysis of methamphetamine and 4-hydroxymethamphetamine in body fluids by gas chromatography/mass spectrometry

Summary Pentodeuterated 4-hydroxymethamphetamine(HMAMP-d5),1-(4-hydroxyphenyl)-2-(methyl-d₃-amino)-propane-1,2-d₂ of high quality was prepared and proved to be a most useful internal standard for quantitative analyses of 4-hydroxymethamphetamine(HMAMP), a main metabolite of methamphetamine(MAMP). Highly reliable results were obtained by gas chromatography/mass spectrometry. Simultaneously we determined also MAMP, amphetamine (AMP), 4-hydroxyamphetamine(HAMP), and HMAMP in body fluids, using two internal standards, HMAMP-d5 for HMAMP and HAMP and pentodeuterated methamphetamine, 1-phenyl-2-(methyl-d₃-amino)-propane-1,2-d₂, for MAMP and AMP.     

Detection of malathion in a victim by gas chromatography/negative ion chemical ionization mass spectrometry

Summary We experienced an autopsy case in which a 53-year-old woman committed suicide by ingesting allegedly a certain agricultural chemical. The blood and stomach contents, after extraction with acetonitrile and chloroform, were subjected to analysis by gas chromatography (GC)/negative ion chemical ionization (CI) mass spectrometry (MS). By total ion monitoring in the negative CI mode, a large peak appeared. The mass spectrum of the peak showed a strong anion at m/z 157, suggesting the presence of an organophosphorus pesticide. By measuring its spectrum in the positive electron impact (EI) mode, it was identified as malathion. The selected ion monitoring in the negative CI mode showed that the malathion peak was not interfered with by any impurities, and its background was very low. The sensitivity in the negative CI mode was about 5–10 times higher than that in the positive EI mode. Our data show that the GC/negative ion CI MS is useful for both screening and sensitive quantitation of organophosphorus pesticides.     

Simultaneous determination of triazolam and its metabolites in human blood and urine by gas chromatography/mass spectrometry

A sensitive and selective method has been developed for simultaneous determination of triazolam and its major metabolites, alpha-hydroxytriazolam and 4-hydroxytriazolam, in human whole blood and urine. The drugs were effectively extracted using a 3-step solvent extraction procedure followed by tert- butyldimethylsilyl derivatization, and subjected to gas chromatography-mass spectrometry in the negative ion chemical ionization mode. Estazolam was used as an internal standard. The calibration curve for each compound was linear in the range from 0.5 to 100 ng/g, and the lower limit of detection was 0.1 ng/g for whole blood and 0.2 ng/g for urine. Within-day precision of this method was evaluated in whole blood and urine samples at the concentration of 10 ng/g; the coefficient of within-day variation ranged from 2.7 to 10.8%.     

Fatal combined anileridine-pethidine poisoning. A gas chromatography,thin layer chromatography and mass spectrometry investigation

Summary Anileridine and pethidine were established by gas and thin layer chromatography and mass spectroscopy. In the mass spectrum the main peak of anileridine is found at m/e 246 and that of pethidine at m/e 71. The determination was made by gas chromatography from the blood, urine, liver, muscle and stomach contents.

---

Zusammenfassung Anileridin und Pethidin wurden mittels Gas- und Dünnschicht-chromatographie sowie massenspektroskopisch festgestellt. Im Massenspektrum liegen die Hauptspitze von Anileridin bei m/e 246 und diejenige von Pethidin bei m/e 71. Die Bestimmung erfolgte gaschromatographisch aus Blut, Harn, Leber, Muskel und Mageninhalt.

     

Thermal degradation of a new synthetic cannabinoid QUPIC during analysis by gas chromatography–mass spectrometry

Quinolin-8-yl 1-pentyl-(1H-indole)-3-carboxylate (QUPIC) is a newly introduced synthetic cannabinoid in the drug market. This drug was found to undergo thermal decomposition during gas chromatography–mass spectrometry (GC–MS), probably because of the presence of an ester bond in its structure. Most notably, when QUPIC dissolved in methanol or ethanol was analyzed by GC–MS, most of the QUPIC decomposed to give thermal degradation products. We identified the products as methyl 1-pentyl-(1H-indole)-3-carboxylate, ethyl 1-pentyl-(1H-indole)-3-carboxylate, and methyl indole-3-carboxylate by comparison of their mass spectra with those of reference standards synthesized in our laboratory. Nonalcoholic solvents such as acetone and chloroform gave a major peak and a minor peak for unchanged QUPIC and the degradation product 8-quinolinol, respectively. Furthermore, we studied the effects of various parameters, such as injection methods (splitless or split, and split ratio), injector temperatures, and injector liners on the thermal degradation of QUPIC. Split injection was effective in avoiding degradation. When performing splitless injection, an injector temperature of 250 °C and a surface deactivated injector liner without glass wool minimized the degradation and enhanced the sensitivity. These results indicate that special attention is required for GC–MS analysis of QUPIC, and the information presented in this study will be very useful for forensic toxicologists using GC–MS.     

Determination and identification of sympathomimetic amines in blood samples from drivers by a combination of gas chromatography and mass spectrometry

Summary Gas chromatographic and mass spectrometric data concerning the analysis for certain sympathomimetic amines in blood samples from drivers are presented. In all cases where gas chromatography gave peaks at the correct retention times for amphetamine or phenmetrazine respectively, mass spectrometry confirmed the presence of the corresponding drugs in the extracts from blood. Drug-free blood samples gave neither gas chromatographic nor mass spectrometric responses at the retention times characteristic for amphetamine or phenmetrazine.Computer-drawn mass spectra of phenmetrazine are shown in Fig. 2. Analytical data obtained from twelve drivers and one hospital patient are collected in the table.

---

Zusammenfassung Blutproben von Kraftfahrern, die sympathomimetische aromatische Amine zu sich genommen hatten, zeigten gaschromatographische Zacken mit den Retentionszeiten von Amphetamin oder Phenmetrazin (Preludin®). Eine Reihe solcher Fälle wurden mit Hilfe einer kombinierten gaschromatographisch-massenspektrometrischen Methodik untersucht. In sämtlichen Fällen konnte die vermutete Identität der beiden Amine massenspektrometrisch einwandfrei bestätigt werden. Blutproben von drogenfreien Personen, auf exakt gleiche Weise untersucht, gaben weder im Gaschromatogramm noch im Massenspektrum irgendwelchen Ausschlag.Massenspektren von Phenmetrazin, rein und nach Isolierung aus Blutproben, wurden durch einen Computer berechnet und gezeichnet. Abb. 2 zeigt die Resultate.Quantitative Analysen und einwandfreie Identifizierung durch Gaschromatographie und Massenspektroskopie sind noch bei Mengen von ca. 1 g Amphetamin oder Phenmetrazin in Blutproben ausführbar.Qualitative und quantitative Resultate der Untersuchung von 12 Kraftfahrern und einem Patienten sind in der Tabelle zusammengestellt.

     

Simultaneous determination of nicotine and cotinine in various human tissues using capillary gas chromatography/mass spectrometry

Summary A reliable and sensitive method for the simultaneous determination of nicotine and cotinine concentrations in various human tissues was developed using capillary gas chromatography/mass spectrometry. Nicotine and cotinine were extracted using a 3-step solvent extraction procedure and quinoline as an internal standard. Quantification was carried out by single ion monitoring using ions of m/z 133 for nicotine, m/z 176 for cotinine and m/z 129 for quinoline. The lower limit of detection was 5 ng/g for nicotine and 10 ng/g for cotinine, in each tissue sample. The calibration curves of various tissues were linear in the concentration range from 5–1,200 ng/g for nicotine and 10–1,500 ng/g for cotinine. The accuracy and precision of this method were examined using human tissues and the results were satisfactory. The distribution of nicotine and cotinine was measured in tissues from 10 human autopsies. Nicotine was detected in every tissue examined at a level seen in habitual smokers. The nicotine concentration was high in the liver, kidney, spleen and lung, and low in adipose tissue. The cotinine level was highest in the liver. The tissue/blood concentration ratios of nicotine and cotinine were most stable in skeletal muscle, where the level of these drugs was close to that in whole blood. Skeletal muscle is, therefore, considered to be the most suitable tissue sample for toxicological examination, when acquisition of blood samples is not feasible.     

Determination of acephate and methamidophos in tissues: appearance of matrix effect in gas chromatography–mass spectrometry

A simple and reliable method to determine acephate and methamidophos in mammalian tissues is presented. The method includes solid-phase extraction of tissue extracts with active carbon cartridges followed by gas chromatography–mass spectrometry analysis. During the study, a matrix effect was observed especially at low concentrations of acephate and methamidophos in serum and in brain. To minimize the effect, we prepared calibration curves with relatively short ranges. The validation data, such as the linearity of calibration curves, limits of detection, and coefficients of variation for recovery rates, were generally satisfactory. The present method is useful for determination of acephate and methamidophos in mammalian tissues because of its simplicity and speed, keeping in mind the presence of the matrix effect.     

LC-MS法检测大鼠血浆中酒石酸美托洛尔的方法学研究

目的：建立准确、灵敏、可靠的LC-MS法检测大鼠血浆中酒石酸美托洛尔的浓度。方法：血浆样品用乙酸乙酯液-液萃取,内标选用盐酸普萘洛尔,液相色谱柱为ThermoODS-C18（5.0μm,100mm×2.1mm）,流动相为含0.1%甲酸的乙腈：甲醇：水（20：20：60,体积比）,流速为0.2ml/min;仪器选用Agilent公司1100LC/MSDSL型液相色谱-质谱联用仪,采用电喷雾离子化电离源（ESI）,选择性离子监测（SIM）方式进行正离子检测,用于定量分析的离子反应分别为m/z267→268（美托洛尔）和m/z259→260（普萘洛尔）。结果：在本实验条件下,美托洛尔与内标盐酸普萘洛尔分离良好,保留时间分别为1.79和4.01min,0.1～50ng/ml范围内线性关系良好（r2=0.99411）,提取回收率均大于80%,日内日间精密度均小于15%（n=5）。结论：该方法快速、准确、灵敏度高,专属性好,可用于酒石酸美托洛尔在大鼠体内药物代谢动力学的研究。     

Analytical method for detection and quantification of new emerging drug etaqualone in human blood and urine by gas chromatography tandem mass spectrometry

Analytical procedure for detection and quantification of etaqualone in human blood and urine using GC–MS/MS was established and applied to authentic human samples obtained from volunteers. A liquid–liquid extraction method was employed. Each 1.0 mL of blood or urine was alkalized and extracted with diethyl ether. The solvent layer was evaporated to dryness and reconstituted with methanol then analyzed by GC–MS/MS. linear relationships within the concentration range of 1–100 ng/mL were obtained in calibrators for both blood and urine, demonstrating correlation coefficients values being>0.999. For blood and urine samples, the intra-day assay precision and accuracy values are each less than 3.65%, 7.13%, and 6.02%, 9.12%; those values of the inter-day assay are each less than 1.82%, 6.74%, and 3.99%, 7.41%. The extraction recovery rates for etaqualone ranged from 98.7% to 106%. The lower limit of quantifications was 1.0 ng/mL in both blood and urine. Stabilities of etaqualone in blood and urine were satisfactory under various temperatures within 15 days. 8.51 and 2.06 ng/mL of etaqualone in blood and urine were detected at 4 h later oral ingestion; 6.91 and 3.94 ng/mL of etaqualone were also detected 30 min and 2 h later smoking from blood and urine.     

Ayahuasca and Kambo intoxication after alternative natural therapy for depression,confirmed by mass spectrometry

Forensic Toxicology - We present a case report about an acute intoxication episode after an oral administration of Ayahuasca and dermal exposure of Kambo for treatment of depression. The clinical...     

Confirmation of natural gas explosion from methane quantification by headspace gas chromatography–mass spectrometry (HS-GC-MS) in postmortem samples: a case report

A new analytical approach for measuring methane in tissues is presented. For the first time, the use of in situ-produced, stably labelled CDH₃ provides a reliable and precise methane quantification. This method was applied to postmortem samples obtained from two victims to help determine the explosion origin. There was evidence of methane in the adipose tissue (82 nmol/g) and cardiac blood (1.3 nmol/g) of one victim, which corresponded to a lethal methane outburst. These results are discussed in the context of the available literature to define an analysis protocol for application in the event of a gas explosion.     

Assessment of bone mineral content and bone mass by non-invasive radiologic methods

Methods for quantitative determination of bone mineral and bone mass in normal subjects and in patients with metabolic bone disorders can be measured by the Compton scattering technique, the neutron activation analysis, by measurement of metacarpal bone mass, by single and dual photon absorptiometry, and by quantitative computed tomography. Measurement on metacarpal bone (radiogrammetry) seems to be able to distinguish between resorption and/or new bone formation at the periosteal and/or endosteal surface. The intraindividual observer variation on combined cortical thickness (D-d), cortical area (D2-d2), metacarpal bone mass (D2-d2)/D2-varies from 0.7 to 2.5 per cent and the interindividual observer variation from 1.0 to 5.8 per cent. Single photon absorptiometry measures bone mineral content in the forearm with great precision. The reproducibility using repeated measurements and automatic selection of the measuring area is about one per cent and can be used to follow changes in mineral content with time in patients with metabolic bone diseases. The dual photon absorptiometry may be used for measurements of bone mineral content in lumbar spine, in the femoral neck and measurement of total body calcium with an accuracy of less than 6 per cent and a precision below 3 per cent. Quantitative computed tomography has the ability to measure trabecular and cortical bone both centrally and peripherally. Using CT scanning, scanner related changes with time (day-to-day variation +/- 4%), patient repositioning (less than 1.5%), and fat concentration (residual uncertainty of approximately 1/6 of the biologic variation) are important factors influencing the accuracy and reproducibility of the values of the measured bone mineral content.(ABSTRACT TRUNCATED AT 250 WORDS)