Chemical-toxicological analysis of butorphanol

The conditions of butorphanol isolation from biological fluids were studied. The method of its extraction with the mix of organic solvents by pH 12 was proposed. How to identify butorphanol with the methods of thin-layer chromatography, ultraviolet spectrometry, high-performance liquid chromatography, gas chromatography with a detector of electron capture, chromato-mass spectrometry was developed. Possibility of use ultraviolet spectrometry for quantitative assessment of butorphanol was shown.     

Detection of azaleptine in forensic chemical examination of cadaveric material

Azaleptine detection and quantitation in cadaveric material in forensic-chemical tests using thin-layer chromatography, UV-spectrophotometry, gas chromatography-mass spectrometry are outlined.     

Concentrations of mustard gas [bis(2-chloroethyl)sulfide] in the tissues of a victim of a vesicant exposure

An Iranian soldier died at a toxicological intensive care unit at Munich seven days after a vesicant exposure. At the autopsy the typical symptoms of mustard gas intoxication were found. The vesicant was detected qualitatively by gas chromatography-mass spectrometry (GC-MS) in the abdominal fat and quantified in the tissues and in the body fluids by the following method: (1) extraction by dichloromethane, (2) cleanup of the extracts by thin-layer chromatography (TLC) on silica plates, (3) extractive derivatization with gold-chloride, and (4) quantitative determination by electrothermal atomic absorption spectrometry (ET-AAS). The equal extracts, after heating, served for blanks. The following concentrations were found (milligrams of mustard gas/kilograms of tissue wet weight): brain 10.7, cerebrospinal fluid 1.9, liver 2.4, kidney 5.6; spleen 1.5, lung 0.8, muscle 3.9, fat 15.1, skin 8.4, skin with subcutaneous fatty tissue 11.8, liquid from a skin blister: below detection limit, blood 1.1, and urine: below detection limit.     

The detection of ephedrine by solid-phase immunoenzyme analytical and gas chromatographic methods

Comparative analysis of ephedrine derivative content in 96 urine specimen obtained from people suspected in abuse with these drugs. Physical and chemical methods of the analysis (gas and thin-layer chromatography) as well as ELISA were used. It was stated that the latter is specific for determination of compounds related to ephedrine by structure and it allows one to detect its analogues in 87 cases. Gas chromatography made it possible to detect ephedrine derivatives in 94 specimen tested and thin-layer chromatography--in 64 specimen tested. The given ELISA may be recommended for medicolegal expert purposes and narcology practice.     

Analysis of Explosives by GC‐UV

A mixture of explosives was analyzed by gas chromatography (GC) linked to ultraviolet (UV) spectrophotometry that enabled detection in the range of 178–330 nm. The gas‐phase UV spectra of 2,4,6‐trinitrotoluene (TNT), 2,4‐dinitrotoluene (DNT), ethylene glycol dinitrate (EGDN), glycerine trinitrate (NG, nitroglycerine), triacetone triperoxide (TATP), and pentaerythritol tetranitrate (PETN) were successfully recorded. The most interesting aspect of the current application is that it enabled simultaneous detection of both the target analyte and its decomposition products. At suitable elevated temperatures of the transfer line between the GC instrument and the UV detector, a partial decomposition was accomplished. Detection was made in real time and resulted in overlaid spectra of the mother compound and its decomposition product. Hence, the presented approach added another level to the qualitative identification of the explosives in comparison with traditional methods that relies only on the detection of the target analyte. As expected, the decomposition product of EGDN, NG, and PETN was NO, while TATP degraded to acetone. DNT and TNT did not exhibit any decomposition at the temperatures used.     

Different assays for hingamine in the study of biological fluids

The authors present a method of hingamine identification in non-biological substances (tablets, powder, syringes) and biological fluids (blood, urine). Isolation was made with chloroform in pH 10. Identification was conducted with thin-layer chromatography, gas chromatography/mass-spectrometry, high-performance liquid chromatography, spectrophotometry in UV region. The quantity was estimated with spectrophotometry in UV region, high-performance liquid chromatography and high-performance thin-layer chromatography. The results of the three methods are comparable.     

生物样品中苯二氮卓类药物检验概述

概述了苯二氮卓类药物的种类、性质和生物样品中苯二氮卓类药物的提取净化及检验方法。提取净化方法包括液-液萃取法、固相萃取(SPE)、固相微萃取(SPME)。检验方法有免疫测定法、TLC、GC、HPLC、GC/MS等。     

Investigations of clobazam (Frisium) by combined gas chromatography/mass spectrometry (author's transl)

Clobazam (Frisium) was hydrolyzed according to three methods commonly used in the determination of 1.4-benzo-diazepines; the reaction products were analyzed by gas chromatography/mass spectrometry and thin-layer chromatography. Five degradation products were obtained for which structure proposals are discussed. After oral intake two of these substances were also detected in human urine. It should be recognized that some of the above mentioned substances may be on-column degradation products of artifacts occurring during hydrolyzation and/or sample clean-up.     

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.     

Analysis of lipsticks

A combination of thin-layer and gas chromatography has been shown to be suitable for the analysis, characterisation and discrimination of the small quantities of lipsticks which may be encountered in forensic casework.     

Analysis of methylbenactyzium bromide in human urine by thin-layer chromatography and pyrolysis gas chromatography.

A rapid and simple method of utilizing thin-layer chromatography (TLC) and pyrolysis gas chromatography (PyGC) for the identification and determination of methylbenactyzium bromide in human urine was studied in this report. Methylbenactyzium bromide was extracted from urine with ODS-cartridge (Sep-Pak C18), then spotted onto a silica gel 60 F254 TLC plate. After development, the separated spot of methylbenactyzium bromide was scraped and wrapped with a ferromagnetic foil without extraction by any organic solvents. The sample was applied into PyGC analysis. The optimum temperature for pyrolysis was 590 degrees C. The main degradation product of methylbenactyzium bromide was identified as diphenylmethane in this procedure by gas chromatography/mass spectrometry (GC/MS). A calibration graph prepared by absolute calibration method showed a good linearity over the concentration range of 1-75 micrograms/spot for methylbenactyzium bromide. The coefficient of variation obtained for eleven replicate analyses of the 3 micrograms/spot of standard methylbenactyzium bromide was 3.8%. The detection limit of this compound by this procedure was 0.1 micrograms/spot.     

The application of chromatography and spectrometry for the analysis of ketorolac and diclofenac in biological fluids

The objective of the present work was to study conditions for isolation of ketorolac and diclofenac from biological fluids. A method of their extraction with a mixture of organic solvents has been developed and the conditions for the identification of these compounds are proposed with the use of high performance liquid chromatography (HPLC), UV spectroscopy, and gas chromatography with electron capture detection (GC/ECD). The possibilities of using HPLC, UV spectrometry, and GC/ECD for quantitative determination of ketorolac and diclofenac are illustrated.     

A carpipramine related fatality

A fatality following ingestion of the tricyclic antidepressant carpipramine (Prazinil) and ethyl alcohol is described. Carpipramine was quantitated by high performance liquid chromatography. The concentration of carpipramine was 2.0 mg/L in blood and 0.44 mg/L in urine. Ethyl alcohol was measured by headspace gas chromatography and found to be 105 mg/dL in blood and 55 mg/dL in the urine. Quantitative analysis of stomach contents was positive for carpipramine by thin-layer chromatography. To our knowledge, this is the first reported fatality involving carpipramine.     

Identification of 10-hydroxy-12-octadecenoic acid in adipocere

Studies are reported on separation and identification of 10-hydroxy-12-octadecenoic acid in human adipocere. The chemical structure was determined by thin-layer chromatography (TLC), gas-liquid chromatography (GLC) and gas chromatography-mass spectrometry (GC-MS).     

Analysis of volatile compounds in heroin samples

Volatile compounds of 32 street heroin samples were analyzed by head space gas-chromatographic (HSGC) technique. The reliability of this procedure coupled with thin-layer chromatography (TLC), gas chromatography (GC), high performance liquid chromatography (HPLC), and its application to forensic casework (comparative sample analysis) is discussed.     

Attempted murder with pancuronium

A nurse was accused of attempting to murder her anesthesiologist husband on two occasions by administering to him a neuromuscular blocking agent. In both episodes, urine specimens were obtained from the victim shortly after the suspected assaults. The samples were initially tested fluorometrically using Rose Bengal dye as a pairing agent. Both were presumptively positive for pancuronium. Confirmation of these results was achieved by pairing the drug with potassium iodide, extracting the complex, and submitting the extract to thin-layer chromatography (TLC) cleanup, elution at the appropriate retardation factor (Rf), and, finally, gas chromatography/mass spectrometry (GC/MS) analysis in the selected-ion monitoring mode. The two quaternary amines of pancuronium appear to undergo pyrolytic N-demethylation in the injection port to yield an entity amenable to capillary column gas chromatography. The mass spectrum of the compound consists of a base peak of m/z 322, with additional fragments of 292, 323, 338, and 397 m/z, each of which was monitored. The confirmed positive findings were instrumental in adjudicating the case.     

Qualitative and quantitative analysis of cephradine in biological materials by high performance liquid chromatography

A reversed phase high performance liquid chromatographic method was developed for the determination of cephradine, one of the commonly used antibiotics, in biological materials. Mimic samples for stomach contents, miso soup, were applied to high performance liquid chromatography (HPLC) after centrifugation and purification by Sep-Pak C18 cartridge treatment. Serum samples deproteinized or urine samples diluted were directly injected into the HPLC. The recoveries of cephradine from these materials were 95-97% and the detection limit was 0.01 microgram/injection. This method was applied to the analysis of cephradine in stomach contents obtained by autopsy. After purification by the cartridge treatment, cephradine in the sample was identified and determined by HPLC and further confirmed by thin-layer chromatography (TLC) and mass spectrometry (MS).     

Determination of chloroquine and monodesethylchloroquine in hair

Using thin-layer and gas chromatography and mass spectrometry, chloroquine and its major metabolite (monodesethylchloroquine) were identified in hair samples of numerous patients who received this antimalarial drug for several months. In two patients the amounts of chloroquine were, respectively, 310 and 145 mg/kg hair and those of the monodesethylchloroquine 23 and 11 mg/kg. The respective proportions (93 and 7%) are the same in the two subjects. The chloroquine percentage was near those in the spleen or stomach wall after poisoning. Other metabolites in hair are being identified. Hair analysis may provide a good toxicologic and forensic science complement to the blood, urine, and tissues. It may be useful for the control of chloroquine therapy.     

高效薄层色谱法检测尿中硝西泮的代谢物7-氨基硝西泮

目的 建立用高效薄层色谱法定性及半定量测定人尿中硝西泮的代谢物7-氨基硝西泮(7ANIZ)含量的方法。方法 人口服治疗量10 mg硝西泮后,在pH 9条件下用乙醚进行提取,分析物斑点用氟罗里丝进行荧光显色,紫外灯下(366nm)观察荧光斑点;根据斑点荧光显色情况及强度进行7ANIZ定性及半定量检测。结果 尿中硝西泮代谢物7ANIZ检出限为5 ng/ml,测量限为15 ng/ml。结论 人口服治疗量10 mg硝西泮,用高效薄层色谱法可定性及半定量测定48 h内排泄尿中的7ANIZ。     

Optimization of solid-phase microextraction (SPME) for the recovery of explosives from aqueous and post-explosion debris followed by gas and liquid chromatographic analysis

Solid-phase microextraction (SPME) has been evaluated for the recovery of explosives residues from aqueous samples and real post-explosion solid debris samples and optimized using gas chromatography with an electron capture detector (GC-ECD) and high-performance liquid chromatography with ultraviolet detection (HPLC-UV). A modified SPME/HPLC interface utilizing dual six-port valves allowed for independent optimization of SPME desorption and injection variables that provided improved chromatographic resolution and sensitivity. A unique combination of cyano and octadecyl columns resulted in the complete separation of the 14 explosives in EPA method 8330 mixture using HPLC with good quantitative results. At the optimum SPME conditions, the limits of detection (LOD) were found to be of 5 ng/mL to 16 ng/mL of explosives in water and 10 microg/kg to 40 microg/kg of explosives from soil. The technique has been successfully applied to the analysis of real post-explosion debris and can be adapted for use in the field utilizing portable chromatographic instruments.