GC/MS determination of pyrolysis products from diacetylmorphine and adulterants of street heroin samples

The inhalation of heroin vapors after heating on aluminium foil ("chasing the dragon") is gaining popularity nowadays among heroin users seeking to avoid the risks of parenteral drug administration. The heroin-smoking procedure was simulated under laboratory conditions by heating the samples on aluminium foil at 250 to 400 degrees C and collecting the vapors in a condenser trap. A total of 72 pyrolysis products of diacetylmorphine, street heroin, residues from aluminium foils used to smoke street heroin, typical by-products, and adulterants were detected by gas chromatography/mass spectrometry (GC/MS). About half of these compounds could be identified. Diacetylmorphine (base and salt) undergoes substantial to complete degradation. Some typical street heroin constituents, like morphine, codeine, acetylcodeine, papaverine, and caffeine, are rather heat-stable. Other compounds, like noscapine and paracetamol, are pyrolyzed to a greater extent. The principal chemical reactions leading to the formation of pyrolysis products are desacetylation, transacetylation, N-demethylation, O-methylation, ring cleavage and oxydation.     

高效液相色谱法测定小鼠血清中可卡因的含量

目的 建立一种测定血清中可卡因含量的高效液相色谱方法。方法 以0.04mol/L磷酸盐缓冲液(含有0.26 mmol/L四丁基胺盐,pH3.2)-乙腈(83:17)为流动相,血清样品采用2％异戊醇正己烷-0.1 mol/L HCl液液反萃取法处理,用Kromasil C18色谱柱分析血清中可卡因的含量。紫外检测波长为235nm。结果可卡因的最小检出浓度为25ng/ml,回收率71％。结论所建方法测定血清中可卡因含量灵敏度高,简便易行。     

An investigation of the potential of high performance liquid chromatography for the comparison of soil samples

A simple presumptive test for the comparison of soil samples, namely the high performance liquid chromatographic comparison of the acetonitrile extract of soil, appears promising. Soils taken from different areas had different chromatograms. Soil taken from the same area had similar chromatograms. The chromatographic profile of one soil sample remained constant over a period of seven weeks.     

High pressure liquid chromatography analysis of heroin

A liquid-solid chromatographic system is described that will separate heroin from 26 substances encountered in heroin seizures. The effects of ammonia and water concentration on the retention of the drug substances were investigated. Three ‘brown’ heroin samples were analyzed by high pressure liquid chromatography (HPLC) and by gas-liquid chromatography (GLC) and the results evaluated and compared.     

Ofloxacin in human hair determined by high performance liquid chromatography.

A procedure is presented for quantitating ofloxacin (OFLX) in human scalp hair by high performance liquid chromatography (HPLC) with a fluorescence detector. An octadecylsilane (ODS) column was used and the mobile phase was a mixture of potassium phosphate buffer (pH 2.6) and acetonitrile. The recovery of OFLX was 90.9-93.8% and within- and between-run precisions were 0.35-1.41% and 1.41-5.49% as the coefficient of variation (CV), respectively, when 5-50 ng OFLX was added to 1 mg blank hair. The calibration curve was linear in the range of 0.5-50 ng/tube (0.5 ml). Interference with other quinolone derivatives could be avoided according to the difference in their retention times or fluorescence spectra. Several pieces of hair were obtained from each of twelve healthy male volunteers, who had taken OFLX (100, 300 or 900 mg total dose) over a 1-3 day period 2 weeks before the hair sampling. In all hair samples except one obtained from a volunteer, who had taken the lowest dose, the 2-cm long segments nearest the scalp contained OFLX (5-45 ng/mg hair), while the upper segments did not. A highly significant positive correlation was observed between the total dose and the concentration of OFLX in the 2-cm long hair segments. Such a positive correlation was also revealed in rat hair sampled after repeated i.p. administration of OFLX over a 5-week period. These results suggest that the measurement of OFLX in hair by the present method would be useful for testing patient compliance in clinical pharmacology as well as for application to forensic science.     

A quantitative densitometric determination of heroin and cocaine samples by high-performance thin-layer chromatography

The traditional thin-layer chromatography (TLC) is a sensitive technique frequently used in chemical analysis for semiquantitative determinations. In the last years a high-performance thin-layer chromatography system (HPTLC) has been developed. It assures quantitative determinations with direct densitometric measurements of chromatographic spots in situ on the plate. Here, we wish to report a method for the drug determination in street samples, that employs a CAMAG TLC/HPTLC Scanner Photodensitometer and a CAMAG LINOMAT III for sample application. Samples of illicit drug traffic (50 samples of street heroin and 30 samples of street cocaine) are tested and the gas-liquid chromatography (GLC) and HPTLC determinations are compared. The HPTLC method has proven to be sensitive, precise and accurate for quantitative determinations of drugs in street samples. Furthermore this method may be useful in forensic chemistry to show a "fingerprint" of each sample.     

Identification of fetal hemoglobin in blood stains by high performance liquid chromatography

A new method for the identification of fetal hemoglobin (Hb F) in blood stains by reverse-phase high performance liquid chromatography is described. Differentiation between fetal and adult blood stains is based on the existence of gamma-chain peaks which are characteristics of Hb F. Very few gamma chains appeared on chromatograms of all the adult blood stains examined. The level of Hb F could be determined by measuring the total of chromatogram gamma-globin chain areas, and expressing it as a percentage of total Hb. Levels in six cord blood stains on filter paper ranged from 81.1% to 91.3% and remained constant for at least 12 weeks. This method is of great value for its simplicity, sensitivity and speed, and most importantly for its reliability in the field of forensic medicine.     

人血浆中更昔洛韦的高效液相色谱快速分析

目的建立人血浆中抗病毒药物更昔洛韦的高效液相色谱快速分析方法。方法在一定pH值下用甲醇和二氯甲烷处理血浆,高速离心后外标法直接对上清液进行更昔洛韦定性、定量分析。以正常人血浆为空白样本添加标准更昔洛韦,优化色谱分析条件并确定检材的前处理方法、工作曲线、线性范围、方法的精密度和回收率。以所建方法对12位受试者血浆中更昔洛韦代谢浓度进行12h监测。结果该方法分析血浆中的更昔洛韦,其线性范围为0.05μg/mL～1.60μg/mL;最低检测限为0.01μg/mL(S/N≥3),日内、日间RSD≤5.1%,加样回收率在90.0%～95.4%之间。结论该分析方法操作便捷、实用、准确度高。适用于更昔洛韦的临床血药浓度监测和法医学药(毒)物快速鉴定。     

Differentiation of coloured inks of inkjet printer cartridges by thin layer chromatography and high performance liquid chromatography

Document examiners are frequently asked to determine whether or not a colour printout has originated from a particular inkjet printer. The printer can rarely be identified unless some unique defects or irregularities of the printer are present on the printout. However, it is possible to decipher the make and/or model of the printer by comparing the ink-profile of the questioned printout with that of a seized inkjet printer cartridge or from one in a database. This paper presents an overview of a systematic approach to characterising and discriminating the inks of different inkjet printer cartridges using thin layer chromatography (TLC) and high pressure liquid chromatography (HPLC) with multi-wavelength ultra-violet/visible (UV/Vis) detection. Ink samples from 23 different inkjet printer cartridges (including originals and substitutes) of different brands and colour printouts, printed by known printers were examined with newly developed chromatographic methods. Subsequently, a database of the ink-profiles was generated. The methods provide a useful tool for discriminating coloured inks in inkjet printer cartridges of different brands.     

血液、尿液中氯胺酮及其代谢物去甲氯胺酮的HPLC分析

目的 建立血液、尿液中氯胺酮及其代谢物去甲氯胺酮的高效液相色谱(HPLC)分析方法.方法 以非那西丁为内标,检材加入10%的氢氧化钠溶液调节pH值为14,用甲苯提取,离心后取有机层,水浴下吹干,乙腈定容后进HPLC仪分析.结果 检测血液中氯胺酮和去甲氯胺酮的线性范围均是0.05～10μg/mL(r2＞0.999 3),检测尿液中氯胺酮和去甲氯胺酮的线性范围均是0.01～50 μg/mL(r2＞0.999 5).氯胺酮和去甲氯胺酮在血液和尿液中的检测限分别是0.006 μg/mL和0.003 μg/mL.血液和尿液中氯胺酮和去甲氯胺酮的回收率不低于82.4%.检测血液和尿液中氯胺酮和去甲氯胺酮的日内精密度和日间精密度均小于10.0%.将所建的方法应用于给大鼠氯胺酮后的血液和尿液中的氯胺酮和去甲氯胺酮的测定,得到了氯胺酮和去甲氯胺酮在大鼠的药时曲线和尿排药速率曲线. 结论本方法简便、快捷,适用于血液、尿液中氯胺酮及其代谢物去甲氯胺酮的分析.     

Rapid extraction of oxazepam from greyhound urine for high performance liquid chromatography analysis

A rapid and efficient procedure is described for the extraction and analysis of oxazepam, the major urinary metabolite of diazepam in greyhounds. Urine was extracted by passing through a bonded silica column (Bond Elut) following enzyme hydrolysis. The adsorbed drug was eluted and then detected and measured by high performance liquid chromatography (HPLC). Recoveries were in excess of 85% at 50 ng/ml concentrations. Detection was possible up to 30 h after a single oral dose of diazepam (5 mg).     

Forensic toxicologic analysis of methamphetamine and amphetamine optical isomers by high performance liquid chromatography

Optical isomers (d and l) and racemic compounds (dl) of methamphetamine (MAMP) and amphetamine (AMP), and biologic materials including those substances, could be analyzed by high performance liquid chromatography. Examining the temperature for the analysis, 40 degrees C was the optimal condition in the reproducibility of separated MAMP-isomers. The reproducibility at the temperature did not vary significantly. The measured values of optical isomers were 0.116 +/- 0.012, 1.082 +/- 0.070 and 8.984 +/- 0.136 for the mixing ratios (l/d) of 0.111, 1.000, and 9.000, respectively. The detection limit for both d- and l-isomers was 25 ng. The analytic result of hair specimens from two stimulant abusers by the present method indicates that they contained only d-MAMP and d-AMP, which is believed to have the strongest pharmacologic effect among the optical isomers of MAMP. The coefficient of variation in the analysis of five replicate standards, prepared by adding 1,000 ng each of racemate MAMP and AMP to hair, was less than 4%. The measured value against l/d = 1.000 was 1.040 +/- 0.040 in MAMP and 0.980 +/- 0.030 in AMP. The detection limit for both racemate MAMP and AMP accumulated in hair was 250 ng. The analysis of the optical isomers by our method would contribute to identifying the smuggling routes or the illicit method.     

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).     

高效液相色谱法分离测定药酒中乌头碱的含量

目的建立药酒中乌头碱的高效液相色谱快速分析方法。方法以白酒添加乌头碱对照品对药酒样品的前处理方法、仪器测试条件、线性范围、精密度、回收率进行全面考察,建立定量分析方法。对药酒中所含乌头碱的浓度进行测定。结果该方法乌头碱在药酒中的线性范围是0.45～9.0μg·mL-1;日内、日间精密度分别小于3.1%和4.7%;回收率在(97.3±2.8)%以上。结论所建方法实用、便捷,可对药酒中乌头碱的含量进行快速检测。     

A new marker for estimation of bloodstain age by high performance liquid chromatography.

The applicability of a new marker for estimation of bloodstain age by reverse-phase high performance liquid chromatography (HPLC) is described. Using a microBondasphere C18 column with a two step linear gradient of 10.5-46.25% acetonitrile in 0.1% trifluoroacetic acid, an intriguing peak (unidentified) at a retention time of about 5 min was observed on chromatograms from human adult bloodstains and designated as 'X'. The area of this peak, which could be detected in extracts of bloodstains, but not in their fresh whole blood, increased with time. The ratios of the X area to heme area in bloodstains stored at room temperature and 4 degrees C for up to 52 weeks old linearly correlated with stain age by plotting on a double logarithmic scale. In bloodstains exposed to fluorescent light at room temperature, the regression equation calculated from the ratios (Rx) and the ages of stains in weeks (W) is ln(1000.Rx) = 1.1084 + 0.3937.ln(7.W), and the coefficient of correlation (r) is 0.9776 (n = 144, P < 0.001). When stains were stored at 37 degrees C, the ratio transformed into logarithms correlated linearly with stain age. The regression equation describing the relationship in bloodstains exposed to fluorescent light at 37 degrees C is ln(1000.Rx) = 2.4477 + 0.0866.W (r = 0.9826, n = 144, P < 0.001). The results of the present study suggest that the HPLC method may be applicable to the estimation of bloodstain age.     

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.     

Heroin, morphine, and hydromorphone determination in postmortem material by high performance liquid chromatography

A procedure has been developed for the simultaneous determination of heroin, morphine, and hydromorphone from postmortem tissues by reversed phase high performance liquid chromatography (HPLC) using electrochemical detection. This method permits the direct determination of unmetabolized heroin from antemortem or postmortem urine as evidence of illegal drug use. Presumptive confirmation of heroin was based on the ability to hydrolyze the HPLC heroin fraction to morphine. Heroin was also confirmed in urine by gas chromatographic/mass spectroscopic (GC/MS) analysis of the HPLC fraction. Analysis of postmortem blood, gastric contents, urine, and injection site tissues have revealed the presence of morphine and hydromorphone, while heroin has only been identified in urine.     

家兔玻璃体和脑脊液中异烟肼的高效液相色谱分析

目的　建立玻璃体和脑脊液中异烟肼的高效液相色谱分析方法。方法　以香草醛为衍生化试剂 ,经柱前衍生为异烟肼 -香草醛腙 ,直接对体液样品中的腙进行定性、定量分析 ,并以空白兔体液添加标准异烟肼对样品的前处理方法、仪器条件、线性范围、精密度、回收率进行全面考查后 ,测定急性染毒家兔玻璃体和脑脊液中的异烟肼浓度。结果　用上述方法分析兔玻璃体和脑脊液中异烟肼 ,其线性范围为 0 2～ 12 0 μg/ml,检测限 0 2 μg/ml,日内、日间精度均小于 4 9% ,回收率均在 97 1%以上。异烟肼在急性染毒家兔玻璃体中的浓度为 74 60± 7 40 μg/ml;脑脊液中为 88 95± 10 12 μg/ml。 结论　本文所建方法适用于异烟肼中毒者玻璃体和脑脊液中异烟肼的检测。