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1.
A new method was developed for pre-concentration, chiral separation and determination of multiple illicit drugs on forensic samples using dispersive liquid-liquid microextraction (DLLME) and capillary electrophoresis (CE) with Ultra Violet (UV) detection. The method was based on the formation of tiny droplets of an organic extractant in the prepared sample solution using water-immiscible organic solvent (chloroform) dissolved in water-miscible organic dispersive solvent (isopropyl alcohol). The organic phase, which extracted heroin, DL-methamphetamine, DL-3, 4-methylenedioxymethamphetamine and dl-ketamine from the prepared sample solution, was separated by centrifuging. The sedimented phase was transferred into a small volume CE auto-sampler vial with 10 μL of 1% HCl methanol solution and evaporated to dryness. The residue was reconstituted in lidocaine hydrochloride aqueous solution (internal standard) and introduced by electrokinetic injection into CE. Parameters affecting extraction efficiency were investigated and optimized. Under optimum conditions, linearity of the method was 0.15-6500 μg/L for all target analytes. The LODs (S/N=3) were 0.05-0.20 μg/L. Excellent repeatability (RSD ≤ 4.4%, n=5) was achieved. The feasibility of this method was demonstrated by analyzing spiked forensic samples. To our knowledge, it is the first time to combine DLLME with CE for chiral separation and determining illicit drugs on forensic samples.  相似文献   

2.
哌嗪类药物N-苄基哌嗪(BZP)、1-(3-氯苯基)哌嗪(mCPP)、1-(3-三氟甲基苯基)哌嗪(TFMPP)具有与MDMA相似的兴奋作用和致幻作用,成了迷幻药的替代品,在各国滥用的报道逐年增多。本文综述了3种哌嗪类药物在各国的管制、滥用情况、毒理作用、检测方法,希望为司法部门打击此类药物犯罪提供参考和借鉴。  相似文献   

3.
Capillary electrophoresis (CE) is a modern separation technique that has some distinct advantages for toxicological analysis, such as a high efficiency, fast analysis, flexibility, and complementary separation mechanisms to chromatographic methods. CE can be applied in various modes, which each have a different separation mechanism or selectivity. The most common mode is capillary zone electrophoresis (CZE), in which charged analytes migrate in a buffer under the influence of an electric field. In micellar electrokinetic chromatography (MEKC), micelles are added to the buffer which interact with the analytes. MEKC can also be used for the separation of neutral compounds. In non-aqueous CE (NACE), the aqueous buffer is replaced by a background of electrolytes in organic solvents. A sample that needs to be screened can easily be analyzed subsequently by these CE modes using the same instrumentation.The aim of the study was to develop procedures for the analysis of basic and acidic drugs in serum and urine using CZE, MEKC, and NACE. A test mixture that consisted of six basic and six acidic compounds was used to study the separation behavior of five CE methods. The results showed that three methods (based on CZE, MEKC, and NACE) were suitable for the analysis of basic compounds and three methods (based on CZE and MEKC) for the analysis of acidic compounds.For the extraction of analytes from serum and urine, a solid-phase extraction (SPE) and a liquid-liquid extraction (LLE) method were compared. Both SPE and LLE methods provided clean extracts after extraction of the basic compounds from serum and urine. The extracts of acidic compounds contained more matrix interferences, especially for urine. The SPE method had some advantages compared to LLE, as it lead to cleaner extracts and higher peaks, and as it elutes basic and acidic compounds in one fraction.The potentials and pitfalls of the various methods for screening purposes in analytical toxicology are discussed.  相似文献   

4.
1-Aryl-piperazine compounds are, depending on their substituents, selective for certain serotonin receptors and together with their easy availability and their so-called legal status, this group of psychoactive compounds are potential designer drugs-of-abuse. Internet in that respect is an important source of information and distribution facilities. Because this development may have consequences for the interpretation of future clinical and forensic toxicological case studies, some analytical aspects of 1-benzyl-piperazine (BZP), 1-[4-methoxyphenyl]-piperazine (pMeOPP) and 1-[3-trifluoromethylphenyl]-piperazine (TFMPP) were studied. BZP was not detected by the AxSYM FPIA technology designed to determine amphetamine-like compounds, but had showed some cross reactivity with EMIT d.a.u.. The cross reactivities at 300 and 12,000ng/ml (RS)-amphetamine equivalents were 0.4 and 1.3%, respectively. Although BZP was not identified directly by the REMEDi HS Drug Profiling System, it can be detected by this HPLC/UV scanning system. Using GC/NPD without derivatisation, BZP, pMeOPP and TFMPP can be analysed for and applying GC/MS without or with acetylation or trifluoroacetylation, these compounds can be identified unambiguously. The usefulness of GC/NPD and GC/MS in this respect was demonstrated by the quantitative and qualitative analysis of the content of a capsule with the synthetic stimulant A2, which proved to contain 86.4mg of BZP.  相似文献   

5.
Due to their high polarity and low vapor pressure, most amine salts of amphetamine-type drugs are not directly amenable to headspace recovery using solid-phase microextraction (SPME). Described in this article is a simple vapor-phase procedure for the conversion of solid drug salt samples into their free bases by the use of triethylamine. This process can be conducted simultaneously with headspace SPME, the outcome being that solid drug salts can be sampled directly for GC-MS without the need for dissolution and chemical processing. Potential applications for this methodology include the noninvasive recovery of drug traces from objects such as banknotes and garments. This new process for recovery of amphetamine-type drugs has been combined with on-fiber derivatization using alkylchloroformates. This extra step was included to improve the chromatographic performance of analytes and allow for the resolution of drug enantiomers.  相似文献   

6.
A number of N‐substituted piperazines have been described as drugs of abuse in recent years. This new drug category includes several series of aromatic ring substituted phenylpiperazines. The wide variety of available precursors makes regioisomerism a significant issue in these totally synthetic compounds. In this study, a complete series of regioisomeric dimethoxyphenylpiperazines were synthesized and evaluated using GC‐MS and FT‐IR. The EI mass spectra show fragments characteristic of both the dimethoxyphenyl and the piperazine portions of the molecules including the dimethoxyphenylaziridinium cation (m/z 180) and dimethoxyphenyl cation (m/z 137). The ion at m/z 56 for the C3H6N+ fragment is characteristic of the piperazine ring and was observed in all the spectra. The perfluoroacyl derivatives were resolved by GC, and their mass spectra showed some differences in relative abundance of ions. FTIR provides direct confirmatory data for differentiation between the regioisomeric dimethoxyphenylpiperazines, and GC separation was accomplished on an Rtx‐200 phase.  相似文献   

7.
The applicability of capillary electrophoresis (CE) with a UV detector using highly sulfated gamma-cyclodextrin as a chiral selector was examined for analysis of impurities in seized methamphetamine. Samples of methamphetamine-hydrochloride dissolved in water at a high concentration (20 mg/mL) were analyzed. Electrokinetic injection has an advantage over hydrodynamic injection for improving the detection of trace impurities. Small peaks of the precursor impurities, such as (1R,2S)-(-)-ephedrine and (1S,2S)-(+)-pseudoephedrine, were detected and quantified without extraction. The seized drugs could be classified into three groups based on the contents of the two impurities.  相似文献   

8.
A capillary electrophoretic (CE) procedure using an electrolyte modified with hydroxypropyl-β-cyclodextrin has been used for the separation and quantitation of (S)- and (R)-methylamphetamine in fifteen laboratory prepared samples and ten `street' samples. Excellent separation of (S)- and (R)-methylamphetamine was achieved and the levels of methylamphetamine in the samples were in good agreement with the levels determined by a separate CE procedure previously developed in our laboratory. Both CE systems showed the presence of impurities in some of the samples suggesting that CE could be used in profiling illicit methylamphetamine seizures. Gas chromatography-mass spectrometry (GC-MS) analysis of two of the samples identified one of the impurities as N-formyl methylamphetamine, however, no conclusive proof for the presence of this compound in the electropherograms was available. The chloride and sulphate content of the ten `street' samples was also determined by CE.  相似文献   

9.
A method for simultaneous enantiomeric separation of ephedrine, pseudoephedrine, and methamphetamine (MA) in a single run by simple capillary zone electrophoresis (CZE) with beta-cyclodextrin as a chiral selector is described. The effects of the buffer pH, phosphate concentration, beta-cyclodextrin concentration, voltage and temperature on the peak resolution were examined. Good enantiomeric resolution was attained for each analyte under our optimized conditions: 15 mM beta-cyclodextrin, 300 mM NaH2PO4 at pH 2.5 with an uncoated capillary (64.5 cm x 50 microm), applied potential at 20 kV and temperature at 30 degrees C. Ultraviolet (UV) detection at a fixed wavelength (200 nm) was employed using a diode array detector. Using phentermine as an internal standard, migration times for all analytes are reproducible within 0.16% for intra-day and 0.6% for inter-day runs. Application of this method to the analysis of confiscated drugs is discussed.  相似文献   

10.
A novel method based on microemulsion electrokinetic chromatography (MEEKC) with diode array detection (DAD) for rapid determination of caffeine in commercial and clandestine stimulants, known as "energy drinks" and "smart drugs", is described. Separations were carried out in 50 cm × 50 μm (ID) uncoated fused silica capillaries. The optimized buffer electrolyte was composed of 8.85 mM sodium tetraborate pH 9.5, SDS 3.3% (w/v), n-hexane 1.5% (v/v) and 1-butanol 6.6% (v/v). Separations were performed at a voltage of 20 kV. Sample injection conditions were 0.5 psi, 3 s. Diprofilline was used as internal standard. The determination of the analytes was based on the UV signal recorded at 275 nm, corresponding to the maximum wavelength of absorbance of caffeine, whereas peak identification and purity check was performed on the basis of the acquisition of UV radiation between 200 and 400 nm wavelengths. Under the described conditions, the separation of the compounds was achieved in 6 min without any interference from the matrix. Linearity was assessed within a caffeine concentration range from 5 to 100 μg/mL. The intra-day and inter-day precision values were below 0.37% for migration times and below 9.86% for peak areas. The present MEEKC method was successfully applied to the direct determination of caffeine in smart drugs and energy drinks.  相似文献   

11.
During a forensic toxicological GC/MS screening, changed compounds of hydroxyzine were found in a man's urine taken about 20 h after ingesting sake (Japanese liquor) and tranquilizers. The structures of those compounds were assigned to 4-chlorodiphenylmethane(I), p-chlorbenzophenone(III), norchlorcyclizine(IV), 7-(p-chloro-alpha-phenylbenzyl)-2-hydroxy-2H,3H-oxazolo-[3,2 -alpha] piperazine(V), 1-(p-chloro-alpha-phenylbenzyl)-4-methylpiperazine-3-one(VI), N-(p-chloro-alpha-phenylbenzyl)-N'-formylmethyl-N'- hydroxyethyl-1,2-ethenediamine(VII) and 1-(p-chloro-alpha-phenylbenzyl)-4-[2-ethoxy(2-ethoxy)-ethyl] piperazine(VIII) on the basis of the fragmentation patterns and relative retention times except VIII which was identified using the synthesized compound. I, V, VI, VII and VIII have not been reported previously, but the possibility of metabolites of hydroxyzine is still uncertain.  相似文献   

12.
A method for the identification of 3,4‐methylenedioxymethamphetamine (MDMA) and meta‐chlorophenylpiperazine (mCPP) was developed employing capillary electrophoresis (CE) with capacitively coupled contactless conductivity detection (C4D). Sample extraction, separation, and detection of “Ecstasy” tablets were performed in <10 min without sample derivatization. The separation electrolyte was 20 mm TAPS/Lithium, pH 8.7. Average minimal detectable amounts for MDMA and mCPP were 0.04 mg/tablet, several orders of magnitude lower than the minimum amount encountered in a tablet. Seven different Ecstasy tablets seized in Rio de Janeiro, Brazil, were analyzed by CE‐C4D and compared against routine gas chromatography‐mass spectrometry (GC‐MS). The CE method demonstrated sufficient selectivity to discriminate the two target drugs, MDMA and mCPP, from the other drugs present in seizures, namely amphepramone, fenproporex, caffeine, lidocaine, and cocaine. Separation was performed in <90 sec. The advantages of using C4D instead of traditional CE‐UV methods for in‐field analysis are also discussed.  相似文献   

13.
The requirement to differentiate between incorporation and external contamination of drugs into hair is undisputed, in particular when dealing with compounds which are administered by sniffing or inhalation (e.g. cocaine). With the aim of making this discrimination, hair samples from cocaine (COC) users (group IN) and seized cocaine samples (group OUT) were compared regarding the parameters benzoylecgonine (BZE), ecgonine methyl ester (EME), ecgonine (ECG), anhydroecgonine methyl ester (AEME), cocaethylene (CE) and norcocaine (NCOC). Since most of these compounds may be minor by-products of COC or be formed by biotransformation or chemical degradation, the stability of each substance was carefully examined. COC was found to be converted into significant amounts of BZE, EME and ECG even under mild extraction conditions, while traces of NCOC proved to be a ubiquitous by-product of COC. Cocaine positive hairs and seized cocaine samples (diluted to relevant concentrations) were equally preprocessed and analyzed by LC-MS-MS. Out of the metabolites listed above, NCOC, CE and AEME (each normalised to COC) were significantly increased in the incorporation group (i.e. hair samples from cocaine users). Based on this approach, a statistical discriminant analysis enabled us to make a prediction (and estimation of uncertainty) for each cocaine positive hair sample as to its likelihood of belonging to the group of cocaine users or of being contaminated.  相似文献   

14.
A micellar electrokinetic chromatography (MEKC) method was optimised for simultaneous analysis of gamma-hydroxybutyric acid (GHB), gamma-butyrolactone (GBL), and 1,4-butanediol (BD). Best conditions for separation and baseline stability were achieved using a carrier electrolyte comprising 30.0mM sodium barbital and 150.0mM sodium dodecyl sulphate (SDS) at pH 10.2. Calibration functions were linear, giving correlation coefficients (r(2)) >0.998 for the three target compounds. Limits of detection (LOD) defined as three times the noise, were 5.1mg/l, 0.34 and 0.25g/l for GHB, GBL and BD, respectively. The repeatability of migration times and peak areas, expressed as the R.S.D. (n = 9) was better than 0.41 and 3.05%, respectively. Some casework samples were analysed using the optimised conditions.  相似文献   

15.
With the use of capillary electrophoresis (CE), high-resolution electrophoretic separation of short tandem repeat (STR) loci can be achieved in a semiautomated fashion. Laser-induced detection of fluorescently labeled PCR products and multicolor analysis enable the rapid generation of multilocus DNA profiles. In this study, conditions for typing PCR-amplified STR loci by capillary electrophoresis were investigated using the ABI Prism 310 Genetic Analyzer (Applied Biosystems). An internal size standard was used with each run to effectively normalize mobility differences among injections. Alleles were designated by comparison to allelic ladders that were run with each sample set. Multiple runs of allelic ladders and of amplified samples demonstrate that allele sizes were reproducible, with standard deviations typically less than 0.12 bases for fragments up to 317 bases in length (largest allele analyzed) separated in a 47 cm capillary. Therefore, 99.7% of all alleles that are the same length should fall within the measurement error window of +/- 0.36 bases. Microvariants of the tetranucleotide repeats were also accurately typed by the analytical software. Alleles differing in size by one base could be resolved in two-donor DNA mixtures in which the minor component comprised > or = 5% of the total DNA. Furthermore, the quantitative data format (i.e., peak amplitude) can in some instances assist in determining individual STR profiles in mixed samples. DNA samples from previously typed cases (typed for RFLP, AmpliType PM+DQA1, and/or D1S80) were amplified using AmpFlSTR Profiler Plus and COfiler and were evaluated using the ABI Prism 310. Most samples yielded typable results. Compared with previously determined results for other loci, there were no discrepancies as to the inclusion or exclusion of suspects or victims. CE thus provides efficient separation, resolution, sensitivity and precision, and the analytical software provides reliable genotyping of STR loci. The analytical conditions described are suitable for typing samples such as reference and evidentiary samples from forensic casework.  相似文献   

16.
Drugged drivers pose a serious threat to other people in traffic as well as to themselves. Reliable oral fluid screening devices for on-site screening of drugged drivers would be both a useful and convenient means for traffic control. In this study we evaluated the appropriateness of Drugwipe 5 and Drugwipe Benzodiazepines oral fluid on-site tests for roadside drug screening. Drivers suspected of driving under the influence of drugs were screened with the Drugwipe tests. Oral fluid and whole blood samples were collected from the drivers and tested for amphetamine-type stimulant drugs, cannabis, opiates, cocaine and benzodiazepines by immunological methods, GC and GC-MS. The performance evaluations of the tests were made by comparing the results of the Drugwipe tests with laboratory GC-MS confirmation results of oral fluid or whole blood. In addition to the performance evaluations of the Drugwipe tests based on laboratory results, a questionnaire on the practical aspects of the tests was written for the police officers who performed the tests. The aim of the questionnaire was to obtain user comments on the practicality of the tests as well as the advantages and weak points of the tests. The results of the performance evaluations were: for oral fluid (sensitivity; specificity; accuracy) amphetamines (95.5%; 92.9%; 95.3%), cannabis (52.2%; 91.2%; 85.1%), cocaine (50.0%; 99.3%; 98.6%), opiates (100%; 95.8%; 95.9%), benzodiazepines (74.4%; 84.2%; 79.2%) and for whole blood accordingly, amphetamines (97.7%; 86.7%; 95.9%), cannabis (68.3%; 87.9%; 84.9%), cocaine (50.0%; 98.5%; 97.7%), opiates (87.5%; 96.9%; 96.6%) and benzodiazepines (66.7%; 87.0%; 74.4%). Although the Drugwipe 5 successfully detected amphetamine-type stimulant drugs and the police officers were quite pleased with the current features of the Drugwipe tests, improvements must still be made regarding the detection of cannabis and benzodiazepines.  相似文献   

17.
Atomoxetine (ATX) is a potent inhibitor of the noradrenaline reuptake transporter approved since 2002 for the treatment of attention-deficit/hyperactivity disorder (ADHD) in children, adolescents, and adults as alternative treatment to methylphenidate. A procedure based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been developed for the determination of ATX and its main metabolites (4-hydroxyatomoxetine - 4 hydroxyATX - and N-desmethylatomoxetine - des-methylATX) in hair of one treated child and five treated adolescents. Since hair samples can be easily collected without the need for specials skills and exposing a patient to discomfort, hair testing of ATX and eventually of its metabolites should be useful, especially in case of pediatric patients, to check compliance in a wider time-window. After addition of duloxetine as internal standard, hair samples were overnight digested with 2ml 1M NaOH at 45°C. Then, analytes were extracted from alkaline solution with two different 2ml aliquots of tert-butyl methyl ether. Chromatographic separation was achieved at ambient temperature using a reverse-phase column and a mobile phase of 40% of water-60% 5mM ammonium acetate, 50mM formic acid, 4mM trifluoroacetic acid in acetonitrile-water (85:15, v/v). The mass spectrometer was operated in positive ion mode using multiple reaction monitoring. The method was linear over the concentration range 0.2-50ng/mg hair for the all analytes under investigation, with an intra- and inter-assay imprecision and inaccuracy always less than 20% and an analytical recovery between 33.1% and 76.1%, depending on the considered analyte. Only ATX and 4-hydroxyATX were detected in hair samples with concentrations varying from 0.2 to 2.0ng/mg hair and from 0.3 to 1.0ng/mg, respectively. Notwithstanding the absence of any dose-hair concentration relationship, hair monitoring of ATX and concomitant medications commonly administrated in ADHD children and adolescents can be crucial in verifying long-term compliance to prescribed medication in individuals displaying a non negligible tendency to refuse drugs and to lie on the adherence to therapy as a specific symptom of the disease.  相似文献   

18.
Abstract: An LC–MS method was developed for benzylpiperazine (BZP) and trifluoromethylphenylpiperazine (TFMPP), constituents of “party pills” or “legal herbal highs,” and their metabolites in human blood plasma. Compounds were resolved using a mixture of ammonium formate (pH 4.5, 0.01 M) and acetonitrile (flow rate of 1.0 mL/min) with a C18 column. Calibration curves were linear from 1 to 50 ng/mL (R2 > 0.99); the lower limit of quantification (LLOQ) was 5 ng/mL; the accuracy was >90%; the intra‐ and interday relative standard deviations (R.S.D) were <5% and <10%, respectively. Human plasma concentrations of TFMPP were measured in blood samples taken from healthy adults (n = 6) over 24 h following a 60‐mg oral dose of TFMPP: these peaked at 24.10 ng/mL (±1.8 ng/mL) (Cmax) after 90 min (Tmax). Plasma concentrations of 1‐(3‐trifluoromethyl‐4‐hydroxyphenyl) piperazine peaked at 20.2 ng/mL (±4.6 ng/mL) after 90 min. TFMPP had two disposition phases (t½ = 2.04 h (±0.19 h) and 5.95 h (±1.63 h). Apparent clearance (Cl/F) was 384 L/h (±45 L/h).  相似文献   

19.
Capillary electrophoresis, the modern approach to instrumental electrophoresis, is probably the most rapidly expanding analytical technique that has appeared in recent years. In the hands of forensic toxicologists, capillary electrophoresis (CE) represents a powerful new analytical tool, which has proved suitable for the investigation of illicit drugs in seized preparations and also in complex biological matrices, among which is hair. CE can be applied according to different separation mechanisms, and among those that are toxicologically relevant are capillary zone electrophoresis and micellar electrokinetic capillary chromatography, which display different selectivities. For the investigation of hair for drugs of abuse, capillary electrophoresis proved effective, providing simultaneous determinations of different drugs without derivatization, with acceptable sensitivity (typically better than 1 ng of drug per mg of hair). The possibility of carrying out determinations of the same analytes, based on different separation mechanisms (capillary zone electrophoresis and micellar electrokinetic chromatography) with the same instrumentation, simply changing the buffer composition, provides an interesting possibility of ‘internal’ confirmation of the results.  相似文献   

20.
目的利用GC/MS、GC/NPD与固相萃取(SPE)技术相结合,建立血液中苯丙胺类毒品的定性定量分析方法。方法采用Bond—ElutCerti{y固相柱、甲醇淋洗、二氯甲烷/异丙醇/氨水(78/20/2)洗脱固相萃取分离提取,比较了不同PH体系、稀释状态、洗脱溶剂对提取回收率的影响,建立血液中苯丙胺类毒品的GC/MS、GC/NPD定性定量分析方法。结果以GC/NPD分析AM、MA、MDA和MDMA浓度在15ng/mL-2000ng/mL、10ng/mL~1600ng/mL、20ng/mL-3000ng/ml、20ng/mL-3000ng/mL范围内线性关系良好,AM、MA、MDA和MDMA的检测限分别为10ng/mL、8ng/mL、15ng/mL、15ng/mL,方法平均回收率大于85%,标准偏差小于5%,GC/MS-Scan检测限分别为40ng/mL、32.0ng/mL、60.0ng/mL、60.0ng/mL。结论此方法可满足苯丙胺类毒品滥用者的血液定性定量分析。  相似文献   

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