Comparison of different approaches for direct coupling of solid-phase microextraction to mass spectrometry for drugs of abuse analysis in plasma

The direct coupling of solid-phase microextraction(SPME)to mass spectrometry(MS)(SPME-MS)has proven to be an effective method for the fast screening and quantitative analysis of compounds in complex matrices such as blood and plasma.In recent years,our lab has developed three novel SPME-MS techniques:SPME-microfluidic open interface-MS(SPME-MOI-MS),coated blade spray-MS(CBS-MS),and SPME-probe electrospray ionization-MS(SPME-PESI-MS).The fast and high-throughput nature of these SPME-MS technologies makes them attractive options for point-of-care analysis and anti-doping testing.However,all these three techniques utilize different SPME geometries and were tested with different MS instruments.Lack of comparative data makes it difficult to determine which of these methodologies is the best option for any given application.This work fills this gap by making a comprehensive comparison of these three technologies with different SPME devices including SPME fibers,CBS blades,and SPME-PESI probes and SPME-liquid chromatography-MS(SPME-LC-MS)for the analysis of drugs of abuse using the same MS instrument.Furthermore,for the first time,we developed different desorption chambers for MOI-MS for coupling with SPME fibers,CBS blades,and SPME-PESI probes,thus illustrating the universality of this approach.In total,eight analytical methods were developed,with the experimental data showing that all the SPME-based methods provided good analytical performance with R^(2)of linearities larger than 0.9925,accuracies between 81%and 118%,and good precision with an RSD%≤13%.

Fulminant Hepatitis Associated with Chronic Consumption of 3,4-Methylenedioxy-Methamphetamine;Case Report

The amphetamine derivative 3,4-methylenedioxymethamphetamine (MDMA), also called ecstasy, is a neurotoxin widely consumed among young people that has increased in recent years because it is a recreational drug, of which immediate effects are known such as a greater sensation of well-being, extroversion, increased sensory perception. However, its long-term effects have been described very little in the medical literature, including damage to the heart, central nervous system, kidney, etc. One of its little-known effects is hepatotoxicity, of which few cases are known associated with fulminant hepatitis, which is a rapidly deteriorating condition that is generally associated with a syndrome of multiple organ dysfunction and death. Therefore, it is very important to know this type of damage in the short and long term. The following case is of a 39-year-old man who came to our service due to jaundice syndrome and the only history of MDMA consumption, who as the days went by met the criteria for fulminant liver failure, with damage to multiple organs (organ dysfunction syndrome).

Studies on Different Hydrolysis Procedures for Drugs of Abuse in Hair

Different hydrolysis and extraction procedures have been studied for the determination of drugs of abuse in hair samples. The results showed that acid and enzymatic hydrolysis gave high extraction recoveries for 6-monoacetylmorphine, morphine, codeine and heroin. Enzymatic hydrolysis was more expensive. After alkaline hydrolysis, 6-monoacetylmorphine, a unique proof of heroin abuse, could not be detected and after methanolic extraction, the extract was dirty and the obtained chromatogram showed an interfering background. It is concluded that acid hydrolysis is the extraction method of choice.

Determination of multiple drugs of abuse in human urine using dispersive liquid–liquid microextraction and capillary electrophoresis with PDA detection

A new method was developed for pre-concentration and determination of multiple drugs of abuse in human urine using dispersive liquid–liquid microextraction(DLLME)and capillary electrophoresis(CE)with photodiode array 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 eight drugs of abuse from the prepared urine solution,was separated by centrifugation.The sedimented phase was transferred into a small volume CE auto-sampler vial with 10μL of 1%HCl methanol solution and evaporated to dryness.The residue was reconstituted in lidocaine hydrochloride(internal standard)aqueous solution and introduced by electrokinetic injection into CE.Under the optimum conditions,acceptable linear relationship was observed in the range of 3.0–500 ng/mL with the correlation coefficient(r)of 0.9982–0.9994 for spiked urine samples.The limit of detection(LOD)(S/N=3)was estimated to be 1.0 ng/mL.A recovery of 75.7%–90.6%was obtained for spiked samples.The mean relative error(MRE)was within±7.0%and the relative standard deviation(RSD)was less than 6.9%.The proposed DLLME-CE procedure offers an alternative analytical approach for the sensitive detection of drugs of abuse in real urine samples.

Modifying current thin-film microextraction(TFME)solutions for analyzing prohibited substances:Evaluating new coatings using liquid chromatography

For identifying and quantifying prohibited substances,solid-phase microextraction(SPME)continues to arouse interest as a sample preparation method.However,the practical implementation of this method in routine laboratory testing is currently hindered by the limited number of coatings compatible with the ubiquitous high-performance liquid chromatography(HPLC)systems.Only octadecyl(C18)and polydimethylsiloxane/divinylbenzene ligands are currently marketed for this purpose.To address this situation,the present study evaluated 12 HPLC-compatible coatings,including several chemistries not currently used in this application.The stationary phases of SPME devices in the geometry of thin filmcoated blades were prepared by applying silica particles bonded with various functional ligands(C18,octyl,phenyl-hexyl,3-cyanopropyl,benzenesulfonic acid,and selected combinations of these),as well as unbonded silica,to a metal support.Most of these chemistries have not been previously used as microextraction coatings.The 48 most commonly misused substances were selected to assess the extraction efficacy of each coating,and eight desorption solvent compositions were used to optimize the desorption conditions.All samples were analyzed using an HPLC system coupled with triple quadrupole tandem mass spectrometry.This evaluation enables selection of the best-performing coatings for quantifying prohibited substances and investigates the relationship between extraction efficacy and the physicochemical characteristics of the analytes.Ultimately,using the most suitable coatings is essential for trace-level analysis of chemically diverse prohibited substances.

Determination of amphetamines,ketamine and their metabolites in hair with high-speed grinding and solid-phase microextraction followed by LC-MS

A novel hair sample pre-treatment method based on high-speed grinding and solid-phase microextraction(SPME)had been applied for the determination of amphetamines,ketamine and their metabolites in hair samples by liquid chromatography mass spectrometry(LC-MS).A 20mg sample of hair was ground with 2 mL of saturated sodium carbonate solution using a high-efficiency hair grinder with 70 Hz osillation for 2min at 4℃.After centrifuging,1.5mL of the supernatant was transferred and treated with SPME by direct immersion(DI-SPME).The target analytes extracted by fibre were desorbed and analysed using LC-MS.Under the optimum conditions,a recovery of 90.2%-95.8%was obtained for all analytes.The analytical method was linear for all analytes in the range from 0.2 to 10 ng/mg with the correlation coefficient ranging from 0.9985 to 0.9993.The detection limits for all analytes were estimated to be 0.067 ng/mg.The accuracy(mean relative error)was within±6.9%and the precision(relative standard error)was less than 6.8%.The combination of high-speed grinding of hair and SPME had the advantages of being easy to perform,environment-friendly and high in detection sensitivity.The proposed method offered an altermative ana lytical approach for the sensitive detection of drugs in hair samples for forensic purposes.

Determination of Methadone and Eight New Psychoactive Substances in Hair Samples by Gas Chromatography/Mass Spectrometry

Many new psychoactive substances(NPSs)with different chemical structures have emerged in the illicit drug market in the last decade.The present work was aimed at the development of a simple method in gas chromatography/mass spectrometry(MS)for the determination of NPS of different classes,the use of cannabinoids,and,at the same time,the evaluation of methadone therapy in hair matrix,within our routine analysis control for methadone treatment or from autopsy cases.The determination of synthetic cannabinoids and methadone therapy used an extraction method based on incubation in concentrated sodium hydroxide(NaOH)solution,providing a dissolution of the keratin matrix.The described method was applied on 15 authentic specimens from our cases:five showed the presence of methadone and 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine(EDDP).The described method can be useful not only in the forensic investigation of NPS-related addiction histories but also in epidemiological and retrospective studies on the spread of NPS among specific safety-sensitive social workers.The GC instrument was an Agilent 7820A(Agilent Technologies,Santa Clara,CA,USA),and the detection system was an Agilent 5977B single quadrupole MS operating in selective ion monitoring mode.Wlidation parameters such as limit of detections(LODs),limit of quantifications(LOQs),repeatability,accuracy,and linearity were satisfactory for its application on real specimens.LODs,LOQs,2?2,%CY standard deviation,and the mean concentration for the analyzed compounds are reported in Table lb.Accuracy and repeatability were acceptable for all the analytes at their respective LOQs.Recovery experiments varied from 58.3%to 103.0%,thus allowing the application on authentic specimens.The described method can be useful not only in the forensic investigation ofNPS-related addiction histories but also in epidemiological and retrospective studies on the spread of NPS among specific safety-sensitive social workers,such as drivers.