Methamphetamine In Human Urine Research Articles

Spectrophotometric method development and validation for methamphetamine in human urine

Spectrophotometric method development and validation for methamphetamine in human urine

Combination of quadrupole isotope dilution mass spectrometry with simultaneous derivatization and spray assisted droplet formation-liquid phase microextraction for the determination of methamphetamine in human urine and serum samples by gas chromatography mass spectrometry

In this study, an analytical method with high accuracy and precision was developed for the determination of methamphetamine in human urine and serum samples by gas chromatography–mass spectrometry (GC–MS). A simultaneous derivatization and spray assisted droplet formation-liquid phase microextraction (SADF-LPME) method was proposed to derivatize and preconcentrate target analyte. Quadruple isotope dilution (ID4) was used to provide high accuracy and precision for methamphetamine determination in the samples. After the optimization studies for the derivatization and microextraction parameters, limit of detection (LOD) and limit of quantitation (LOQ) for the developed SADF-LPME method were found to be 48.0 and 159.9 μg/kg, respectively. Recovery studies were implemented to verify the applicability and accuracy of the developed method for human urine and serum samples. The SADF-LPME method gave low percent recovery results (30.5–61.0%) for the spiked urine and serum samples showing that it failed to minimize or eliminate matrix effects for the analyte. Hence, methamphetamine acetamide-d3 was synthesized and purified in our research laboratory to be used as methamphetamine isotopic analogue in the ID4 method. When the SADF-LPME method was combined with ID4, the percent recovery values for urine and serum samples were calculated as 99.7–100.0% and 99.4–100.2%, respectively. These results demonstrated the applicability and accuracy of the proposed method for urine and serum samples.

Two-side slug-flow microextraction coupled with ion mobility spectrometry for fast quantification of amphetamine and methamphetamine in human urine

In this study, first time a novel slug-flow microextraction (SFME) procedure named two-side SFME was developed and followed by ion mobility spectrometry equipped with corona discharge source (CD-IMS) for quantification of two abused drugs (amphetamine (AM) and methamphetamine (ME)) in urine samples. Regarding technique workflow, the organic extraction solvent (10 μL) was sandwiched between two portions of aqueous sample solution (the volume of each portion of sample solution was 5 μL) into a disposable glass capillary tube. The extraction of analytes was performed via the slug flows induced by the movements of the three liquids, which was conducted by tilting the glass capillary tube for several cycles. Finally, the extraction solvent was collected by a microsyringe and then injected (5 μL) into the CD-IMS. The effects of the effective parameters, including type of extraction solvent, number of tilting the glass capillary tube, and concentration of salt in sample solution were investigated. Under the optimized extraction condition (organic solvent: toluene; number of tilting the glass capillary tube: 10 times; concentration of salt: 5% (w/v)), the proposed two-side SFME/CD-IMS provided good linearity with coefficients of determination ≥0.993 over a concentration range of 25.0–2000.0 ng mL−1. Accordingly, acceptable limits of detection (S/N = 3) were 10.0 and 2.5 ng m‌‌L−1 for AM and ME, respectively. Furthermore, acceptable recoveries were ≥ 81.5, and ≥ 88.0% for AM and ME in a human urine sample, respectively, while repeatability and reproducibility ranged from 6.7 to 14.7% (n = 3).

Fabrication of Au Nanorods by the Oblique Angle Deposition Process for Trace Detection of Methamphetamine with Surface-Enhanced Raman Scattering.

Oblique angle deposition (OAD) is a simple, low cost, effective, and maskless nanofabrication process. It can offer a reliable method for the mass fabrication of uniform metal nanorods which can be used as the surface-enhanced Raman scattering (SERS) substrate with an excellent enhancing performance. Up to now, Ag nanorods SERS substrates have been extensively studied. However, Ag is chemically active and easy to oxidize under atmospheric conditions. Comparatively, Au is chemically stable and has better biocompatibility than Ag. In this paper, we in detail, studied the electromechanical (EM) field distribution simulation, fabrication, and application of Au nanorods (AuNRs) on trace detection of methamphetamine. According to the finite-difference time-domain (FDTD) calculation results, the maximum EM intensity can be obtained with the length of AuNRs to be 800 nm and the tilting angle of AuNRs to be 71° respectively. The aligned Au nanorod array substrate was fabricated by the OAD process. The two key process parameters, deposition angle, and deposition rate were optimized by experiments, which were 86° and 2 Å/s, respectively. Using 1,2-bis (4-pyridyl) ethylene (BPE) as the probe molecule, the limit of detection (LOD) was characterized to be 10−11 M. The AuNRs were also used to detect methamphetamine. The LOD can be down to M (i.e., 14.92 pg/ml), which meet the requirements of the on-site rapid detection of the methamphetamine in human urine (500 ng/ml).

Ultra-trace detection of methamphetamine in biological samples using FFT-square wave voltammetry and nano-sized imprinted polymer/MWCNTs -modified electrode

An efficient voltammetric method for trace level monitoring of methamphetamine (MTM) stimulant drug in the human urine and serum samples is established. This method is based on fast fourier transform square wave voltammetric (FFT-SWV) determination of MTM at a molecularly imprinted polymer (MIP)/multi-walled carbon nanotube (MWCNTs)-modified carbon paste electrode. Voltammetric techniques development for electrochemical assay of MTM is a challenge, due to the weak electroactivity of this drug. Herein, MTM-imprinted nanopolymer was synthesized, using a simple precipitation polymerization method. The resulting polymer, along with MWCNT was then used to fabricate the modified carbon paste electrode which showed a well-defined anodic peak for MTM at about +1.0 V(vs. Ag/AgCl); whereas, the related blank electrode exhibited considerably lower signal at the same conditions. Utilizing the highly efficient MIP, MWCNTs (which increased the charge transfer phenomenon at the electrode surface) and the advanced electrochemical technique of FFT-SWV (which increased the created signal intensity) caused this method to be a high sensitive and selective approach for MTM measurement. In the optimum experimental conditions, the proposed sensor, exhibited linear response range of 1.0 × 10−8 −1.0 × 10−4 mol L−1 and the detection limit of 8.3 × 10−10 mol L−1 with acceptable relative standard deviations (RSD%) for real samples (1.0–3.5%). Herein, the first MIP-based voltammetric sensor for MTM which also exhibits the lowest detection limit, ever reported, is introduced. This approach seems to provide an effective way for rapid screening of MTM in human urine and serum samples.

Rapid and accurate quantification of amphetamine and methamphetamine in human urine by antibody decorated magnetite nanoparticles coupled with matrix-assisted laser desorption ionization time-of-flight mass spectrometer analysis

In this study, a novel method for the simultaneous determination and accurate quantification of abused drugs in human urine was developed. Antibody conjugated boronic acid modified magnetite nanoparticles (Fe3O4, MNPs) were prepared for the selectively purification of illicit drugs in combination with high resolution matrix-assisted laser desorption ionization time-of-flight mass spectrometer (MALDI-TOF MS) analysis. Illicit drugs, amphetamine (AM) and methamphetamine (MA), were used as model analytes to demonstrate the feasibility of our strategy. Boronic acid functionalized MNPs were first prepared via one-pot synthesis to simplify and improve the efficiency of a chemical reaction. Anti-amphetamine antibody (anti-AM antibody) and anti-methamphetamine antibody (anti-MA antibody) was conjugated onto boronic acid modified MNPs, respectively, through the formation of boronate ester bond that could maintain the correct orientation to maximally capture their antigens. The capacity of antibody conjugation to boronic acid modified MNPs was at least 24 μg antibody/mg MNPs. Antibody-conjugated MNPs were designed to specifically capture AM and MA in human urine samples, both of which can be directly eluted to MALDI target plate by adding MALDI CHCA matrix solution for the following MALDI-MS analysis. The linear range of detection of the proposed method were 25–400 ng/mL and 25–1000 ng/mL with coefficients of determination between 0.9923 and 0.9997 for AM and MA, respectively. The lowest detectable concentrations of AM and MA were 1.87 and 3.75 ng/mL, respectively. More importantly, the proposed method allows rapid and accurate quantification of AM and MA from three suspects' urine samples. The obtained results are consistent with traditional GC/MS analysis. Antibody-conjugated MNPs could thus prove to be powerful tools for important applications such as forensic science, food safety and clinical diagnosis of disease.

Bio-dispersive liquid liquid microextraction based on nano rhaminolipid aggregates combined with magnetic solid phase extraction using Fe3O4@PPy magnetic nanoparticles for the determination of methamphetamine in human urine.

In the present investigation, extraction and preconcentration of methamphetamine in human urine samples was carried out using a novel bio-dispersive liquid liquid microextraction (Bio-DLLME) technique coupled with magnetic solid phase extraction (MSPE). Bio-DLLME is a kind of microextraction technique based nano-materials which have potential capabilities in many application fields. Bio-DLLME is based on the use of a binary part system consisting of methanol and nano rhaminolipid biosurfactant. Use of this binary mixture is ecologically accepted due to their specificity, biocompatibility and biodegradable nature. The potential of nano rhaminolipid biosurfactant as a biological agent in the extraction of organic compounds has been investigated in recent years. They are able to partition at the oil/water interfaces and reduce the interfacial tension in order to increase solubility of hydrocarbons. The properties of the prepared Fe3O4@PPy magnetic nanoparticles were characterized using Fourier transform infrared spectroscopy and X-ray diffraction methods The influences of the experimental parameters on the quantitative recovery of analyte were investigated. Under optimized conditions, the enrichment factor was 310, the calibration graph was linear in the methamphetamine concentration range from 1 to 60μgL-1, with a correlation coefficient of 0.9998. The relative standard deviations for six replicate measurements was 5.2%.

Dynamic surface-enhanced Raman spectroscopy and Chemometric methods for fast detection and intelligent identification of methamphetamine and 3, 4-Methylenedioxy methamphetamine in human urine

Conventional Surface-Enhanced Raman Spectroscopy (SERS) for fast detection of drugs in urine on the portable Raman spectrometer remains challenges because of low sensitivity and unreliable Raman signal, and spectra process with manual intervention. Here, we develop a novel detection method of drugs in urine using chemometric methods and dynamic SERS (D-SERS) with mPEG-SH coated gold nanorods (GNRs). D-SERS combined with the uniform GNRs can obtain giant enhancement, and the signal is also of high reproducibility. On the basis of the above advantages, we obtained the spectra of urine, urine with methamphetamine (MAMP), urine with 3, 4-Methylenedioxy Methamphetamine (MDMA) using D-SERS. Simultaneously, some chemometric methods were introduced for the intelligent and automatic analysis of spectra. Firstly, the spectra at the critical state were selected through using K-means. Then, the spectra were proposed by random forest (RF) with feature selection and principal component analysis (PCA) to develop the recognition model. And the identification accuracy of model were 100%, 98.7% and 96.7%, respectively. To validate the effect in practical issue further, the drug abusers'urine samples with 0.4, 3, 30ppm MAMP were detected using D-SERS and identified by the classification model. The high recognition accuracy of >92.0% can meet the demand of practical application. Additionally, the parameter optimization of RF classification model was simple. Compared with the general laboratory method, the detection process of urine's spectra using D-SERS only need 2 mins and 2μL samples volume, and the identification of spectra based on chemometric methods can be finish in seconds. It is verified that the proposed approach can provide the accurate, convenient and rapid detection of drugs in urine.

Ionic-liquid-based dispersive liquid-liquid microextraction coupled with high-performance liquid chromatography for the forensic determination of methamphetamine in human urine.

Determination of methamphetamine in forensic laboratories is a major issue due to its health and social harm. In this work, a simple, sensitive, and environmentally friendly method based on ionic liquid dispersive liquid-liquid microextraction combined with high-performance liquid chromatographywas established for the analysis of methamphetamine in human urine. 1-Octyl-3-methylimidazolium hexafluorophosphate with the help of disperser solvent methanol was selected as the microextraction solvent in this process. Various parameters affecting the extraction efficiency of methamphetamine were investigated systemically, including extraction solvent and its volume, disperser solvent and its volume, sample pH, extraction temperature, and centrifugal time. Under the optimized conditions, a good linearity was obtained in the concentration range of 10-1000 ng/mL with determination coefficient >0.99. The limit of detection calculated at a signal-to-noise ratio of 3 was 1.7 ng/mL and the relative standard deviations for six replicate experiments at three different concentration levels of 100, 500, and 1000 ng/mL were 6.4, 4.5, and 4.7%, respectively. Meanwhile, up to 220-fold enrichment factor of methamphetamine and acceptable extraction recovery (>80.0%) could be achieved. Furthermore, this method has been successfully employed for the sensitive detection of a urine sample from a suspected drug abuser.

Ionic liquid-based fluorescence sensing paper: rapid, ultrasensitive, and in-site detection of methamphetamine in human urine

A low cost sensing paper chip was developed to perform a rapid and ultrasensitive in-site methamphetamine test in human urine.

Application of a new nanocarbonaceous sorbent in electromembrane surrounded solid phase microextraction for analysis of amphetamine and methamphetamine in human urine and whole blood

Application of a new carbon-based sorbent was studied for the first time for extraction and quantification of amphetamine and methamphetamine as model analytes by means of electromembrane surrounded solid phase microextraction (EM-SPME). Since the basis of this microextraction method is adsorption of target analytes on the sorbent surface (after transferring across a supported liquid membrane) in an electrical field, the sorbent, which also performs the electrical potential, should have a conductive nature. On the other hand, using a synthesized fiber is a suitable solution to eliminate the interfering compounds existing in the fiber. To extract the model analytes from acidic sample solution through a thin layer of organic phase and into the aqueous acceptor phase and their final adsorption, 150V electrical potential was applied for 15min. Regardless of the high sample cleanup ability of the proposed method, which makes the analysis of complicated biological fluids possible, admissible extraction recoveries (9.0–18.8%) and suitable detection limits (less than 2.0ngmL−1) were obtained. Repeatability and reproducibility of the method were studied and intra- and inter-assay precisions were in the ranges of 2.0–7.3% and 7.5–12.5%, respectively. Coefficients of determination larger than 0.9964 were achieved by scrutinizing of the linearity up to 500ngmL−1 and calibration curves were utilized for quantification of analytes of interest in human urine and whole blood samples.

Analysis of Methamphetamine in Human Urine Using Ionic Liquid Dispersive Liquid-Phase Microextraction Combined with HPLC

A specific and sensitive method using ionic liquid dispersive liquid-phase microextraction coupled with high-performance liquid chromatography was developed and applied in the analysis of methamphetamine in human urine. In this experiment, 1-butyl-3-methylimidazolium bis (trifluoromethyl) imide ([BMIM]TF2N) was selected as the extraction solvent and parameters affecting the extraction efficiency such as the volume of ionic liquid, percentage of dispersant, dissolving temperature, extraction time, sample pH, centrifuging time and salting-out effect have been investigated in detail. Under optimized conditions, good linear relationship of methamphetamine was obtained in the range 0.04–20.00 μg mL−1, the correlation coefficient (r) was 0.9987, the limit of detection and limit of quantitation were 0.01 and 0.04 μg mL−1, respectively, and the enrichment factor was 44. The results showed that the method was simple, time-saving, special, clean, sensitive and it could be applied in the analgesics analysis of forensic trace evidences and addicted cases.

Erratum to: Colorimetric and bare eye determination of urinary methylamphetamine based on the use of aptamers and the salt-induced aggregation of unmodified gold nanoparticles

Methamphetamine (METH) is second only to marijuana as a widely used illicit drug. We are presenting a simple colorimetric assay for sensitive and visual detection of METH in human urine using a METH-specific aptamer as the recognition element and unmodified gold nanoparticles as indicators. The method is based on the finding that the presence of METH results in AuNPs solution’s color change from red to blue. Normally, aptamers attach to the surface of AuNPs and thereby increasing their resistance to NaCl-induced aggregation. If, however, the aptamer bind to METH via G-quartets, rapid salt induced aggregation occurs associated with the formation of a blue colored solution. Urinary METH can be quantified via this effect either visually or by measurement of the absorbance ratios at 660 and 525 nm, respectively. It works in the 2 μM to 10 μM concentration range with a detection limit at 0.82 μM. The method is fast and also works well in human urine. It is believed to represent a widely applicable aptamer-based detection scheme.

Novel fiber coated with β-cyclodextrin derivatives used for headspace solid-phase microextraction of ephedrine and methamphetamine in human urine

Heptakis (2,6-di- O-methyl)-β-cyclodextrin (DM-β-CD) blending with hydroxy-terminated silicone oil (OH-TSO) coated solid-phase microextraction (SPME) fiber (DM-β-CD/OH-TSO) was first prepared with sol–gel technology and applied to headspace SPME for analysis of ephedrine (EP) and methamphetamine (MA) in human urine by gas chromatography (GC). By exploiting the advantages of the unique cavity-shaped cyclic molecular structure of CD and the superiorities of sol–gel coating technique, the novel fiber showed desirable extraction ability and operational stability. Influence of relevant experimental parameters (extraction time, extraction temperature, basicity, ionic strength, etc.) was systematically investigated. In the optimal conditions the proposed headspace SPME–GC method provided good linearity over four orders of magnitude with limit of detection (LOD) of ng/ml (0.33 ng/ml for EP, 0.60 ng/ml for MA). The recoveries of EP and MA in urine were 98.0% and 98.2%. And the relative standard deviations (R.S.D., n = 6) for EP and MA were 3.9% and 5.0%, respectively.

Determination of Methamphetamine in Human Urine by HPLC Using Post-Column Simon's Reaction

An HPLC method using post-column Simon's reaction (SR-HPLC) for the determination of methamphetamine (MA) has been developed. The detection limit was 1ng, which is about 100 times more sensitive than TLC using Simon's reaction (SR-TLC). The calibration curve was linear in the range of 0.1-1000μg/ml, and the intermediate precision of within-run and between-run assays was 1.15% and 2.12%, respectively. MA in 13 urine samples was determined by SR-HPLC and GC with flame ionization detection, and these quantitative values were strongly correlated (r2=0.995). MA could be analyzed without interference peaks. The proposed method is highly selective and quantitative.

Enantiomeric determination of amphetamine and methamphetamine in urine by precolumn derivatization with Marfey's reagent and HPLC.

An analytical method was developed for enantiomeric determination of amphetamine and methamphetamine in human urine. The enantiomers were isolated from urine by solid-phase extraction, and diastereomers were formed by derivatization with the chiral Marfey's reagent (1-fluoro-2,4-dinitrophenyl-5-l-aniline amide). The diastereomers were separated by reversed-phase high-performance liquid chromatography in a water/methanol mobile phase and detected by absorbance spectrophotometry at 340 nm. Linear standard curves were obtained for all four enantiomers over a concentration range of 0.16-1.00 mg/L in urine. The detection limit was 0.16 mg/L urine for each enantiomer, and the limit of quantitation was 0.40 mg/L. The urine of 10 decedents was analyzed by this method and by a previously published precolumn derivatization procedure using (-)-1-(9-fluorenyl)ethyl chloroformate (FLEC) as the derivatizing agent and fluorescence detection. Comparison of the results of the two methods by linear regression showed comparable results for both d-amphetamine and d-methamphetamine. Neither method detected the presence of the l-enantiomers in the urine samples.

Piezoelectric crystal immunosensor for sensitive detection of methamphetamine (stimulant drug) in human urine

We have developed an immunosensor based on a piezoelectric quartz resonator, which detects methamphetamine (MA) in liquids from a shift of the resonant frequency. The sensor has MA-albumin conjugates immobilized on the resonator and its resonant frequency shifts downward on contact with the monoclonal antibody to MA dissolved in the phosphate buffer solution. Under the condition of a fixed concentration of the antibody, the frequency shift is attenuated by mixing MA with the antibody solution. Based on this principle, it has been possible to detect 0.02–100 ppm MA with a detection time of about 7 min. The sensor has proved to be sensitive and stable enough to detect the critical concentration (1 ppm) of MA in human urine.

Determination of amphetamine-related compounds by high-performance liquid chromatography with chemiluminescence and fluorescence detections

High-performance liquid chromatography with chemiluminescence detection has been established for the determination of trace levels of amphetamine-related compounds (APs) after fluorigenic derivatization. Bis(2,4,6-trichlorophenyl) oxalate and hydrogen peroxide in acetonitrile was used as a post-column chemilumigenic reagent. As derivatization reagents, dansyl chloride (Dns-Cl), 4-fluoro-7-nitrobenzoxadiazole (NBD-F)_and naphtalene-2,3-dicarbaldehyde (NDA) were compared. Dns-Cl was the most suitable of the three for the simultaneous determination of both primary and secondary amino APs. The on-column detection limits for Dns-derivatives were 3 · 10 −15 − 4 · 10 −15 mol. NDA gave the most sensitive derivatives (cyanobenz[ f]isoindole, CBI derivatives) with only primary amino APs. The detection limits for CBI derivatives were as low as 2 · 10 −16 mol. The present method was applied to the determination of methamphetamine in human urine. Only diethyl ether extraction was necessary as a clean-up treatment before Dns derivatization, because diethyl ether extracted methamphetamine quantitatively from urine at strong alkaline pH and the extract showed few interfering peaks around the retention time of methamphetamine after the derivatization. Methamphetamine concentrations as low as 1 · 10 −7 M in urine were determined after the above treatments.

Extraction of trace methamphetamine in human urine.

Extraction of trace methamphetamine in human urine.

High performance liquid chromatographic determination of methamphetamine in human urine using polyvinylalcohlic column.

Methamphetamine in the human urine wasdirectly determined by high performance liquid chromatography (HPLC) by using a polyvinylalcohlic column and alkali mobile phase. The detailed conditions were as follows : column : Asahipak GS-320M 7.6 mm i.d.×100 mm, column temp. : 40°C, mobile phase : 80% {0.02 M NaHCO3+0.02 M Na2CO3 (8 : 2)} +20% CH3CN, flow rate : 1.0 ml/min, detector : UV photometer (207 nm). The urine was directly injected into HPLC. Methamphetamine was eluted by adsorption chromatography, and separated from endogenous urine constituents. Determination of methamphetamine was carried out successfully by using the calibration curve by peak high (1-10μg/ml). The recovery of methamphetamine added to the human urine (5μg/ml) was 92.0±1.0%.