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Mass Spectrometry Determination (mass + spectrometry_determination)
Selected AbstractsComparison of analytical approaches for liquid chromatography/mass spectrometry determination of the alcohol biomarker ethyl glucuronide in urineRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 12 2010Anders Helander Official guidelines originating from a European Union directive regulate requirements for analytical methods used to identify chemical compounds in biological matrices. This study compared different liquid chromatography/electropray ionization mass spectrometry (LC/ESI-MS) and tandem mass spectrometry (LC/ESI-MS/MS) procedures for accurate determination of the conjugated ethanol metabolite and alcohol biomarker ethyl glucuronide (EtG) in urine, and the value of combined EtG and ethyl sulfate (EtS) measurement. Analysis was carried out on 482 urines following solid-phase extraction (SPE) sample cleanup or using direct injection of a diluted sample. SPE combined with LC/MS/MS was demonstrated to be the most selective and sensitive method and was chosen as reference method. The EtG results by different methods showed good correlation (r,=,0.96,0.98). When comparing five reporting limits for EtG in the range 0.10,1.00,mg/L, the overall agreement with the reference method (frequency of true positives plus true negatives) was 82,97% for direct-injection LC/MS/MS, 90,97% for SPE-LC/MS, 86,98% for direct-injection LC/MS, and 86,98% for direct-injection LC/MS analysis of EtG and EtS. Most deviations were attributable to uncertainty in quantitation, when the value was close to a cutoff but the respective results were slightly above and below, or vice versa, the critical limit. However, for direct-injection LC/MS/MS, despite earning 4 identification points, equally many negative results were due to a product ion ratio outside the ±20% deviation accepted by the guidelines. These results indicate that the likelihood of different analytical methods to provide reliable analytical results depends on the reporting limit applied. Copyright © 2010 John Wiley & Sons, Ltd. [source] Determination of 13C/12C ratios of urinary excreted boldenone and its main metabolite 5,-androst-1-en-17,-ol-3-oneDRUG TESTING AND ANALYSIS, Issue 5 2010Thomas Piper Abstract Boldenone (androsta,1,4,dien,17,,ol,3,one, Bo) is an anabolic steroid known to have been used in cattle breeding or equine sport as a doping agent for many years. Although not clinically approved for human application, Bo or its main metabolite 5,-androst-1-en-17,-ol-3-one (BM1) were detected in several doping control samples. For more than 15 years the possibility of endogenous Bo production in human beings has been discussed. This is a challenging issue for doping control laboratories as Bo belongs to the list of prohibited substances of the World Anti-Doping Agency and therefore the chance for false positive testing is significant. By GC/C/IRMS (gas chromatography/combustion/isotope ratio mass spectrometry) it should be possible to analyze the 13C/12C ratio of either Bo or BM1 and to distinguish whether their source is endogenous or exogenous. Therefore a method was developed to determine the 13C/12C ratios of Bo, BM1, pregnanediol, androsterone, etiocholanolone, and testosterone from a single urine specimen. The validity of the method was ensured by repeated processing of urine fortified with 2,50 ng/mL Bo and BM1. The specificity of the method was ensured by gas chromatography/mass spectrometry determinations. Out of 23 samples investigated throughout the last four years, 11 showed 13C/12C ratios of Bo or BM1 inconsistent with an exogenous origin. Two of these samples were collected from the same athlete within a one-month interval, strongly indicating the chance of endogenous Bo production by this athlete. Copyright © 2010 John Wiley & Sons, Ltd. [source] Optimization of solid-phase microextraction methods for GC-MS determination of terpenes in wineJOURNAL OF THE SCIENCE OF FOOD AND AGRICULTURE, Issue 7 2005Rosa M Peña Abstract Solid-phase microextraction using a 100 µm poly(dimethylsiloxane) fiber, followed by gas chromatography,mass spectrometry determination, has been optimized for the analysis of some terpenes in wine samples. The best results were obtained by direct immersion of the fiber using a sampling period of 15 min with constant magnetic stirring (1100 rpm) and an extraction temperature of 20 °C. The sample volume was 7 ml with 25% NaCl, in a 15 ml capped vial. Desorption was performed directly in the gas chromatograph injector port over 5 min at 250 °C using the splitless mode. The method is sensitive, with detection limits between 11 and 25 µg l,1, precise, with variation coefficients in the range 1.28,3.71%, and linear over more than one order of magnitude. The related conditions were used for wine sample analyses with recoveries between 71.8 and 90.9%. Solid-phase microextraction remains an attractive alternative technique due to its rapidity and because it is a solvent-free extraction. Copyright © 2005 Society of Chemical Industry [source] Potentials of ion trap collisional spectrometry for liquid chromatography/electrospray ionization tandem mass spectrometry determination of buprenorphine and nor -buprenorphine in urine, blood and hair samplesRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 8 2006Donata Favretto A liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) method has been developed for the analysis of buprenorphine (BUP) and nor -buprenorphine (NBUP) in biological fluids. Analytes are isolated from urine and blood, after addition of d4 -buprenorphine (d4 -BUP) as internal standard, by solid-phase extraction. Preparation of hair involves external decontamination, mechanical pulverization, overnight incubation in acidic medium, and neutralization prior to extraction. Enzymatic hydrolysis with , -glucuronidase may be performed to distinguish between free and total BUP. Chromatographic separation is accomplished by gradient elution on a cyanopropyl 2.1,×,150,mm column. Positive ion ESI and MS analyses are carried out in an ion trap mass spectrometer. The use of this mass analyzer allows effective collisional experiments to be performed on ESI-generated MH+ species. Abundant product ions are produced, which can be monitored together with precursor ions without losing sensitivity. Thus, assay selectivity is definitely increased with respect to LC/ESI-MS/MS methods in which only precursor ions are monitored. The method has good linearity (calibration curves were linear in the range 0.1,10,ng/mL in urine and blood, in the range 10,160,pg/mg in hair) and limits of detection of 0.05,ng/mL for both BUP and NBUP in blood and urine samples, of 4,pg/mg for both analytes in hair. Both intra- and inter-assay precision and accuracy were satisfactory at three concentrations studied: relative standard deviations were <13.7% in urine, <17.3% in blood, <17.8% in hair; percent deviation of the mean from the true value was always <10.5% in urine and blood, <16.1% in hair. The method can be used to determine both analytes in the urine and hair of drug addicts on replacement therapy, and in post-mortem blood specimens when there is suspicion of drug-related death. Copyright © 2006 John Wiley & Sons, Ltd. [source] | ||||||||||