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1.
Current role of LC–MS(/MS) in doping control 总被引:1,自引:0,他引:1
Liquid chromatography–(tandem) mass spectrometry (LC–MS/MS) has revolutionized the detection assays used in doping control
analysis over the last decade. New methods have enabled the determination of drugs that were formerly difficult to detect
or undetectable at preceding sample concentrations, and complex and/or time-consuming procedures based on alternative chromatographic–mass
spectrometric or immunochemical principles have been replaced by faster, more comprehensive and robust assays. A critical
overview of the contributions of LC–MS(/MS) to sports drug testing is provided, including recent developments regarding low
and high molecular weight drugs. 相似文献
2.
Liquid chromatography–(tandem) mass spectrometry [(LC-MS(/MS)] has become an integral part of modern sports drug testing as
it offers unique capabilities complementing immunological and gas chromatography–(tandem) mass spectrometry [(GC-MS(/MS)]-based
detection methods for prohibited compounds. The improved options of fast and sensitive targeted analysis as well as untargeted
screening procedures utilizing high resolution/high accuracy mass spectrometry have considerably expanded the tools available
to anti-doping laboratories for initial testing and confirmation methods. One approach is to focus on pre-selected target
analytes that are measured with utmost specificity and sensitivity using diagnostic precursor–product ion pairs in low resolution
tandem mass spectrometers. The other scenario is to measure and plot extracted ion chromatograms of protonated or deprotonated
molecules as well as product ions as recorded in the full scan mode with high resolution/high accuracy mass spectrometry.
Examples of recent applications of sports drug testing procedures published between 2007 and 2010 are presented and discussed,
outlining the particular advantages of the selected approaches as well as their limitations in a short- and long-term perspective. 相似文献
3.
Clinical and forensic toxicology and doping control deal with hundreds or thousands of drugs that may cause poisoning or are
abused, are illicit, or are prohibited in sports. Rapid and reliable screening for all these compounds of different chemical
and pharmaceutical nature, preferably in a single analytical method, is a substantial effort for analytical toxicologists.
Combined chromatography–mass spectrometry techniques with standardised reference libraries have been most commonly used for
the purpose. In the last ten years, the focus has shifted from gas chromatography–mass spectrometry to liquid chromatography–mass
spectrometry, because of progress in instrument technology and partly because of the polarity and low volatility of many new
relevant substances. High-resolution mass spectrometry (HRMS), which enables accurate mass measurement at high resolving power,
has recently evolved to the stage that is rapidly causing a shift from unit-resolution, quadrupole-dominated instrumentation.
The main HRMS techniques today are time-of-flight mass spectrometry and Orbitrap Fourier-transform mass spectrometry. Both
techniques enable a range of different drug-screening strategies that essentially rely on measuring a compound’s or a fragment’s
mass with sufficiently high accuracy that its elemental composition can be determined directly. Accurate mass and isotopic
pattern acts as a filter for confirming the identity of a compound or even identification of an unknown. High mass resolution
is essential for improving confidence in accurate mass results in the analysis of complex biological samples. This review
discusses recent applications of HRMS in analytical toxicology. 相似文献
4.
Doménech-Carbó MT Osete-Cortina L de la Cruz Cañizares J Bolívar-Galiano F Romero-Noguera J Fernández-Vivas MA Martín-Sánchez I 《Analytical and bioanalytical chemistry》2006,385(7):1265-1280
The alterations produced by microbiological attack on terpenoid resin-based varnishes from panel and canvas paintings have
been evaluated using pyrolysis–gas chromatography–mass spectrometry (Py–GC–MS) and gas chromatography–mass spectrometry (GC–MS).
The proposed methods include the on-line derivatisation of drying oils and diterpenoid resins using hexamethyldisilazane during
pyrolysis and the application of methyl chloroformate as a derivatisation reagent for triterpenoid resins in GC–MS. Two types
of specimens, consisting of model oil medium prepared from linseed oil and model spirit varnishes prepared from colophony
and mastic resins dissolved in turpentine, have been used as reference materials. For a series of specimens upon which different
genera of bacteria and fungi were inoculated and encouraged to grow, analyses indicated that no mechanisms that commonly occur
during the attack of enzymes on drying oils and terpenoid biodegraders were observed to occur in the oil medium and varnishes
studied. Thus, the degradation pathways observed in the performed trials usually occur as consequence of natural ageing. Specific
trials consisting of the application of biocides to uninoculated colophony varnish resulted in the identification of processes
that produce undesirable degradation of the varnish due to interactions between the biocide and the varnish components. Finally,
the studied biocides—Biotin, New-Des and Nipagine—generally exhibited good inhibiting effects on the microorganisms studied,
although some interesting differences were found between them regarding the application method and type of biocide. 相似文献
5.
Bonet-Domingo E Grau-González S Martín-Biosca Y Medina-Hernández MJ Sagrado S 《Analytical and bioanalytical chemistry》2007,387(7):2537-2545
Three main aspects of internal quality—internal method validation, internal quality control (IQC), and sample result uncertainty—have
been established for a multi-residue method for determination of 46 organic micropollutants (pesticides and polycyclic aromatic
hydrocarbons) in water by stir-bar-sorptive extraction (SBSE) and thermal desorption (TD) coupled to capillary gas chromatography–mass
spectrometry (GC–MS). From data obtained with increasing time, the process mean and standard deviation were used to harmonize
the internal quality statistics. The relationship between these statistics and the hydrophobicity of the compounds was evaluated. 相似文献
6.
Maurer HH 《Analytical and bioanalytical chemistry》2009,393(1):97-107
Driving under the influence of prescribed or illegal drugs increases the risk of having road accidents, just like driving
under the influence of alcohol. In forensic toxicology, an increasing number of blood samples must be analyzed for drugs.
Immunoassays tailored for a limited number of drugs (of abuse) are usually applied as prescreening tests at the roadside and/or
in the laboratory. However, many other common drugs, such as anesthetics, antidepressants, antiepileptics, antihistamines,
newer designer drugs, herbal drugs, neuroleptics (antipsychotics), opioids, or sedative-hypnotics, can also impair drivers.
Therefore, this paper reviews multianalyte single-stage and tandem gas or liquid chromatography–mass spectrometry (GC-MS or
LC-MS) procedures for the screening, identification, and validated quantification of such drugs in blood that have been reported
since 2003. Basic information about the biosample assayed, workup, chromatography, the mass spectral detection mode, and validation
data is summarized in tables. The pros and cons of the reviewed procedures are critically discussed, particularly with respect
to their probable usefulness in impaired driving toxicology.
Parts of this review were presented as a plenary lecture at T2007, the joint meeting of the International Council on Alcohol,
Drugs, and Traffic Safety (ICADTS) and The International Association of Forensic Toxicologists (TIAFT), Seattle (WA), August
26–30, 2007. 相似文献
7.
Assessment of commutability for candidate certified reference material ERM-BB130 “chloramphenicol in pork” 总被引:1,自引:0,他引:1
Reinhard Zeleny Håkan Emteborg Heinz Schimmel 《Analytical and bioanalytical chemistry》2010,398(3):1457-1465
Chloramphenicol (CAP), an effective antibiotic against many microorganisms, is meanwhile banned in the EU for treatment of
food-producing animals due to adverse health effects. The Institute for Reference Materials and Measurements (IRMM) is currently
developing a certified reference material (CRM) for CAP in pork, intended for validation and method performance verifications
of analytical methods. The material will be certified using liquid chromatography–tandem mass spectrometry (LC–MS/MS) and
gas chromatography–mass spectrometry (GC–MS) methods and has a target CAP level around the minimum required performance limit
(MRPL) of 0.3 μg/kg. To prove that the material can be applied as a quality control tool for screening methods, a commutability
study was conducted, involving five commercially available enzyme-linked immunosorbent assay kits and one biosensor assay
(BiaCore kit). Meat homogenates (cryo-milled wet tissue) with CAP concentrations around the MRPL and the candidate CRM (lyophilised
powder) were measured by LC–MS/MS and GC–MS as well as the six screening methods. Pairwise method comparisons of results obtained
for the two sample types showed that the CRM can successfully be applied as quality control (QC) sample to all six screening
methods. The study suggests that ERM-BB130 is sufficiently commutable with the investigated assays and that laboratories applying
one of the investigated kits therefore benefit from using ERM-BB130 to demonstrate the correctness of their results. However,
differences among the assays were observed, either in the abundance of bias between screening and confirmatory LC and GC methods,
the repeatability of test results, or goodness of fit between the methods. 相似文献
8.
Krystyna Srogi 《Mikrochimica acta》2006,154(3-4):191-212
This article reviews the analysis of drugs and drug metabolites in hair by chromatographic procedures, including the pretreatment
steps, and the extraction methods. The general tendency in the last years, to highly sophisticated techniques (GC–MS–NCI,
HPLC–MS, GC–MS–MS) illustrates the constant fight for sensitivity. 相似文献
9.
Barr DB Leng G Berger-Preiss E Hoppe HW Weerasekera G Gries W Gerling S Perez J Smith K Needham LL Angerer J 《Analytical and bioanalytical chemistry》2007,389(3):811-818
The objective of our study was to compare three vastly different analytical methods for measuring urinary metabolites of pyrethroid
and pyrethrum insecticides to determine whether they could produce comparable data and to determine if similar analytical
characteristics of the methods could be obtained by a secondary laboratory. This study was conducted as a part of a series
of validation studies undertaken by the German Research Foundation’s Committee on the Standardization of Analytical Methods
for Occupational and Environmental Medicine. We compared methods using different sample preparation methods (liquid–liquid
extraction and solid-phase extraction with and without chemical derivatization) and different analytical detection methods
(gas chromatography–mass spectrometry (single quadrupole), gas chromatography–high resolution mass spectrometry (magnetic
sector) in both electron impact ionization and negative chemical ionization modes, and high-performance liquid chromatography–tandem
mass spectrometry (triple quadrupole) with electrospray ionization). Our cross validation proved that similar analytical characteristics
could be obtained with any combination of sample preparation/analytical detection method and that all methods produced comparable
analytical results on unknown urine samples.
Cross-method comparison using unknown urine samples revealed reasonably good agreement for any combination of the methods
tested 相似文献
10.
Boguslaw Buszewski Pawel Olszowy Tomasz Ligor Malgorzata Szultka Jacek Nowaczyk Maciej Jaworski Marek Jackowski 《Analytical and bioanalytical chemistry》2010,397(1):173-179
Five adrenolytic drugs have been analyzed by liquid chromatography–mass spectrometry (LC–MS). Samples were prepared by solid-phase
microextraction (SPME) using polypyrrole fibers coated on stainless steel support as an adsorbent for the drugs. Adsorption
efficiencies were 95% and were close for all the drugs investigated. Relative standard deviations (RSD), calculated for samples
prepared in standard solutions, were in the range 2.5–13%, however RSD values for the drugs in human plasma were 2.5–4.5%.
Using LC–MS the limit of detection (LOD) and the limit of quantification (LOQ) were in the ranges 0.11–0.18 and 0.39–0.54 ng mL−1, respectively, for the five drugs. 相似文献
11.
R. J. B. Peters J. E. Oosterink A. A. M. Stolker C. Georgakopoulos M. W. F. Nielen 《Analytical and bioanalytical chemistry》2010,396(7):2583-2598
A unification of doping-control screening procedures of prohibited small molecule substances—including stimulants, narcotics,
steroids, β2-agonists and diuretics—is highly urgent in order to free resources for new classes such as banned proteins. Conceptually
this may be achieved by the use of a combination of one gas chromatography–time-of-flight mass spectrometry method and one
liquid chromatography–time-of-flight mass spectrometry method. In this work a quantitative screening method using high-resolution
liquid chromatography in combination with accurate-mass time-of-flight mass spectrometry was developed and validated for determination
of glucocorticosteroids, β2-agonists, thiazide diuretics, and narcotics and stimulants in urine. To enable the simultaneous
isolation of all the compounds of interest and the necessary purification of the resulting extracts, a generic extraction
and hydrolysis procedure was combined with a solid-phase extraction modified for these groups of compounds. All 56 compounds
are determined using positive electrospray ionisation with the exception of the thiazide diuretics for which the best sensitivity
was obtained by using negative electrospray ionisation. The results show that, with the exception of clenhexyl, procaterol,
and reproterol, all compounds can be detected below the respective minimum required performance level and the results for
linearity, repeatability, within-lab reproducibility, and accuracy show that the method can be used for quantitative screening.
If qualitative screening is sufficient the instrumental analysis may be limited to positive ionisation, because all analytes
including the thiazides can be detected at the respective minimum required levels in the positive mode. The results show that
the application of accurate-mass time-of-flight mass spectrometry in combination with generic extraction and purification
procedures is suitable for unification and expansion of the window of screening methods of doping laboratories. Moreover,
the full-scan accurate-mass data sets obtained still allow retrospective examination for emerging doping agents, without re-analyzing
the samples. 相似文献
12.
Fekete A Frommberger M Rothballer M Li X Englmann M Fekete J Hartmann A Eberl L Schmitt-Kopplin P 《Analytical and bioanalytical chemistry》2007,387(2):455-467
N-Acylated homoserine lactones (AHLs) are produced by Gram-negative bacteria as communication signals and are frequently studied
as mediators of the “quorum sensing” response of bacterial communities. Several reports have recently been published on the
identification of AHLs from different species and attempts have been made to study their role in natural habitats, for example
the surface of plant roots in the rhizosphere. In this article, different analytical methods, including bacterial biosensors
and chromatographic techniques, are reviewed. A concept for assignment of the structures of AHLs is also presented. The retention
behaviour of derivatives of AHLs containing β-keto or hydroxyl groups and/or double bonds has been evaluated in relation to
the separation behaviour of AHLs with saturated and unsubstituted alkanoyl chains. Samples have also been analysed by high
resolution mass spectrometry (Fourier-transform ion-cyclotron-resonance mass spectrometry, FTICR-MS), nano liquid chromatography–electrospray
ionization ion trap mass spectrometry (nano-LC–MS) and by the aid of a biosensor. The results obtained from ultra performance
liquid chromatography (UPLC), FTICR-MS, nano-LC–MS, and bioassays have been compared to attempt structural characterisation
of AHL without chemical synthesis of analytical standards. The method was used to identify the major AHL compound produced
by the rhizosphere bacterium Acidovorax sp. N35 as N-(3-hydroxydecanoyl)homoserine lactone. 相似文献
13.
Two methods were developed for the quantitative analysis of phenolic acids in herb extracts. The methods were based on liquid
chromatography–time-of-flight mass spectrometry (LC–TOFMS) and gas chromatography–mass spectrometry (GC–MS). The methods were
compared in terms of their linearity, repeatability, selectivity, sensitivity and the speed of the analysis. The sensitivity
was good for both methods, with limits of detection of <80 ng/ml for most of the compounds. The relative standard deviations
(RSD) of the peak areas were on average 7.2% for the LC–TOFMS method and 1.4% for the GC–MS method. Both methods were found
to be suitable for the determination of the target analytes, although GC–MS was better suited to the quantitative determination
of compounds present at low concentrations. 相似文献
14.
P. López S. Martello A. M. Bermejo Eleonora De Vincenzi M. J. Tabernero M. Chiarotti 《Analytical and bioanalytical chemistry》2010,397(4):1539-1548
This article describes an easy and innovative extraction procedure for cocaine and its primary metabolite, benzoylecgonine
(BE), from hair consisting of sonication with H2O/0.1% formic acid for 4 h. The same extract was used for screening with an enzyme-linked immunoassay (ELISA) and confirmation
by liquid chromatography–tandem mass spectrometry (LC–MS/MS). For the ELISA screening test a cutoff of 0.5 ng/mg was used
according to the Society of Hair Testing recommendations. LC–MS/MS limits of detection (LODs) were established to be 10 pg/mg
and 1 pg/mg for cocaine and BE, respectively. Linearity was obtained over a range of 0.2–5 ng/mg for BE (target analyte) in
the ELISA screening test, while in the LC–MS/MS method the range was 0.10–10 ng/mg for cocaine and 0.01–10 ng/mg for BE. Intra-
and interbatch coefficients of variation and mean relative errors were less than 20% for all analytes and concentrations studied.
The validated ELISA and LC–MS/MS methods were applied to 48 hair samples and the results of both methods were compared; ELISA
demonstrated a sensitivity and specificity of 89.2% and 10.8%. 相似文献
15.
Gustavo Merola Stefano Gentili Franco Tagliaro Teodora Macchia 《Analytical and bioanalytical chemistry》2010,397(7):2987-2995
A simple procedure combining headspace solid-phase microextraction (HS-SPME) and gas chromatography–mass spectrometry (GC/MS)
to detect and quantify amphetamines, ketamine, methadone, cocaine, cocaethylene and ∆9-tetrahydrocannabinol (THC) in hair is described. This procedure allows, in a single sample, even scant, analysis of drugs
requiring different analytical conditions. A hair sample (10 mg) is washed and subjected to acidic hydrolysis. Then the HS-SPME
is carried out (10 min at 90 °C) for amphetamines, ketamine, methadone, cocaine and cocaethylene. For derivatization of analytes,
the fibre is introduced into the headspace of another closed vial containing acetic anhydride. After a chromatographic run,
an alkaline hydrolysis for THC analysis is carried out in the same vial containing the hair sample previously used. For adsorption,
the solid-phase microextraction needle is inserted into the headspace of the vial and the fibre is exposed for 30 min at 150 °C.
For derivatization of analytes, the fibre is introduced into the headspace of another closed vial containing N-methyl-N-(trimethylsilyl)trifluoroacetamide. The GC/MS parameters were the same for both chromatographic runs. The linearity was proved
to be between 0.01 and 10.00 ng/mg. The repeatability (intra- and interday precision) was below 10% as the coefficient of
variation for all compounds. The accuracy, as the relative recovery, was 96.2–103.5% (spiked samples) and 88.6–101.7% (quality
control sample). The limit of detection ranged from 0.01 to 0.12 ng/mg, and the limit of quantification ranged from 0.02 to
0.37 ng/mg. Application of the procedure to real hair samples is described. To the best of our knowledge, the proposed procedure
combining HS-SPME and GC/MS is the first one be to successfully applied to the simultaneous determination of most of the common
recreational drugs, including THC, in a single hair sample. 相似文献
16.
Selenium is an essential element for human health. The benefits of selenium are many including protection against cancer,
heart diseases and other cardiovascular and muscle disorders. Selenium is also helpful in controlling gastrointestinal disorders,
enhancing immunity of the human body and reducing age-related diseases. The health-promoting properties of Se are due to vital
functions of selenoproteins in which selenium is present as selenocysteine, the 21st amino acid. To date, dozens of selenoprotein
families have been described though many have roles that have not been fully elucidated. Selenoproteins research has attracted
tremendous interest from different scientific areas. Analytical chemists have not remained indifferent to the attractive features
of these unique proteins. Different analytical techniques, such as multidimensional chromatography–inductively coupled plasma
mass spectrometry (ICPMS), electrospray (tandem) mass spectrometry (ESI-MS/MS), matrix-assisted laser desorption ionization
time-of flight (MALDI-TOF) and sodium dodecyl sulphate polyacrylamide gel electrophoresis–laser ablation inductively coupled
plasma mass spectrometry (SDS-PAGE-LA-ICPMS), have been applied to the determination of selenoproteins and selenium-containing
proteins. This review describes the best-characterized selenoproteins to date in addition to the major contributions of analytical
chemistry to the field of selenoproteins. The article also highlights the challenges of combining elemental and molecular
mass spectrometry for the determination of selenoproteins and selenium-containing proteins. 相似文献
17.
This paper reviews scientific contributions on the identification and/or quantification of metabolites of drugs of abuse in
in vitro assays or various body samples using hyphenated mass spectrometry. Gas chromatography–mass spectrometry (GC-MS) as
well as liquid chromatography–mass spectrometry (LC-MS) approaches are considered and discussed if they have been reported
in the last five years and are relevant to clinical and forensic toxicology or doping control. Workup and artifact formation
are discussed, and typical examples of studies of the metabolism of designer drugs, doping agents, herbal drugs, and synthetic
cannabinoids are provided. Procedures for quantifying metabolites in body samples for pharmacokinetic studies or in enzyme
incubations for enzyme kinetic studies are also reviewed. In conclusion, the reviewed papers showed that both GC-MS and LC-MS
still have important roles to play in research into the metabolism of drugs of abuse, including doping agents. 相似文献
18.
Barroso M Gallardo E Vieira DN Queiroz JA López-Rivadulla M 《Analytical and bioanalytical chemistry》2011,400(6):1665-1690
The use and abuse of illegal drugs affects all modern societies, and therefore the assessment of drug exposure is an important
task that needs to be accomplished. For this reason, the reliable determination of these drugs and their metabolites in biological
specimens is an issue of utmost relevance for both clinical and forensic toxicology laboratories in their fields of expertise,
including in utero drug exposure, driving under the influence of drugs and drug use in workplace scenarios. Most of the confirmatory
analyses for abused drugs in biological samples are performed by gas chromatographic–mass spectrometric methods, but use of
the more recent and sensitive liquid chromatography–(tandem) mass spectrometry technology is increasing dramatically. This
article reviews recently published articles that describe procedures for the detection of opiates in the most commonly used
human biological matrices, blood and urine, and also in unconventional ones, e.g. oral fluid, hair, and meconium. Special
attention will be paid to sample preparation and chromatographic analysis. 相似文献
19.
Tang Zekun Ye Fanfan Wan Huihui Song Yuming Fan Weiwei Chi Zhanyou Du Qinqin Cai Rui Xu Qiang Zhang Hua 《Chromatographia》2022,85(5):395-403
Chromatographia - Liquid chromatography–mass spectrometry (LC–MS) technique has been widely used for the determination of trace carbohydrate compounds in biological samples. However,... 相似文献
20.
Dumont E Ogra Y Vanhaecke F Suzuki KT Cornelis R 《Analytical and bioanalytical chemistry》2006,384(5):1196-1206
Liquid chromatography (LC) hyphenated with both elemental and molecular mass spectrometry has been used for Se speciation
in Se-enriched garlic. Different species were separated by ion-pair liquid chromatography–inductively coupled plasma mass
spectrometry (LC–ICP–MS) after hot-water extraction. They were identified by on-line reversed-phase liquid chromatography–electrospray
ionization tandem mass spectrometry (RPLC–ESI–MS–MS). Se-methionine and Se-methylselenocysteine were determined by monitoring
their product ions. Another compound, γ-glutamyl-Se-methylselenocysteine, shown to be the most abundant form of Se in the
garlic, was determined without any additional sample pre-treatment after extraction and without the need for a synthesized
standard. Product ions for this dipeptide were detected by LC–ESI–MS–MS for three isotopes of Se—78
Se, 80Se: and 82Se. The method was extended to the species extracted during in-vitro gastrointestinal digestion. Because both Se-methylselenocysteine
and γ-glutamyl-Se-methylselenocysteine have anticarcinogenic properties, their extractability and stability during human digestion
are very important. Garlic was also treated with saliva, to enable detection and analysis of species extracted during mastication.
Detailed information on the extractability of selenium species by both simulated gastric and intestinal fluid are given, and
variation of the distribution of Se among the different species with time is discussed. Although the main species in garlic
is the dipeptide γ-glutamyl-Se-methylselenocysteine, Se-methylselenocysteine is the main compound present in the extracts
after treatment with gastrointestinal fluids. Two more, so far unknown compounds were observed in the chromatogram. The extracted
species and their transformations were analysed by combining LC–ICP–MS and LC–ESI–MS–MS. In both the simulated gastric and
intestinal digests, Se-methionine, Se-methylselenocysteine, and γ-glutamyl-Se-methylselenocysteine could be determined by
LC–ESI–MS–MS by measuring their typical product ions.
相似文献