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1.
This study concerns the detection of natural steroid hormones in hair of cattle. Estradiol (E2) and testosterone (T) were chosen as representatives of estrogens and androgens. In particular, the influence of age, sex
and hair pigmentation on the steroid concentrations was investigated. Samples were obtained from numerous steers, cows, bulls,
and female and male calves. The extraction procedure for E2 and T from hair comprised liquid-liquid and solid-phase extraction and was followed by an essential high-performance liquid
chromatography (HPLC) step for further purification of the extracts. Final quantification was performed with specific enzyme
immunoassays (EIA). Lower E2-concentrations were detected in the hair of some steers, cows, and bulls (approximately 1 ng/g), in several of these hair
samples the concentrations of E2 were below the limit of detection. Testosterone was measured in the hair of steers (approximately 3 ng/g), cows (approximately
6 ng/g), and bulls (in average 15 ng/g). There was a significant difference in the testosterone concentrations of white (approximately
8 ng/g) and of black hair (approximately 33 ng/g) of bulls. In hair from all male and female calves, E2 and T were measured. The concentrations amounted approximately to 9 ng E2/g and 3 ng T/g for female calves and to 5 ng E2/g and 7 ng T/g for male calves. There was no significant influence of sex or hair colour on the steroid concentrations in
hair of calves. The results suggest that the method is a powerful means to detect natural steroid hormones in hair of animal
origin.
Received: 2 August 1996/Revised: 30 August 1996/Accepted: 5 September 1996 相似文献
2.
This study concerns the detection of natural steroid hormones in hair of cattle. Estradiol (E2) and testosterone (T) were chosen as representatives of estrogens and androgens. In particular, the influence of age, sex
and hair pigmentation on the steroid concentrations was investigated. Samples were obtained from numerous steers, cows, bulls,
and female and male calves. The extraction procedure for E2 and T from hair comprised liquid-liquid and solid-phase extraction and was followed by an essential high-performance liquid
chromatography (HPLC) step for further purification of the extracts. Final quantification was performed with specific enzyme
immunoassays (EIA). Lower E2-concentrations were detected in the hair of some steers, cows, and bulls (approximately 1 ng/g), in several of these hair
samples the concentrations of E2 were below the limit of detection. Testosterone was measured in the hair of steers (approximately 3 ng/g), cows (approximately
6 ng/g), and bulls (in average 15 ng/g). There was a significant difference in the testosterone concentrations of white (approximately
8 ng/g) and of black hair (approximately 33 ng/g) of bulls. In hair from all male and female calves, E2 and T were measured. The concentrations amounted approximately to 9 ng E2/g and 3 ng T/g for female calves and to 5 ng E2/g and 7 ng T/g for male calves. There was no significant influence of sex or hair colour on the steroid concentrations in
hair of calves. The results suggest that the method is a powerful means to detect natural steroid hormones in hair of animal
origin.
Received: 2 August 1996/Revised: 30 August 1996/Accepted: 5 September 1996 相似文献
3.
Gratacós-Cubarsí M García-Regueiro JA Castellari M 《Analytical and bioanalytical chemistry》2007,387(6):1991-1998
Enrofloxacin is a synthetic bacteriostatic administered in veterinary therapy. It can also be used illegally as a growth promoter
to enhance feed efficiency and weight gain. This practice is banned in several countries due to its potential negative effects
on the environment and human health. A suitable method for extracting and quantifying enrofloxacin (ENR) and its main metabolite
ciprofloxacin (CPR) in cattle and pig hair by high-performance liquid chromatography–fluorimetric detection (HPLC–FLD) had
been proposed. ENR and CPR were extracted from hair samples with methanol acidified with trifluoroacetic acid for 24 h at
70 °C. The extracts were evaporated and redissolved in the mobile phase before injection. This simplified procedure enabled
the detection of both CPR and ENR at ng g−1 levels (limit of detection 4–5 ng g−1) without further purification. Detectable residues of ENR were found in calf and pig hairs after the pharmacological treatment
was started. Mean concentrations of quinolone (ENR, CPR) in contaminated hairs ranged from 20 to 2,518 ng g−1 in calves and from 152 to 1,140 ng g−1 in pigs. Hair pigmentation enhanced quinolone accumulation significantly. Hair analysis seems to increase the time window
available for the retrospective detection of illegal ENR administration compared to edible tissue analysis. 相似文献
4.
Monitoring anabolic steroids in meat-producing animals is a challenging task. It implies very specific and sensitive analytical methods able to detect and identify sub-μg kg?1 residue levels in complex biological matrices such as meat, urine, or hair. Gas and liquid chromatography coupled to mass spectrometry are the most efficient means of achieving these objectives. In this paper we review how developments in mass spectrometry have been rapidly applied to this problem, how efficient analysis of anabolic steroids in urine, edible tissue, and hair has been achieved, and, later, how measurement of conjugate steroids and determination of the origin of natural steroid hormones has been achieved. The performance characteristics of different mass spectrometers (quadrupole, ion-trap, electromagnetic, isotope-ratio, tandem, and hybrid instruments), the efficiency of different acquisition techniques (LR-SIM, HR-SIM, MRM), and, finally, sample introduction (gas chromatography and liquid chromatography, with discussion of alternative interfaces) are discussed, with numerous applications. 相似文献
5.
Benzylpiperazine (BZP) is an amphetamine-type stimulant, which was legally available in New Zealand and widely used in “Party
Pills” until reclassification as a Class C drug in April 2008. BZP was included as part of a multi-analyte method developed
for hair screening using high-performance liquid chromatography triple quadrupole mass spectrometry (LC-MS/MS). A 20-mg sample
of hair is extracted and partially purified using mixed-mode solid-phase extraction cartridges prior to analysis by LC-MS/MS.
The method was developed as a broad screen for drugs of abuse (including amphetamines, opiates, and benzodiazepines), with
only the BZP results being presented here. The assay was validated and found to be linear over the range of 0.085 to 8.65 ng/mg
with correlation coefficient of r
2 ≥ 0.99. Blank hair samples spiked with BZP at 0.22 and 2.16 ng/mg gave intra- and inter-day precision coefficients of variation
of ≤10% (n = 6 per day, 3 days) at both levels and calculated extraction efficiencies of 78% and 91%, respectively. The results from
the samples submitted to the laboratory for BZP analysis showed 11% were positive (n = 126). The mean BZP level was 3.9 ng/mg (range, 0.4–33 ng/mg; the result was extrapolated when above the calibration). These
data are the first available showing the levels expected from users of BZP. 相似文献
6.
Determination of residual anabolic steroid in meat by gas chromatography-ion trap-mass spectrometer 总被引:2,自引:0,他引:2
The use of natural and synthetic anabolic steroids in animal fattening has been prohibited in Taiwan and many countries because of their potential toxic effect on public health. This paper describes a newly developed gas chromatography-ion trap-mass spectrometry (GC-IT-MS) method for the quantitative determination of various residual anabolic steroids in meat. Anabolic steroid was derivatized with N-methyl-N-trimethylsilytrifluoroacetamide prior to GC-IT-MS analysis. MS2 was employed for quantitative measurement. In addition, 2d-estradiol was used as an internal standard. Quantitative determination was based on the ratio of peak area of steroid derivative to peak area of internal standard derivative. Good linearity of each compound, 0.03-1.0 μg/ml, was determined. Solvent extraction was used to extract residual anabolic compounds in meat samples and a solid phase extraction (SPE) procedure was utilized for sample cleanup and pre-concentration. The limits of detection of anabolic compounds approximately ranged from 0.1 to 0.4 μg/kg. The detection limit was comparable with or better than reported methods and was below the minimum required performance limits (MRPLs) established by the European Community (EC). The application of this newly developed method was demonstrated by analyzing various beef, pork, chicken and several animal internal organ samples from local markets. 相似文献
7.
Norlida Harun Robert A. Anderson Peter A. G. Cormack 《Analytical and bioanalytical chemistry》2010,396(7):2449-2459
An anti-ketamine molecularly imprinted polymer (MIP) was synthesized and used as the sorbent in a solid-phase extraction protocol
to isolate ketamine and norketamine from human hair extracts prior to LC-MS/MS analysis. Under optimised conditions, the MIP
was capable of selectively rebinding ketamine, a licensed anaesthetic that is widely misused as a recreational drug, with
an apparent binding capacity of 0.13 μg ketamine per mg polymer. The limit of detection (LOD) and lower limit of quantification
(LLOQ) for both ketamine and norketamine were 0.1 ng/mg hair and 0.2 ng/mg hair, respectively, when 10 mg hair were analysed.
The method was linear from 0.1 to 10 ng/mg hair, with correlation coefficients (R
2) of better than 0.99 for both ketamine and norketamine. Recoveries from hair samples spiked with ketamine and norketamine
at a concentration of 50 ng/mg were 86% and 88%, respectively. The method showed good intra- and interday precisions (<5%)
for both analytes. Minimal matrix effects were observed during the LC-MS/MS analysis of ketamine (ion suppression −6.8%) and
norketamine (ion enhancement +0.2%). Results for forensic case samples demonstrated that the method successfully detected
ketamine and norketamine concentrations in hair samples with analyte concentrations ranging from 0.2 to 5.7 ng/mg and from
0.1 to 1.2 ng/mg, respectively. 相似文献
8.
Javier Adrian Marta Gratacós-Cubarsí Francisco Sánchez-Baeza Jose-Antonio Garcia Regueiro Massimo Castellari M.-Pilar Marco 《Analytical and bioanalytical chemistry》2009,395(4):1009-1016
The use of hair to trace use of unauthorized substances, therapeutic agents, or their misuse is becoming very attractive since
residues can be detected for a long time after treatment. For this purpose, an indirect enzyme-linked immunosorbent assay
(ELISA) has been evaluated for its capability to trace sulfonamide antibiotic treatment by analyzing cattle and pig hair samples.
Pigmented and nonpigmented hair samples from control and sulfamethazine (SMZ)-treated pigs and calves were collected, extracted
under different alkaline conditions, and analyzed by ELISA after just diluting the extracts with the assay buffer. Data analysis
following the European recommendations for screening methods demonstrates that the ELISA can detect SMZ in hair samples with
a limit of detection (90% of the zero dose (IC90)) between 30 and 75 ng g−1. The same samples have been analyzed by HPLC after a dual solid-phase extraction. The ELISA results matched very well those
obtained by the chromatographic method, demonstrating that the immunochemical method can be used as a screening tool to trace
animal treatments. Between the benefits of this method are the possibility to directly analyze hair extracts with sufficient
detectability and its high-throughput capability. Preliminary validation data are reported using an experimental approach
inspired on the Commission Decision 2002/657/EC criteria for screening methods. 相似文献
9.
The detection of the abuse of anabolic steroids in equine sport is complicated by the endogenous nature of some of the abused steroids, such as testosterone and nandrolone. These steroids are commonly administered as intramuscular injections of esterified forms of the steroid, which prolongs their effects and improves bioavailability over oral dosing. The successful detection of an intact anabolic steroid ester therefore provides unequivocal proof of an illegal administration, as esterified forms are not found endogenously. Detection of intact anabolic steroid esters is possible in plasma samples but not, to date, in the traditional doping control matrix of urine. The analysis of equine mane hair for the detection of anabolic steroid esters has the potential to greatly extend the time period over which detection of abuse can be monitored. 相似文献
10.
A fast immunoassay for the screening of beta-agonists in hair. 总被引:4,自引:0,他引:4
Hair has been shown to be an excellent site for the accumulation of clenbuterol residues. Compared with other matrices, hair sampling is very easy and this might result in large numbers of samples. In this study, a simple digestion-extraction procedure was combined with a sensitive clenbuterol ELISA, which resulted in an easy screening procedure suitable for the detection of at least four beta-agonists. Hair from untreated cows (n = 40) resulted in low blank levels (0.9 +/- 0.7 and 0.5 +/- 0.2 ng g-1 for black and white hair, respectively). The detection limits for clenbuterol, bromobuterol, mapenterol and mabuterol were determined as 1-1.5 ng g-1 for white and 3-4 ng g-1 for black hair. The accumulation of mabuterol and mapenterol in black and white hair from treated calves was demonstrated by GC-MS. The screening assay is not suitable for the detection of cimbuterol (owing to the low extraction efficiency) and for salbutamol and terbutaline (owing to the low cross-reactivity of the antibodies used for the ELISA and the low extraction efficiency). Black hair samples from cows treated with clenbuterol were still found to be positive (> 5 ng g-1) at 23 weeks after treatment. The fast screening procedure is a powerful means to detect and track the illegal use of clenbuterol, bromobuterol, mabuterol and mapenterol in animal production. 相似文献
11.
Summary Adapalene, the active constituent of Differin?, is a novel potent retinoid (vitamin A analogue) for the topical treatment of acne vulgaris. The clinical usefulness of retinoids
is limited by a number of side effects, such as teratogenicity and skin irritation. A method has been developed for simultaneous
determination of adapalene and retinol in plasma and tissue in in vivo and in vitro studies for the determination of the pharmacokinetic
profile and the influence of adapalene on the endogenous retinol level. The new method was developed by coupling an autosampler
to an automated solid-phase extraction unit on-line with a gradient HPLC system using UV and fluorescence detection. The low
detection limit (0.25 ng mL−1 for adapalene), the small sample weight (50 mg) and the high degree of automation make this method convenient for analysis
of biological samples in animal and human studies.
Presented at the 21st ISC held in Stuttgart, Germany, 15th–20th September, 1996. 相似文献
12.
The work presented in this paper deals with the combination of capillary electrophoresis (CE) with electrospray mass spectrometry (MS) for the determination of drug residues in water. CE/MS methods have been developed based on either aqueous or non-aqueous ammonium acetate solutions as the carrier electrolyte for the separation of selected drugs. The different separation conditions were compared in terms of selectivity and detection limits; both aqueous and non-aqueous CE proved to be suitable for the present analytical task, exhibiting detection limits between 3 and 93 μg/dm3 (injected standard concentration) corresponding to concentrations between 5 and 19 ng/dm3 in the sample. A combination of liquid-liquid extraction and solid-phase extraction was investigated for sample pretreatment, yielding enrichment factors of 10000. The applicability of CE/MS was demonstrated for the analysis of several river water samples. 相似文献
13.
Summary Selective on-line solid phase extraction (SPE) and liquid chromatography determination (HPLC) of diquat, paraquat and difenzoquat
from environmental water samples has been accomplished with Graphitized Carbon Black (GCB) as both extraction and analytical
columns. The method involved passing of 50 mL of water through a cartridge filled with Carbograph. In the elution step, the
herbicides were transferred from the cartridge to the analytical column (Hypercarb) by mean of a gradient of pH 3 aqueous
solution of tetramethylammonium hydroxide (TMAOH) and ammonium sulphate and methanol. Hypercarb columns were found to give
a low probability of false positives for bypiridylium herbicides and are very selective for polar compounds. Recovery was
better than 80 %. The breakthrough volume was studied with distilled water spiked with the herbicides at various concentration
levels (from 0.1 to 20 μg L−1). The limits of quantification of the method were lower than 0.1 μg L−1. The total analytical method was applied to surface waters from Torreblanca Nature Park (Castelló, Spain).
Presented at the 21st ISC held in Stuttgart, Germany, 15th–20th September, 1996. 相似文献
14.
S. Hegstad E. Lundanes R. Reistad L. S. Haug G. Becher J. Alexander 《Chromatographia》2000,52(7-8):499-504
Summary A method for the determination of the food mutagen 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) in human hair has been developed and validated. Hair samples (200 mg) were dissolved in NaOH (1 M) and PhIP
was isolated by successive solid-phase extraction on a polystyrene-divinylbenzene column and on a silica-based mixed-mode
column with C8 and-SO3
− functional groups. Quantification was performed by gas chromatography-electron-impact ionization high-resolution mass spectrometry
in selected-ion-monitoring mode. The method was validated for determination of PhIP in the concentration range 0.5–25 ng g−1 hair with [2H3]PhIP as internal standard. The limit of quantification was 0.26 ng g−1 hair. Within-day and between-day precision were in the ranges 1–27% and 2–15% relative standard deviation, respectively.
The hair sample used for method validation was found to contain 0.26 ng PhIP g−1 hair. 相似文献
15.
The detection of steroid residues in hair is a powerful strategy to demonstrate long-term administration of these growth promoters in meat production animals. A fast and reliable method was developed for monitoring anabolic steroids and their esters in hair. A 100 mg hair sample was converted into powder and extracted at 50 °C with methanol (sebum fraction). The remaining hair was digested with 1 M NaOH for further extraction of bound steroids. The two fractions were separately purified onto an aminopropyle solid-phase extraction column and onto a silica SPE cartridge. Steroids were detected either by gas chromatography-tandem mass spectrometry after silylation using N-methyl-N-(trimethylsilyl)-trifluoroacetamide/trimethyliodosilane/dithiothreitol or liquid chromatography-tandem mass spectrometry. This method was applied to hair samples collected over a three months period after treatment of three cows respectively with 17α-methyltestosterone, medroxyprogesterone acetate and 17β-estradiol-3-benzoate. The fixation kinetic into hair of the three steroids have been deeply examined and discussed; relation in-between concentration and distance from the injection site, influence of hair colour and sample treatment consequences have been discussed. 相似文献
16.
A method based on liquid-liquid extraction (LLE) and automated large volume injection (LVI)-GC-MS analysis was developed for the trace determination of phthalate di-esters in water samples at sub-g L–1 (ppb) levels. Strategies applied to reduce contamination include (i) careful selection of tools, glassware and solvents, (ii) systematic blank checks of the chromatographic system, glassware and solvents and (iii) frequent verifications of blanks during sequences. Background levels could be reduced to those present in the extraction solvent. For phthalates not present in the extraction solvent the limits of quantitation (LOQ) are 6 ng L–1 for di-methyl phthalate (DMP), 3 ng L–1 for benzylbutyl phthalate (BzBP) and 45 ng L–1 for the isomeric phthalate mixtures di-isononyl phthalate (DiNP) and di-isodecyl phthalate (DiDP). For the other phthalates, the LOQ was set at twice the blank (extraction solvent) level and are 20 ng L–1 for di-ethyl phthalate (DEP), 60 ng L–1 for di-isobutyl phthalate (DiBP), 80 ng L–1 for di-n-butyl phthalate (DBP) and 30 ng L–1 for bis-(2-ethylhexyl) phthalate (DEHP).Dedicated to Professor K. Jinno on the occasion of his 60th birthday 相似文献
17.
A simple and reliable method has been established for determination of cis and trans-1,3-dichloropropene (1,3-DCP) in water by headspace solid-phase microextraction (HS-SPME) then GC–ECD. An experimental design
with two steps was performed to determine the best experimental conditions for extraction of the 1,3-DCP isomers. First, a
26−2 fractional factorial design was conducted to screen for significant conditions. Second, a central composite design (CCD)
was performed to optimise the variables. The best experimental extraction conditions were: polydimethylsiloxane–divinylbenzene
(PDMS–DVB)-coated fibre, 20-min extraction time, 12 °C extraction temperature, 300 g L−1 NaCl, and 20 mL headspace volume in 40-mL vial. Under these conditions the method detection limit (MDL) was 0.5 ng L−1 for cis-1,3-DCP and 1.0 ng L−1 for trans-1,3-DCP. The method quantification limit (MQL) was 1.2 ng L−1 for cis-1,3-DCP and 3.0 ng L−1 for trans-1,3-DCP. For both isomers the relative standard deviation (RSD) for analysis of 50 ng L−1 or 0.5 μg L−1 of the isomer mixture was less than 8%. When the proposed method was applied to surface (river) water and tapwater samples
from Gipuzkoa province (Spain) the target analytes were not detected. The method was also used to investigate the presence
of the isomers in leachates from agricultural soil. A mixed solution was added to samples of two different soils and 1,3-DCP
isomers were quantified in leachate obtained from the samples. 相似文献
18.
Anielski P Thieme D Schlupp A Grosse J Ellendorff F Mueller RK 《Analytical and bioanalytical chemistry》2005,383(6):903-908
Growing interest among several horse-breeder associations has initiated the development of a screening procedure to test for
anabolic agents in hair, which has the advantage over blood and urine specimens of allowing long-term detection. An analytical
method was established to monitor in tails or manes several anabolic substances available as veterinary medicines or as so-called
nutritional supplements (clenbuterol, different esters or prohormones of nandrolone and testosterone). The analytical procedure
to detect steroids in hair samples consists of the following steps: decontamination of the hair strand or segment with methanol/water
(1:1), milling, extraction of the hair material in an ultrasonic bath using methanol, purification by liquid–liquid extraction
(n-pentane/methanol, 25:1) and HPLC cleanup, derivatisation of the relevant LC fractions with MSTFA, and measurement using
GC-MS/MS technique. The first objective of our study was the detection of exogenous nandrolone (nortestosterone, NT) in the
horse hair; therefore nandrolone-associated compounds [nandrolone dodecanoate administered intramuscularly (i.m.) and a mixture
of 4-estrenediol and 4-estrenedione, transdermal] were administered to four geldings. The highest concentrations of NT following
i.m. treatment were measured after 10 days in a 2-cm hair segment (up to 18 pg/mg); NT was detectable for up to 120 days and
in some cases up to 330 days in tail hair (limit of detection 0.3 pg/mg). Following transdermal application, nandrolone as
well as the administered prohormones were identified in tail and mane until the latest sampling at 3 months. Furthermore,
untreated stallions (128) were investigated to estimate the range of endogenous levels of NT and testosterone (T) in hair.
Maximum values of 3 pg/mg (NT) and 1 pg/mg (T) were quantified originating from endogenous formation in the male horse. Additionally,
a possible relationship between steroid concentrations in hair specimens and the age of stallions was appraised. NT and T
were not detected in hair samples of control geldings. Following nandrolone treatment of geldings, highest values in hair
exceeded the endogenous amount detected in untreated stallions. Therefore comparison of concentrations measured in control
samples with the estimated endogenous levels could give a clue to exogenous application in cases of abnormally high amounts
of NT or T. The possibility of the evaluation of threshold values is discussed as a means to verify an exogenous administration
of NT and T in hair samples. Furthermore, the detection of a synthetic substance in hair, e. g. the parent steroid ester by
itself, would be unequivocal proof of an exogenous origin of NT or T and the previous medication of the stallion. 相似文献
19.
Within the scope of the European Community member states' residue monitoring plan, illicit administration of anabolic steroids is monitored at slaughterhouse level as well as on living animals. At farm level, urine is one of the target matrices to detect possible abuse of anabolic steroid growth promoters. Optimisation of the routinely applied analysis method resulted in a procedure for which high performance liquid chromatographic (HPLC) fractionation prior to GC-MS(n) analysis was no longer required. Analytical results could be obtained within 1 day and only 5 mL urine was needed to carry out the screening procedure. Using the downscaled methodology, all validation criteria described in the European Commission document 2002/657/EC could be fulfilled, and the minimum required performance limits (MRPLs) established for anabolic steroids in urine, could be achieved. A higher GC-MS technique's specificity was achieved by detecting the steroids using GC-MS3. Nevertheless, it was decided to screen routinely sampled urine with GC-MS2 whereas GC-MS3 was applied to confirm the presence of anabolic steroid residues in suspected sample extracts. 相似文献
20.
Summary. The work presented in this paper deals with the combination of capillary electrophoresis (CE) with electrospray mass spectrometry
(MS) for the determination of drug residues in water. CE/MS methods have been developed based on either aqueous or non-aqueous
ammonium acetate solutions as the carrier electrolyte for the separation of selected drugs. The different separation conditions
were compared in terms of selectivity and detection limits; both aqueous and non-aqueous CE proved to be suitable for the
present analytical task, exhibiting detection limits between 3 and 93 μg/dm3 (injected standard concentration) corresponding to concentrations between 5 and 19 ng/dm3 in the sample.
A combination of liquid-liquid extraction and solid-phase extraction was investigated for sample pretreatment, yielding enrichment
factors of 10000. The applicability of CE/MS was demonstrated for the analysis of several river water samples.
Received August 25, 2000. Accepted October 17, 2000 相似文献