An improved hollow fiber solvent-stir bar microextraction for the preconcentration of anabolic steroids in biological matrix with determination by gas chromatography-mass spectrometry
JOURNAL OF CHROMATOGRAPHY A
Authors: Liu, Wei; Zhang, Lan; Fan, Liangbiao; Lin, Zian; Cai, Yimin; Wei, Zhenyi; Chen, Guonan
Abstract
In this paper, a convenient and self-assembled hollow fiber solvent-stir bar microextraction (HF-SSBME) device was developed, which could stir by itself. In the extraction process, the proposed device made the solvent "bar" not floating at the sample solution and exposing to air while organic solvents outside hollow fiber always wrapped with donor phase solvent, which reduced the vaporization of organic solvents. This design could improve the precisions and recoveries of experiments. For evaluating the device, seven anabolic steroids (prasterone, 5 alpha-androstane-3 alpha, 17 beta-diol, methandriol, 19-norandrostenediol, androstenediol, methyltestosterone and methandienone) were used as model analytes and extraction conditions such as type and volume of organic solvents, agitation speed, extraction time, extraction temperature and salt addition were studied in detail. Under the optimum conditions (15 mu L toluene, 40 degrees C, stirring at 750 rpm for 30 min with 1.5g sodium chloride addition in 20.0 mL donor phase), the linear ranges of anabolic steroids were 0.25-200 ng mL(-1) with gas chromatography-mass spectrometry. The limits of detection were lower than 0.10 ng mL(-1). The recoveries and precisions in spiked urine and hair samples were between 73.97-93.56% and 2.18-4.47% (n = 5). HF-SSBME method combined the intrinsical merits of hollow fiber with the superiority of the proposed self-stirring device which can be developed to two-phase, three-phase and in situ derivatization modes with wide prospect of application. Besides, the pedestal of this proposed device can be converted to fix stir bar in stir bar sorptive extraction (SBSE) method. (C) 2012 Elsevier B.V. All rights reserved.
METABOLISM OF ANABOLIC-STEROIDS IN MAN - SYNTHESIS AND USE OF REFERENCE SUBSTANCES FOR IDENTIFICATION OF ANABOLIC-STEROID METABOLITES
ANALYTICA CHIMICA ACTA
Authors: SCHANZER, W; DONIKE, M
Abstract
The use of anabolic steroids was banned by the International Olympic Committee for the first time at the Olympic Games in Montreal in 1976. Since that time the misuse of anabolic steroids by athletes has been controlled by analysis of urine extracts by gas chromatography-mass spectrometry (GC-MS). The excreted steroids or their metabolites, or both, are isolated from urine by XAD-2 adsorption, enzymatic hydrolysis of conjugated excreted metabolites with beta-glucuronidase from Escherichia coli, liquid-liquid extraction with diethyl ether, and converted into trimethylsilyl (TMS) derivatives. The confirmation of an anabolic steroid misuse is based on comparison of the electron impact ionization (EI) mass spectrum and GC retention time of the isolated steroid and/or its metabolite with the EI mass spectrum and GC retention time of authentic reference substances. For this purpose excretion studies with the most common anabolic steroids were performed and the main excreted metabolites were synthesized for bolasterone, boldenone, 4-chlorodehydromethyltestosterone, clostebol, drostanolone, fluoxymesterone, formebolone, mestanolone, mesterolone, metandienone, methandriol, metenolone, methyltestosterone, nandrolone, norethandrolone, oxandrolone and stanozolol. The metabolism of anabolic steroids, the synthesis of their main metabolites, their GC retention and El mass spectra as TMS derivatives are discussed.