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Examination of Firearms Review: 2007 to 2010 - Interpol

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2 ng/mL <strong>of</strong> 19-NA was concluded <strong>to</strong> be a fair upper acceptable limit in doping<br />

control tests for female athletes.<br />

The metabolism <strong>of</strong> methyltes<strong>to</strong>sterone has been reinvestigated by the use <strong>of</strong> a<br />

precursor ion scan method in LC-ESI-MS/MS [388]. Two metabolites have<br />

been detected using this method, namely epimethyltes<strong>to</strong>sterone and a<br />

dehydrogenated compound. Comparison with the synthesized reference<br />

standard revealed that the structure <strong>of</strong> the dehydrogenated metabolite is<br />

6-ene-epimethyltes<strong>to</strong>sterone. 6-Ene-epimethyltes<strong>to</strong>sterone was found in all<br />

samples, demonstrating its applicability in the detection <strong>of</strong> methyltes<strong>to</strong>sterone<br />

misuse.<br />

An approach based on precursor ion scanning <strong>of</strong> m/z 105, 91, and 77<br />

corresponded <strong>to</strong> the methyl tropylium, tropylium, and phenyl ions, respectively,<br />

for the detection <strong>of</strong> unknown anabolic steroids, their metabolites and<br />

prohormones, was proposed [ 389 ]. In general, only compounds with a<br />

steroidal structure showed a signal at all three selected m/z values, although<br />

some exceptions have been found. A new doping control screening method<br />

has been developed using HPLC/orbitrap with in-source collision-induced<br />

dissociation and atmospheric pressure chemical ionization, for the detection <strong>of</strong><br />

29 compounds, including agents with antiestrogenic activity, beta(2) agonists,<br />

exogenous anabolic steroids, and other anabolic agents [390]. The mass<br />

accuracy <strong>of</strong> this method is better than 2 ppm using an external reference, with<br />

LODs for all compounds tested better than 100 pg/mL. Ten steroids<br />

(11-beta-hydroxyandrosterone, 5-alpha-androst-16-en-3-alpha-ol,<br />

pregnanediol, androsterone, etiocholanolone, tes<strong>to</strong>sterone, epites<strong>to</strong>sterone,<br />

5-alpha-androstan-3-alpha,17-beta-diol,<br />

5-beta-androstan-3-alpha,17-beta-diol and dehydroepiandrosterone) were<br />

measured from a single urine specimen by a GC/thermal conversion<br />

(TC)/IRMS method for deuterium/hydrogen ratio [391]. For a 20 mL specimen,<br />

the LODs ranged from 10-15 ng/mL. The applicability <strong>of</strong> comprehensive<br />

two-dimensional gas chroma<strong>to</strong>graphy (GCxGC) for sterol analysis was<br />

investigated by separation and identification <strong>of</strong> endogenous sterols in<br />

standards, and spiked in human urine [ 392 ]. The match quality <strong>of</strong><br />

GCxGC-TOFMS spectra was reported <strong>to</strong> be superior <strong>to</strong> that for analysis using<br />

1D GC-TOFMS for sterols spiked in urine at 10 ng/mL. The LOD for estrone<br />

was 0.1 ng/mL, while the highest LOD was for<br />

5-alpha-androstan-3-alpha,11-beta-diol-17-one, epites<strong>to</strong>sterone, and<br />

661

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