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Examination of Firearms Review: 2007 to 2010 - Interpol

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sports. A method was described for unequivocal identification <strong>of</strong> DPO in<br />

human plasma [ 398 ]. The analyte was extracted from plasma by<br />

immunoaffinity separation with anti-rhEPO antibodies, digested by trypsin<br />

followed by peptide-N-glycoside F (PNGase F), and analyzed by LC-MS/MS;<br />

the LOD for DPO was 0.1 ng/mL. Four proposed new markers for detection <strong>of</strong><br />

rhEPO abuse were reported. Preliminary data showed that concentrations <strong>of</strong><br />

asymmetrical dimethylarginine (ADMA), symmetrical dimethylarginine (SDMA),<br />

citrulline, and arginine in human urine were increased after administration <strong>of</strong> a<br />

single intravenous erythropoietin injection, up <strong>to</strong> 40-270 µg /mL, 40-240 µg/ mL,<br />

10-60 µg /mL and 12-140 µg/ mL, respectively [399].<br />

While samples containing endogenous growth hormone (GH) yield up <strong>to</strong> four<br />

is<strong>of</strong>orms, samples with recombinant GH contain the main 22 kDa spot only. A<br />

method was reported <strong>to</strong> separate different is<strong>of</strong>orms by two-dimensional<br />

polyacrylamide gel electrophoresis (2-D PAGE) after isolation <strong>of</strong> GH from<br />

plasma, using an immunoaffinity purification system which detected discrete<br />

is<strong>of</strong>orms <strong>of</strong> GH from plasma, thereby discriminating endogenous GH from its<br />

recombinant analog [400]. A mass spectrometric approach was developed <strong>to</strong><br />

determine the nondegraded hormone, gonadotropin-releasing hormone<br />

(GnRH), in doping control samples with SPE, immunoaffinity purification, and a<br />

subsequent analysis by LC-ESI-MS/MS [401]. The method <strong>of</strong>fered an LOD <strong>of</strong><br />

about 5 pg/mL, and urinary concentrations <strong>of</strong> the intact peptide in<br />

post-administration samples ranged from 20 - 100 pg/mL.<br />

Doping control analysis <strong>of</strong> performance-enhancing peptides in urine<br />

represents a challenging requirement in modern sports drug testing: Low<br />

doses and short half-lives lead <strong>to</strong> low concentrations (in fmol/mL range) in<br />

urine. Immunoaffinity purification with UPLC-MS/MS (high resolution/high<br />

mass accuracy) <strong>of</strong> Synacthen from urinary specimens is described and<br />

validated with LOD <strong>of</strong> 3 pg/mL [402].<br />

A study was conducted on the intra-individual variance <strong>of</strong> <strong>to</strong>tal hemoglobin<br />

mass (tHb-mass) in elite athletes during a training year as the basis <strong>to</strong><br />

measure tHb-mass as an effective screening parameter for detecting blood<br />

doping [403]. Results showed that tHb-mass was very low for individuals<br />

during a training year (

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