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Examination of Firearms Review: 2007 to 2010 - Interpol

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achiral separation <strong>of</strong> methadone, EDDP and EMDP was achieved, using a<br />

capillary coated with a polycation <strong>of</strong> poly(diallyldimethylammonium chloride)<br />

and a polyanion <strong>of</strong> dextran sulfate, with migration times <strong>of</strong> approximately 4 min<br />

[260]. To further separate enantiomers <strong>of</strong> methadone and EDDP, another CE<br />

method was developed using 0.2% highly sulphated gamma-cyclodextrins as<br />

chiral selec<strong>to</strong>rs, giving LODs <strong>of</strong> 2.3-2.4 ng/mL with a 5 min runtime [261]. The<br />

prevalence <strong>of</strong> elevated levels <strong>of</strong> CDT, a marker <strong>of</strong> chronic alcohol abuse in<br />

serum <strong>of</strong> DUI drivers, was studied by CE. With a cut-<strong>of</strong>f set at 2.00% (CDT<br />

index), 24 out <strong>of</strong> 40 drunken drivers were identified as chronic alcohol abusers<br />

[262].<br />

Due <strong>to</strong> its selectivity and sensitivity, CE coupled <strong>to</strong> MS (CE-MS) has evolved<br />

as a useful analytical <strong>to</strong>ol for determining drugs and metabolites in biological<br />

samples. Non-aqueous CE online coupled with a mass spectrometer for the<br />

analysis <strong>of</strong> phosphatidylethanol (Peth), another biomarker <strong>of</strong> chronic alcohol<br />

abuse in blood, was developed. With the use <strong>of</strong> phosphatidylbutanol as an<br />

internal standard, the estimated LOD was 0.1 µM, while LOQ was 0.4 µM [263].<br />

Determinations <strong>of</strong> illicit drugs and/or metabolites (opiates, cocaine,<br />

amphetamines, and methadone) in blood [264] and in hair [265] by CE-MS,<br />

were accomplished. LODs in blood were in the range <strong>of</strong> 2-10 ng/mL, while in<br />

hair were 0.1 ng/mg. With the use <strong>of</strong> protein precipitation (PP) prior <strong>to</strong> a<br />

hydrodynamic injection (HD) or liquid-liquid extraction (LLE) with electrokinetic<br />

injection (EK), CE-ESI-MS methods for analysis <strong>of</strong> ecstasy and methadone in<br />

plasma, were developed. Methods were linear over the concentration range <strong>of</strong><br />

0.50-175 ng/mL and 0.25-5 µg/mL for LLE-EK and PP-HD procedures,<br />

respectively [266].<br />

3.2 Extraction Techniques<br />

3.2.1 Liquid-phase microextraction (LPME)<br />

Liquid-liquid extraction (LLE) was one <strong>of</strong> the conventional sample preparation<br />

techniques extensively used for biological sample analysis, particularly for<br />

post-mortem <strong>to</strong>xicology. This method, however, is relatively time-consuming<br />

and produces relatively large amount <strong>of</strong> organic solvent waste. Liquid-phase<br />

microextraction (LPME), which requires much less organic solvent in the<br />

pretreatment procedure, was recently developed [267,268,269]. There are<br />

several types <strong>of</strong> LPME, including single-drop microextraction (SDME) [270],<br />

dispersive liquid-liquid microextraction (DLLME) [ 271 ], and hollow-fiber<br />

649

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