Page 38 - Advances in Forensic Applications of Mass Spectrometry - Jehuda Yinon

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gency toxicology. However, some compounds were destroyed or altered dur-
ing acid hydrolysis. 57,59,328 Therefore, the standard procedure 63 had to be
modified. Before extraction, half of the native urine volume was added to
the hydrolyzed part. The extraction solvent used has proved to be very effi-
cient in extracting compounds with very different chemical properties from
biomatrices, so that it has been used for a STA procedure for basic and neutral
analytes. 32,91,92,172,319 AC has proved to be very suitable for robust derivatiza-
tion in order to improve the GC properties and thereby the detection limits
32
of thousands of drugs and their metabolites. The use of microwave irradi-
ation reduced the incubation time from 30 to 5 min 59,329 so that derivatization
should no longer be renounced due to time consumption.
This comprehensive full scan GC/MS screening procedure allows, within
one run, the simultaneous screening and confirmation of the following cat-
egories of drugs: amphetamines, 130–132 designer drugs, 60,61,139,166,172,174 barbitu-
rates and other sedative–hypnotics, 223 benzodiazepines, 219 opiates, opioids
and other potent analgesics, 199,207 anticonvulsants, 218 antidepressants, 58,235
phenothiazine and butyrophenone neuroleptics, 236,330 nonopioid analge-
sics, 213,214 antihistamines, 224,237–239 antiparkinsonian drugs, 240 beta-blockers, 244
antiarrhythmics, 251,331 diphenol laxatives, 254 and, finally, herbal drugs like
62
32
atropine, scopolamine, lauroscholtzin, or protopine. In addition, series of
93
further compounds can be detected if they are present in the extract and
their mass spectra are contained in the used reference libraries. 92,94–96
Eight to ten ions per category were individually selected from the mass
spectra of the corresponding drugs and their metabolites identified in
authentic urine samples. Table 1.2 summarizes these target ions, which have
been updated and optimized. Generations of mass chromatograms can be
started by clicking the corresponding pull-down menu which executes the
91
user-defined macros. The procedure is illustrated in Figure 1.7 to Figure
1.16. In Figure 1.7, mass chromatograms are depicted corresponding to frag-
ment ions typical for opioids, indicating the peaks 5 to 9. Figure 1.8 to Figure
1.12 show the unknown mass spectra underlying peaks 5 to 9 (upper part,
each), the reference spectra (middle part, each), and the structures and the
hit lists found by library search in Reference 92 (lower part, each). As already
discussed for the plasma screening, besides the opioids oxycodone and dihy-
drocodeine, a compound not belonging to the monitored drug class is indi-
cated and could be identified as the muscle relaxant carisoprodol. Figure 1.13
shows mass chromatograms generated from the same data file, corresponding
to fragment ions typical for nonopioid analgesics. Besides the already known
compounds underlying the peaks 6, 7, and 9, peak 10 appears, which could
be identified as acetaminophen (paracetamol [INN], Figure 1.14). This
example illustrates again that the selective mass chromatograms provide only
a more or less selective screening and only the comparison of the peak

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