Page 83 - Advances in Forensic Applications of Mass Spectrometry - Jehuda Yinon

1522_C02.fm Page 71 Wednesday, November 12, 2003 9:36 AM

quadrupole, working in the selected ion monitoring mode. The advantage
of the ion trap was that it provided a full spectra of substances. The ion ratios
were slightly more precise for quadrupole. These data may be also useful for
the assessment of ion trap LC/MS.

2.3 LC/MS Analysis of Illicit Drugs

2.3.1 Opiate Agonists
2.3.1.1 Analysis of Street Drugs
35
Dams et al. applied sonic spray LC/MS (ion trap) for profiling of street
heroin samples. Chromatographic separation was performed on monolithic
silica column (chromolith performance 100 ¥ 4.6 mm) in gradient elution
in acetonitrile–water at a flow of 5 ml/min. A postcolumn split of 1/20 was
applied; the analysis time was 5 min. The protonated molecular ions of
seven constituents of street heroin (morphine, codeine, 6-MAM, heroin,
acetylcodeine, papaverine, noscapine, and levallorphan, used as internal
standard) were monitored. The limits of SSI/MS detection ranged from 0.25
to 1 ng on-column.

2.3.1.2 Analysis of Biological Fluids
The advent of LC/MS brought very important progress in determination of
opiates and its metabolites in biological fluids. The most important opiate
agonist — heroin — is very rapidly deacetylated to 6-monoacetylmorphine
and consecutively to morphine. Morphine in turn is demethylated to nor-
morphine. Both active heroin metabolites — morphine and normorphine —
are then glucuronidated to 3- and 6-glucuronides. A similar process applies
to all natural and semi-synthetic opiates. 36 LC/MS is the only analytical tech-
nique which allows specific detection of parent opiates and all polar metab-
olites without derivatization and without acidic or enzymatic cleavage.
37
Zuccaro et al. developed an LC/ESI/MS method for the simultaneous
determination of heroin, 6-MAM, morphine, M3G, and M6G in serum. The
drugs were extracted with SPE C cartridges and separated on a straight-
2
phase silica column in a methanol–ACN–formic acid mobile phase. The
authors used a silica column in order to separate all substances in one run
under isocratic conditions. The LOD for heroin was 0.5 mg/l, for 6-MAM, 4
mg/l. The method was applied for a pharmacokinetic study on heroin-treated
38
mice. Bogusz et al. used atmospheric pressure chemical ionization
LC/APCI/MS for a determination of heroin metabolites (6-MAM, morphine,
M3G, and M6G) in blood, cerebrospinal fluid, vitreous humor, and urine of
heroin victims. The drugs were extracted with C18 cartridges; the LOD for
6-MAM was 0.5 mg/l. Low molar ratios of M3G/morphine and M6G/mor-

© 2004 by CRC Press LLC