Page 102 - Advances in Forensic Applications of Mass Spectrometry - Jehuda Yinon

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standard. This was associated with much better accuracy and precision.
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The LOD (0.5 mg/l) has not been improved. Hoja et al. applied ESI-LC-MS
for determination of LSD and N-demethyl-LSD in urine after Extrelut extrac-
tion. The LOQ was 0.05 and 0.1 mg/l for LSD and metabolite, respectively.
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De Kanel et al. extracted LSD and its demethylated metabolite from 1 ml
blood, serum, plasma, and urine with automated mixed-phase SPE. The drugs
were detected with LC/ESI/MS/MS using phenyl column for separation. The
LOD of 0.025 mg/l for both substances was reported. In the study of Bodin
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et al. LSD was extracted from urine with organic solvent, back extracted
to an acetate buffer and subjected to LC/ESI/MS. The LOD was 0.02 mg/l.
Since only small fraction of LSD is eliminated with urine, its window of
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detection in urine following use is not longer than 12 to 22 h. The turning
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point in the analysis of LSD came when Poch et al. demonstrated the
importance of determination of 2-oxo-3-hydroxy-LSD, a prevalent metabolite
of LSD excreted with urine. This metabolite, as well as LSD, nor-LSD, and
iso-LSD were determined in urine with LC/APCI/MS (ion trap). The con-
centrations of 2-oxo-3-hydroxy-LSD were distinctly higher than those of the
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parent drug and other metabolites. In the next study, Poch et al. compared
three detection methods for LSD and metabolites: LC/APCI/MS,
LC/APCI/MS/MS (ion trap), and GC/MS. The latter method was used only
for the parent drug. Very good agreement between both LC/MS methods was
found. According to the authors, the detection window for LSD use may be
significantly increased due to determination of the metabolite. Sklerov et al. 112
determined LSD and 2-oxo-3-hydroxy-LSD in blood and urine. The drugs
were isolated from urine with alkaline solvent extraction; for blood a solvent
extraction followed by SPE was used. LC/ESI/MS was applied with in-source
collision-induced dissociation and monitoring of three ions for each com-
pound. LOD was 0.1 mg/l for LSD and 0.4 mg/l for metabolite in urine. In
authentic cases, 2-oxo-3-hydroxy-LSD was found in high concentrations in
urine but was not present in blood samples. A LC/ESI/MS/MS technique was
applied by Canezin et al. for determination of LSD and iso-LSD in plasma
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with LOD of 0.02 mg/l for both compounds. In urine metabolites also were
detected, such as 2-oxo-3-hydroxy-LSD, nor-LSD, nor-iso-LSD, 13- and 14-
OH-LSD-glucoronides, lysergic acid ethylamide, trioxydated-LSD, and lyser-
gic acid ethyl-2-hydroxyethylamide. The method was applied in two cases of
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drug abuse. Klette et al. studied the specificity of LC/MS assay of 2-oxo-3-
hydroxy-LSD. Fifteen compounds structurally related to LSD, as well as a
wide range of unrelated compounds, were studied. None of the examined
drugs interfered with the detection of the LSD metabolite. It was also found
that 2-oxo-3-hydroxy-LSD is stable for 60 days in urine samples stored in a
freezer or in a refrigerator at pH 4.6 to 8.4. Recent chromatographic methods
for cannabinoids and LSD are depicted in Table 2.3.
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