Page 108 - Advances in Forensic Applications of Mass Spectrometry - Jehuda Yinon

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(amphetamine, methamphetamine, MDMA, MDEA, and MDA), and opiates
(morphine, codeine, 6-MAM), as well as cocaine and benzoylecgonine were
isolated from spiked saliva with three protein precipitation procedures. In
each case, serious ionization suppression was observed. The author warned
that during the use of a highly selective method like LC/MS/MS in an MRM
mode, the influence of the matrix may go unnoticed and he postulated the
use of optimized sample preparation methods. The same Belgian group 126
established a LC/ESI/qTOF/MS method for the determination of various
drugs of abuse: opiates (morphine and codeine), and amphetamines
(amphetamine, methamphetamine, MDMA, MDEA, and MDA) as well as
cocaine and benzoylecgonine in oral fluid. For a mixed-mode SPE, 200 ml of
sample was used. The drugs were separated in a methanol–ammonium for-
mate gradient on a narrow-bore phenyl column. The recoveries varied from
52 to 99%; the LOQ was 2 mg/l for all compounds. The method was applied
for real samples obtained from car drivers suspected of drug use.

2.4 LC/MS Analysis of Therapeutic Drugs
of Forensic Relevance

2.4.1 Incapacitating Drugs
Some drugs may be used as a chemical weapon to render a victim defenseless,
usually in the cases of forced sexual abuse. These compounds are known as
“date rape drugs.” The drugs belonging to this category cause fast loss of
consciousness after a low dose. The victims often develop amnesia and are
not able to give a reliable report of the attacks. All groups of drugs used for
127
incapacitating purposes were presented in a recent monograph. The most
important drugs used for incapacitation are flunitrazepam and other benzo-
diazepines, usually used together with alcoholic beverages, gamma-hydroxy-
butyrate (GHB), and related products; and hallucinogens and opioids.

2.4.1.1 Benzodiazepines
Flunitrazepam, a potent hypnotic drug, is of particular toxicological impor-
tance due to its high toxicity in combination with ethyl alcohol and subse-
quent misuse in drug-facilitated sexual assaults. Since flunitrazepam quickly
disappears from the blood, simultaneous determination of its active metab-
olites, particularly of the prevalent 7-aminoflunitrazepam, is very important.
Contrary to GC/MS, LC/MS allowed determination of polar metabolites of
flunitrazepam without derivatization. Bogusz et al. 128 developed a
LC/APCI/MS method for determination of flunitrazepam and its metabolites
7-aminoflunitrazepam, N-desmethylflunitrazepam, and 3-OH-fluni-

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