Message from the chief editor
Content TypeJournal Article
JournalForensic ToxicologyOnline ISSN 1860-8973Print ISSN 1860-8965
Journal VolumeVolume 24
Journal IssueVolume 24, Number 1 / July, 2006 (Source: Forensic Toxicology)
Abstract Psilocin glucuronide (PCG) was directly identified in serum specimens of a “magic mushroom” user by liquid chromatography/mass
spectrometry (LC/MS) and LC/MS/MS, together with the free (unconjugated) psilocin (PC). A major part of serum PC existed in
the conjugated form. To quantify the total (conjugated plus free) PC in serum, enzymatic hydrolysis conditions were optimized
using the user’s urine as the source of PCG; PCG in serum could be completely hydrolyzed by Escherichia coli β-glucuronidase. Using the established procedure, both total and free PC in the serum specimens of the user collected at
various intervals were quantified. For the first specimen collected 5h after magic mushroom ingestion, 71.0 ng/ml of total
PC and 13.3 ng/ml of free PC were detected. The ratio of free PC to total PC decreased with time after ingestion. The β-glucuronidase
treatment of serum was found to clearly extend the detectable period of the serum PC; PC could be detected even 52 h after
ingestion of magic mushroom.
Content TypeJournal Article
JournalForensic ToxicologyOnline ISSN 1860-8973Print ISSN 1860-8965
Journal VolumeVolume 24
Journal IssueVolume 24, Number 1 / July, 2006 (Source: Forensic Toxicology)
Abstract Conversion of γ-hydroxybutyric acid (GHB) to a fluorescent derivative using 3-bromomethyl-6,7-dimethoxy-1-methyl-1,2-dihydroquinoxaline-2-one
(Br-DMEQ), and its application to drug screening were studied. Br-DMEQ reacted with the carboxyl group of sodium GHB in the
presence of a potassium salt and crown ether to produce a fluorescent derivative, which could be easily detected by thin-layer
chromatography (TLC). An electrospray ionization mass spectrum of the fluorogenic product supported the expected structure.
The Br-DMEQ-derivatized GHB gave an Rf value of 0.49 on TLC, which was easily distinguished from 19 other carboxylic acids;
all of the latter had Rf values over 0.61. Various sodium carboxylates including sodium GHB reacted with Br-DMEQ in the presence
of KCl, but the free forms of the carboxylic acids did not react under these conditions. When aqueous solution containing
GHB was pretreated with sulfuric acid, GHB was converted to γ-butyrolactone, resulting in removal of its reactivity with Br-DMEQ.
By such analysis following the derivatization, with and without the above pre-treatment with sulfuric acid, GHB added to human
urine could be specifically detected, although the limit of detection was about 100μg/ml, which was 20 times higher than the
endogenous blood GHB level. Therefore, the present method seems useful for screening GHB present in a solid state such as
powder and tablets, and also in urine samples obtained in overdose cases.
Content TypeJournal Article
JournalForensic ToxicologyOnline ISSN 1860-8973Print ISSN 1860-8965
Journal VolumeVolume 24
Journal IssueVolume 24, Number 1 / July, 2006 (Source: Forensic Toxicology)
Abstract Gas chromatography-mass spectrometry (GCMS) is the preferred method for the analysis of drugs/metabolites in biological specimens
with use of isotopically labeled analogs of the analytes as internal standards (ISs). An important aspect of the chemical
derivatization (CD) for GC-MS analysis is that the CD products derived from the analyte and the selected IS must generate
ions suitable for designating the analyte and the IS. These ions should not have significant cross contribution (CC), i.e.,
IS contribution to the intensities of the ions designated for the analyte, and vice versa. With this in mind, the authors
have conducted a search of isotopically labeled analogs of commonly abused cocaine and related compounds (cocaine, norcocaine,
benzoylecgonine, cocaethylene, ecgonine, ecgonine methyl ester, anhydroecgonine methyl ester) that are commercially available.
These ISs and analytes were derivatized with various groups of reagents, and the CD products were analyzed by GC-MS. MS data
are presented in two forms: (1) systematic presentation of fullscan spectra; and (2) tabulation of CC data for ions with potential
for designating the ISs and analytes. Many (if not most) of these full-scan spectra are not yet available in the open literature
and should be of routine reference value to forensic and clinical laboratories that are engaged in the analysis of these drugs/metabolites.
Fullscan MS data were further used to select ion pairs with potential for designating the analytes and ISs in quantitative
analysis protocols. The CC data of these ion pairs were evaluated using data collected under the selected ion-monitoring mode
and summarized in table format. The data exhibited similar CC characteristics in each alkyl, acetyl, or TMS series. Among
the potentially usable ion pairs derived from a specific CD group, there was a trend that the ion pairs with higher mass showed
better CC data. The CC data derived from the use of ISs labeled with more deuterium atoms were generally more favorable. These
data should save enormous amounts of time and effort for practicing laboratories in their search for optimal analytical parameters.
Content TypeJournal Article
JournalForensic ToxicologyOnline ISSN 1860-8973Print ISSN 1860-8965
Journal VolumeVolume 24
Journal IssueVolume 24, Number 1 / July, 2006 (Source: Forensic Toxicology)
