RECiQ: A Rapid and Easy Method for Determining Cyanide Intoxication by Cyanide and 2-Aminothiazoline-4-carboxylic Acid Quantification in the Human Blood Using Probe Electrospray Ionization Tandem Mass Spectrometry.

In this study, we developed a rapid and easy method to determine cyanide (CN) intoxication by quantification of CN and 2-aminothiazoline-4-carboxylic acid (ATCA), which is a new and reliable indicator of CN exposure, in the human blood using probe electrospray ionization tandem mass spectrometry (PESI/MS/MS) named RECiQ. For CN, we applied the previously reported one-pot derivatization method using 2,3-naphthalenedialdehyde and taurine, which can directly derivatize CN in the blood. The analytical conditions of the CN derivatization were optimized as a 10 min reaction time at room temperature. In contrast, ATCA could be directly detected in the blood by PESI/MS/MS. We developed quantitative methods for the derivatized CN and ATCA using an internal standard method and validated them using quality control samples, demonstrating that the linearities of each calibration curve were greater than 0.995, and intra- and interday precisions and accuracies were 5.1-15 and 1.1-14%, respectively. Moreover, the lower limit of detections for CN and ATCA were 42 and 43 ng/mL, respectively. Finally, we applied RECiQ to three postmortem blood specimens obtained from victims of fire incidents, which resulted in the successful quantification of CN and ATCA in all samples. As PESI/MS/MS can be completed within 0.5 min, and the sample volume requirement of RECiQ is only 2 µL of blood, these methods are useful not only for the rapid determination of CN exposure but also for the estimation of the CN intoxication levels during an autopsy.

Analysis of pyrolysis products of methamphetamine.

This study examined the pyrolysis products of d-methamphetamine (d-MA) and the pyrolysis mechanism. A sealed glass tube, in which MA-HCl was placed, was wrapped with pyrolysis-foil and heated at the Curie point of the pyrolysis-foil. The pyrolysis products of MA were detected by gas chromatography-mass spectrometry and liquid chromatography-electrospray ionization-mass spectrometry. MA-d(3)-HCl, in which all the hydrogen atoms of N-methyl group of MA were substituted with deuterium atoms, was pyrolyzed to investigate the transformation of a methyl group of MA. Amphetamine (AM) and dimethylamphetamine (DMA) were produced via demethylation and methylation reactions, respectively, at temperatures above 315 degrees C. The demethylation and methylation reactions were the major pyrolysis processes at temperatures below 358 degrees C. At temperatures above 315 degrees C, the reaction of DMA with a methyl group eliminated from the methylamino group of MA resulted in the formation of benzylethyltrimethylammonium (BEMA). This transformation reveals that demethylation and methylation reactions occur in the form of a methyl cation. The thermal degradation of BEMA, the abstraction of a proton at the beta-position and the elimination of a trimethylamine, produced allylbenzene, cis-beta-methylstyrene, and trans-beta-methylstyrene at temperatures above 315 degrees C. At temperatures above 445 degrees C, the optical isomers, or l-isomers of AM, MA, and DMA, were produced as pyrolysis products.

Rapid and sensitive determination of morphine in street opium samples by thermal desorption gas chromatography using a microfurnace pyrolyzer.

Thermal desorption of the alkaloids in opium samples at 300 degrees C using a vertical microfurnace pyrolyzer was followed by their on-line gas chromatographic (GC) analysis on a large-bore glass capillary column. This method permitted rapid and sensitive determination of the content of the main alkaloid, morphine, in the small (ca. 100 microg) opium samples with a relative standard deviation within 4% for 5 runs. The observed morphine contents of about 12 to 15 w/w% in the given opium samples were in fairly good agreement with those estimated by a conventional GC-MS method.

Analysis of dimethylamphetamine and its metabolites in human urine by liquid chromatography-electrospray ionization-mass spectrometry with direct sample injection.

An analytical method to identify and determine dimethylamphetamine (DMA) and its metabolites in human urine was developed with liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) involving the direct injection of a urine sample. The urine samples were directly injected by using a gel permeation column, whose stationary phase was polyvinyl alcohol with a small amount of a carboxyl group, so DMA and its metabolites were analyzed rapidly and simply without pretreatment such as extraction, concentration and derivatization. DMA and its metabolites were identified in drug-free human urine spiked with 1 microg of DMA, dimethylamphetamine N-oxide (DMANO) and methamphetamine (MA), and 3 microg of amphetamine (AM) in 1 ml of urine under the full-scan mode. Under the selected ion monitoring (SIM) mode, the limits of detection (signal-to-noise ratio=5) for DMA, DMANO, MA and AM were 20, 20, 20 and 60 ng in 1 ml of urine, respectively. This method was applied to the identification and determination of DMA and its metabolites in urine samples of 10 DMA abusers. The concentrations of DMANO were higher than those of unchanged DMA in all urine samples; thus, DMANO is considered to be a useful metabolite as an indicator to prove DMA intake.