Cathinone-type designer drugs are a newly-encountered drug family that has a β-ketophenethylamine skeleton. Recently, the abuse of these drugs has been increasingly common among young adults, and this has caused a serious social problem in many countries. Many of those drugs have become regulated by the Pharmaceutical Affairs Act, and some of them were later banned by the Narcotics and Psychotropics Control Act in Japan, depending on their structures. In this paper, a total of 98 standards of cathinone-type designer drugs were synthesized, and their EI-mass spectra were acquired by GC/MS, with and without trifluoroacetylation. For their free bases, a major fragment ion formed from the α-cleavage of the amine nitrogen was commonly observed. Also, a small fragment ion generated by the α-cleavage of the carbonyl group, followed by the elimination of CO was detectable. For the analogs having an N-alkyl chain longer than methyl group and/or the alkyl side-chain longer than methyl group, a characteristic ion formed from the α-cleavage of the amine nitrogen, followed by the elimination of the olefin moiety was observed. For the trifluoroacetyl derivatives, the intensity of fragment ion formed from the α-cleavage of carbonyl group significantly increased, while that of the fragment ion generated from the α-cleavage of nitrogen decreased, when compared with those of free bases. Also, the ion at m/z 110 was specifically observed for the cathinone analogs having a methylamino group. Those typical fragmentation patterns revealed by analyzing a series of analogs provide useful information for the characterization of cathinone-type designer drugs.

View full abstract

  The in vivo metabolism of 2,5-dimethoxy-4-ethylthiophenethylamine (2C-T-2) and 2,5-dimethoxy-4-isopropylthiophenethylamine (2C-T-4), new psychoactive drugs, were studied using rats. 2C-T-2 hydrochloride and 2C-T-4 hydrochloride were administered separately to male Sprague-Dawley rats via the oral route (10 mg/kg), and the urinary extracts were analyzed by liquid chromatography/mass spectrometry. Fourteen and ten metabolites for 2C-T-2 and 2C-T-4 were detected in the urinary extracts, respectively. Our results suggested that sulfoxidation, sulfone formation, S-dealkylation followed by S-methylation, N-acetylation and deamination followed by oxidation were the major metabolic pathways of 2C-T-2 and 2C-T-4 in rat.

View full abstract

  OC-Hemocatch (HC), an immunochromatographic test device for fecal occult blood, has been used for the forensic identification of human blood. However, an improved kit, OC-Hemocatch S (HC-S), is currently available and HC was discontinued. Therefore, the applicability of HC-S for the forensic identification of human blood was evaluated. In addition, false-positive reactions with disinfectants and detergents, which were observed when using HC, were tested in HC-S. Similar to HC, HC-S was highly sensitive and specific for the detection of human blood. False-negative results due to high concentrations of human hemoglobin were not observed in 100-fold diluted blood. However, distilled water was not suitable as a diluent. The effects of heating treatment of blood and bloodstains and long-term storage of bloodstains on HC-S were similar with HC. However, no false-positive results were observed when disinfectants and detergents were used for HC-S. In conclusion, HC-S is a suitable and highly efficient test kit for the forensic identification of human blood.

View full abstract

  Methylamphetamines (methylamphetamine (Me-AP) and methylmethamphetamine (Me-MA)) have three ringpositional isomers. Among them, 4-Me-AP has been controlled as a designated substance (Shitei-Yakubutsu) in Japan since November 2012. Furthermore, Me-APs are a structural isomer of methamphetamine (MA), controlled as a stimulant. Because of the increasing number of structural isomer of designer drugs encountered in forensic science laboratories, analytical differentiation of structural isomers is a significant issue. In this study, a method for differentiation of methylamphetamines using gas chromatography/mass spectrometry (GC/MS) was developed. DB-1ms and DB-5ms columns could not separate free bases and trifluoroacetyl (TFA) derivatives of methylamphetamines while the columns incompletely separated their trimethylsilyl (TMS) derivatives. On the other hand, the mid-polar DB-17ms column separated free bases, TFA and TMS derivatives of 6 methylamphetamines though peak shapes of the free bases were tailing. The best separation was obtained from the analysis of the TMS derivatives on DB-17ms column. The mass spectra showed a little difference between the 2-, 3-Me-AP and 4-Me-AP after TFA derivatization. Also the structural isomers of Me-AP and MA could be differentiated by their EI mass spectra. The results indicated that differentiation of regioisomeric methylamphetamines could be accomplished well by GC/MS of their TMS derivatives on the mid-polar capillary column.

View full abstract

  Instrumental neutron activation analysis (INAA) and inductively coupled plasma-mass spectrometry (ICP-MS) were applied to determine minor and trace elements in human nail samples. Validation of each method was performed by measuring NIES No. 5 Human Hair certified reference material. Good agreements were observed between certified and measured values for these methods. Nail samples collected from 18 healthy volunteers were washed, dried and cut into small pieces. The samples were divided into two portions, one of which was analyzed by INAA and the other by ICP-MS. In INAA, Na, Mg, Al, Cl, K, Ca, V, Mn and Cu were recognized and the concentrations of these elements were calculated. On the other hand, peaks of Cu, Zn, Sr, Ag, Sn, Sb, Ba, Ce Hg and Pb were observed in the spectrum by ICP-MS. Copper, Zn, Sr, Ag and Pb were determined by ICP-MS because these elements showed sufficiently high intensity without spectrum interference. Nine and five elements were determined by INAA and ICP-MS. Copper was determined by both methods, and good correlation was observed. Combination of INAA and ICP-MS has an advantage to provide more information of elemental contents for nail samples if more than only one of the two methods is employed.

View full abstract

  Kinship analysis using DNA typing plays an important role in the identification of an unknown decedent. We have developed a tool based on Microsoft Office Excel to support kinship analysis. The tool calculates likelihood ratios (LRs) based on Wenk's equation when the STR (short tandem repeat) types of the unknown decedent and those of the alleged relative are entered. We validated the tool by calculating LRs for 100 cases of unknown person-alleged child relationships and 100 cases of unknown person-alleged sibling relationships. The values of the LRs calculated with this tool were consistent with those calculated using the DNA-VIEW software. Further, the distribution of the LRs was almost the same as the distribution of simulated LRs in paternity and sibling tests reported in a previous study. This tool should expedite the fast and efficient identification of an unknown decedent.

View full abstract

  Glass fragments are valuable evidence in the criminal investigation of hit-and-run, murder and burglary cases. Screening of glass fragments should be carried out by refractive index (RI) measurement after the identification of unknown fragments of glass by analysis using electron probe microanalysis (EPMA), scanning electron microscopy with an energy dispersive X-ray spectrometer (SEM-EDS) and/or X-ray fluorescence spectrometry (XRF). However, it has been pointed out that RI values of glass fragments can be influenced by electron beam and/or X-ray of the instrumental analysis, although the effect of them on RI values of glass has not been sufficiently examined.
  In this work, we compared the RI values of glass fragments before and after irradiation by electron beam and/or X-ray using these devices. Glass fragments were collected from 3 different uses (windowpane of building, windshield and beer bottle). No significant difference was recognized in the RI values of these glass fragments before and after 30 minutes of irradiation.
  We have ascertained that the effect of electron beam and/or X-ray on the RI values is negligible in the conditions of the present study and that comparison of RI values is still useful for the forensic screening of glass fragments even after the instrumental analysis described above.

View full abstract

[in Japanese]

View full abstract