A rapid and sensitive detection method using matrix-assisted laser desorption ionization (MALDI)–quadrupole time-of-flight–mass spectrometry (Q-TOF–MS) was developed for the analysis of six pyrrolidino cathinone derivatives, α-pyrrolidinopentiothiophenone (PVT), 4′-fluoro-α-pyrrolidinopentiophenone (F-PVP), 4′-methyl-α-pyrrolidinohexanophenone (MPHP), α-pyrrolidinoheptanophenone (PV8), α-pyrrolidinooctanophenone (PV9) and 4′-fluoro-α-pyrrolidinooctanophenone (F-PV9), that were newly designated as illegal drugs in Japan. In this method, α-cyano-4-hydroxycinnamic acid was used as the matrix to assist the ionization of cathinones. MS spectra of these cathinones showed a protonated molecule [M+H]+ and iminium, respectively, and hence the main ions of MALDI–MS were a mixture of the main ions detected by liquid chromatography–electrospray ionization–mass spectrometry and that by gas chromatography–electron ionization–mass spectrometry. The quantification of these cathinones was performed using α-pyrrolidinopentiophenone as the internal standard. The limit of detection was 1 ng/ml and the quantification range was 2–100 ng/ml for these cathinones using 20 μl of blood. We encountered a fatal poisoning case where PV9 was abused. The PV9 levels in postmortem blood samples from the right heart, left heart and femoral vein were 198, 209 and 163 ng/ml, respectively. The metabolites of PV9 were detected, and the peak height of an oxidized metabolite was higher than those of the protonated molecule and the other metabolites.
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This work was supported by a Grant-in-Aid for Scientific Research (Number 2560867) from the Ministry of Education, Science, Sports and Culture of Japan.
Conflict of interest
The authors state that they have no financial or other relations that could lead to a conflict interest.
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Minakata, K., Yamagishi, I., Nozawa, H. et al. Determination of new pyrrolidino cathinone derivatives, PVT, F-PVP, MPHP, PV8, PV9 and F-PV9, in human blood by MALDI-Q-TOF mass spectrometry. Forensic Toxicol 33, 148–154 (2015). https://doi.org/10.1007/s11419-014-0248-3
- α-Pyrrolidinooctanophenone (PV9)
- Pyrrolidino cathinone derivatives
- MALDI–Q-TOF mass spectrometry
- α-Cyano-4-hydroxy cinnamic acid