Determination of new pyrrolidino cathinone derivatives, PVT, F-PVP, MPHP, PV8, PV9 and F-PV9, in human blood by MALDI-Q-TOF mass spectrometry

Abstract

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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Acknowledgments

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.

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The authors state that they have no financial or other relations that could lead to a conflict interest.

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Correspondence to Kayoko Minakata.

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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

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Keywords

  • α-Pyrrolidinooctanophenone (PV9)
  • Pyrrolidino cathinone derivatives
  • MALDI–Q-TOF mass spectrometry
  • α-Cyano-4-hydroxy cinnamic acid
  • Blood