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The internal standard diquat-d4 causes errors in diquat analysis by LC–MS/MS

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Abstract

Purpose

We report a more reliable method for determination of the herbicide diquat (DQ) in human biological samples using stable isotope dilution liquid chromatography–tandem mass spectrometry (LC–MS/MS). DQ-d8, a newly synthesized stable isotope was used as the internal standard (IS) for quantification of DQ instead of DQ-d4 typically used so far. The use of DQ-d8 could completely prevent errors like the misdetection of DQ and inaccurate quantification probably caused by using DQ-d4. Additionally, we developed a method for simultaneous determination of DQ and the similar herbicide paraquat (PQ) in urine, serum and whole blood by stable isotope dilution LC–MS/MS after solid-phase extraction.

Methods

The stable isotopes DQ-d8 and PQ-d6 were synthesized and used as ISs. The DQ and PQ in the samples were extracted by solid-phase extraction using an EVOLUTE® WCX. The extracted DQ and PQ were separated and detected by LC–MSMS using a ZIC®-pHILIC column.

Results

The recovery rates ranged from 82.0 to 99.7%. Calibration curves showed good linearity in the 0.01–2 μg/mL. The intraday accuracy and intraday precision [% relative standard deviation (RSD)] ranged from 92.1 to 106% and from 0.4 to 4.7%, respectively. The interday precision (%RSD) ranged between 0.8 and 6.7%.

Conclusions

The stable isotopes DQ-d8 and PQ-d6 allowed for accurate and precise quantification. Especially for analysis of DQ, the use of DQ-d8 could completely prevent errors caused by using DQ-d4. Therefore, the proposed method would be of great use in criminal investigations and emergency medicine.

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Authors and Affiliations

  1. Forensic Science Laboratory, Chiba Prefectural Police Headquarters, 71-1 Chuoko 1-chome, Chuo-ku, Chiba-shi, Chiba, 260-0024, Japan

    Yusuke Suzuki & Tsuyoshi Kaneko

  2. Department of Analytical Chemistry, Faculty of Pharmaceutical Sciences, Hoshi University, 4-41 Ebara 2-chome, Shinagawa-ku, Tokyo, 142-8501, Japan

    Koichi Saito

Authors
  1. Yusuke Suzuki
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  2. Tsuyoshi Kaneko
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  3. Koichi Saito
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Correspondence to Yusuke Suzuki.

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Suzuki, Y., Kaneko, T. & Saito, K. The internal standard diquat-d4 causes errors in diquat analysis by LC–MS/MS. Forensic Toxicol 36, 458–466 (2018). https://doi.org/10.1007/s11419-018-0423-z

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  • DOI: https://doi.org/10.1007/s11419-018-0423-z

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