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Stir-bar-sorptive extraction, with in-situ deconjugation, and thermal desorption with in-tube silylation, followed by gas chromatography-mass spectrometry for measurement of urinary 4-nonylphenol and 4-tert-octylphenol glucuronides

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Abstract

A novel method, stir-bar-sorptive extraction (SBSE), with in-situ deconjugation and thermal desorption (TD) with in-tube silylation, followed by gas chromatography-mass spectrometry (GC-MS), for determination of trace amounts of 4-nonylphenol glucuronide (NP-G) and 4-tert-octylphenol glucuronide (OP-G) in human urine, is described. The method involved correction by use of stable isotopically labeled internal standards 4-(1-methyl)octylphenol-d5 (NP-d) and deuterium 4-tert-octylphenol (OP-d). A human urine sample to which β-glucuronidase had been added was extracted for 90 min at 37 °C using a stir bar coated with a 500-μm-thick layer of polydimethylsiloxane (PDMS). NP-G and OP-G were deconjugated, becoming free 4-nonylphenol (NP) and 4-tert-octylphenol (OP). The analytes were then extracted with the PDMS stir bar and the stir bar was subjected to TD with in-tube silylation; this was followed by GC-MS in selected-ion-monitoring (SIM) mode. To optimize the conditions for SBSE with in-situ deconjugation and to test recovery, NP-G and OP-G were synthesized by a biochemical technique in our laboratory. Average recoveries from human urine samples spiked with NP-G and OP-G were between 91.9 and 95.6% with correction using the added surrogate standards. Limits of detection were 0.11 ng mL−1 for NP and 0.01 ng mL−1 for OP. We also measured background levels of NP-G and OP-G in six urine samples from healthy volunteers. NP and OP were detected in the samples at concentrations of 0.62–1.95 ng mL−1 and <0.04–0.18 ng mL−1, respectively.

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Acknowledgment

This study was supported by Health Sciences Research grants from the Ministry of Health, Labour and Welfare of Japan, Research Fellowships of the Japan Society for the Promotion of Science for Young Scientists, Grant-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science and Technology, and The Hoshi University Otani Research Grant.

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Authors and Affiliations

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

    Migaku Kawaguchi, Rie Ito, Norihiro Sakui, Noriya Okanouchi, Koichi Saito & Hiroyuki Nakazawa

  2. Yokogawa Analytical Systems Inc., Kinryo Bldg., 3-3-11 Niitaka, Yodogawa-ku, Osaka, 532-0033, Japan

    Norihiro Sakui

  3. National Research Institute of Police Science, 6-3-1 Kashiwanoha, Kashiwa-shi, Chiba, 277-0882, Japan

    Yasuo Seto

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  1. Migaku Kawaguchi
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  2. Rie Ito
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  3. Norihiro Sakui
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  4. Noriya Okanouchi
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  5. Koichi Saito
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  6. Yasuo Seto
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  7. Hiroyuki Nakazawa
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Correspondence to Hiroyuki Nakazawa.

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Kawaguchi, M., Ito, R., Sakui, N. et al. Stir-bar-sorptive extraction, with in-situ deconjugation, and thermal desorption with in-tube silylation, followed by gas chromatography-mass spectrometry for measurement of urinary 4-nonylphenol and 4-tert-octylphenol glucuronides. Anal Bioanal Chem 388, 391–398 (2007). https://doi.org/10.1007/s00216-007-1225-z

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