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Development of a two-dimensional LC–MS/MS system for the determination of proline and 4-hydroxyproline enantiomers in biological and food samples

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  • Novel Analytical Technologies Contributing to Clinical and Pharmaceutical Research Fields
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Abstract

A two-dimensional LC–MS/MS system has been developed for the enantioselective determination of proline (Pro), cis-4-hydroxyproline (cis-4-Hyp) and trans-4-hydroxyproline (trans-4-Hyp) in a variety of biological samples. The amino acids were pre-column derivatized with 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F), and the NBD-derivatives were separated by a reversed-phase column (Singularity RP18) as their d plus l mixtures in the first dimension. The collected target fractions were then introduced into the second dimension where the enantiomers were separated by a Pirkle-type enantioselective column (Singularity CSP-001S) and determined by a tandem mass spectrometer (Triple Quad™ 5500). The method was validated by the standard amino acids and also by human plasma, and sufficient results were obtained for the calibration, precision and accuracy. The method was applied to human plasma and urine, bivalve tissues and fermented food/beverages. d-Pro was widely found in the human physiological fluids, bivalves and several fermented products. Although trans-4-d-Hyp was not found in all the tested samples, cis-4-d-Hyp was present in human urine and tissues of the ark shell, and further studies focusing on the origin and physiological significance of these d-enantiomers are expected.

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Acknowledgements

This study was partly supported by JSPS KAKENHI Grant Numbers JP22H02752, JP22K06547 and JP23K14335. The authors appreciate KAGAMI, Inc. (Ibaraki, Osaka, Japan) for their technical support.

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Authors and Affiliations

  1. Graduate School of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka, 812-8582, Japan

    Chiharu Ishii, Komei Iwasaki, Takeyuki Akita & Kenji Hamase

  2. MIRAI Technology Institute, Shiseido Co., Ltd., 1-2-11 Takashima, Nishi-ku, Yokohama, 220-0011, Japan

    Yosuke Tojo

  3. Sakamoto Kurozu, Inc., 21-15 Uenosono-cho, Kagoshima, 890-0052, Japan

    Akira Fujii & Masanobu Nagano

  4. KAGAMI, Inc., 7-7-15, Saito-asagi, Ibaraki, Osaka, 567-0085, Japan

    Masashi Mita

  5. Graduate School of Medical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka, 812-8582, Japan

    Tomomi Ide

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  1. Chiharu Ishii
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Correspondence to Kenji Hamase.

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Ishii, C., Tojo, Y., Iwasaki, K. et al. Development of a two-dimensional LC–MS/MS system for the determination of proline and 4-hydroxyproline enantiomers in biological and food samples. ANAL. SCI. 40, 881–889 (2024). https://doi.org/10.1007/s44211-024-00530-w

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  • DOI: https://doi.org/10.1007/s44211-024-00530-w

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