Development of two-dimensional LC/IRMS for organic solvents

• Project/Area Number: 20K20639
• Research Category: Grant-in-Aid for Challenging Research (Pioneering)
• Allocation Type: Multi-year Fund
• Review Section: Medium-sized Section 64:Environmental conservation measure and related fields
• Research Institution: Shibaura Institute of Technology (2023); Akita Prefectural University (2020-2022)
• Principal Investigator: Kawashima Hiroto 芝浦工業大学, システム理工学部, 教授 (60381331)
• Project Period (FY): 2020-07-30 – 2024-03-31
• Project Status: Completed (Fiscal Year 2023)
• Budget Amount: ¥25,870,000 (Direct Cost: ¥19,900,000、Indirect Cost: ¥5,970,000); Fiscal Year 2023: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000); Fiscal Year 2022: ¥6,630,000 (Direct Cost: ¥5,100,000、Indirect Cost: ¥1,530,000); Fiscal Year 2021: ¥9,880,000 (Direct Cost: ¥7,600,000、Indirect Cost: ¥2,280,000); Fiscal Year 2020: ¥6,370,000 (Direct Cost: ¥4,900,000、Indirect Cost: ¥1,470,000)
• Keywords: LC/IRMS / 安定同位体 / 炭素安定同位体 / 有機溶媒 / 食品 / 安定同位体比 / 液体クロマトグラフ / 二次元LC / マルチアイソトープ

Outline of Research at the Start

近年開発された液体クロマトグラフ/安定同位体比質量分析計（LC/IRMS）は水溶性成分の炭素安定同位体比の高精度分析を可能にした。その結果，様々な食品偽装を見分ける応用研究等が現在，海外では報告され始めている。しかし，装置の制約として，対象物質は水溶性成分に限られることや，炭素安定同位体のみを対象としていることなど，未だに多くの課題がある。本研究では，LC/IRMSの用途拡大を目的として，2次元LC/IRMSを開発し，溶離液に有機溶媒を使用することで疎水性成分を対象にし，また炭素，窒素，硫黄の安定同位体比を対象元素にする等，革命的な装置開発を目指す。

Outline of Final Research Achievements

In 2004, a liquid chromatograph/stable isotope ratio mass spectrometer (LC/IRMS) was developed and commercialized for the high-precision analysis of carbon stable isotope ratios of water-soluble components using a wet combustion method. The objective of this study was to develop a more innovative LC/IRMS instrument capable of utilizing organic solvents as eluents. The results suggest that LC/IRMS can separate and analyze multiple water-soluble vitamins by combining first and second dimensional columns. The availability of organic solvents will expand the utility of LC/IRMS across various fields and for analyzing complex components that have been challenging to analyze previously.

Academic Significance and Societal Importance of the Research Achievements

既存のLC/IRMSでは，δ13Cは二酸化炭素の状態で分析するため，炭素を含んだ有機溶媒は今まで全く使用できなかったが，2次元LC/IRMSを利用することで有機溶媒の使用が出来る可能性を示すことが出来た。一般的に，HPLCやLC/MSでは溶離液は水ではなく，有機溶媒の使用が想定されているため，多様なLCカラム（順相，逆相，イオン交換等）を選択できるようになり，疎水性の農薬類，核酸，アミノ酸，脂肪酸，ビタミン，医薬品等まで対象成分が飛躍的に広がることが予想される。

Research Products

• [Journal Article] Discrimination for sake brewing methods by compound specific isotope analysis and formation mechanism of organic acids in sake (2022)
  • Author(s): Suto Momoka、Kawashima Hiroto
  • Journal Title: Food Chemistry Volume: 381 Pages: 132295-132295
  • DOI: 10.1016/j.foodchem.2022.132295
  • Peer Reviewed
• [Journal Article] Measurement report: Source characteristics of water-soluble organic carbon in PM2.5 at two sites in Japan, as assessed by long-term observation and stable carbon isotope ratio (2021)
  • Author(s): Nana Suto, Hiroto Kawashima
  • Journal Title: Atmospheric Chemistry and Physics Volume: 21 Issue: 15 Pages: 11815-11828
  • DOI: 10.5194/acp-21-11815-2021
  • Peer Reviewed
• [Journal Article] Carbon isotope ratio of organic acids in sake and wine by solid-phase extraction combined with LC/IRMS (2021)
  • Author(s): Momoka Suto, Hiroto Kawashima
  • Journal Title: Analytical and Bioanalytical Chemistry Volume: 413 Issue: 2 Pages: 355-363
  • DOI: 10.1007/s00216-020-03003-x
  • Peer Reviewed / Open Access
• [Journal Article] Analysis of malto-oligosaccharides and related metabolites in rice endosperm during development (2020)
  • Author(s): Yasunori Nakamura, Masami Ono, Momoka Suto, Hiroto Kawashima
  • Journal Title: Planta Volume: 251 Issue: 6
  • DOI: 10.1007/s00425-020-03401-6
  • Peer Reviewed / Open Access
• [Journal Article] Determination of Organic Acids in Honey by Liquid Chromatography with Tandem Mass Spectrometry (2020)
  • Author(s): Momoka Suto, Hiroto Kawashima, Yasunori Nakamura
  • Journal Title: Food Analytical Methods Volume: 13 Issue: 12 Pages: 2249-2257
  • DOI: 10.1007/s12161-020-01845-w
  • Peer Reviewed / Open Access
• [Presentation] 新たな安定同位体比分析と応用研究～エアロゾル分野と食品分野～ (2024)
  • Author(s): 川島洋人
  • Organizer: 産業技術総合研究所（招待講演）
  • Invited
• [Presentation] Determination of carbon stable isotope ratios of free amino acids in commercial soy sauce samples (2022)
  • Author(s): Kohei Sasaki, Hiroto Kawashima
  • Organizer: 8th Conference of the Forensic Isotope Ratio Mass Spectrometry Network
  • Int'l Joint Research
• [Presentation] 大気環境分野における有害物質の炭素，窒素安定同位体比の最新の分析法及び発生源解析の研究 (2022)
  • Author(s): 川島洋人
  • Organizer: 大気環境学会年会，酸性雨分科会
  • Invited
• [Presentation] 安定同位体比を用いた環境中有害化学物質の発生源解析と食品の異同識別 (2021)
  • Author(s): 川島洋人
  • Organizer: 日本質量分析学会 同位体比部会2021
  • Invited
• [Remarks] 秋田県立大学システム科学技術学部 環境鑑識学研究室HP
  • URL: http://www.akita-pu.ac.jp/system/mse/sac/kawa/index.html
• [Remarks] 秋田県立大学システム科学技術学部 環境鑑識学研究室HP
  • URL: http://www.akita-pu.ac.jp/system/mse/sac/kawa/index.html