1999 Fiscal Year Annual Research Report

HPLC/タンデムMSによるドーピング薬物の迅速高感度検出法の確立

Research Project

Project/Area Number	10770188
Research Institution	Nagoya University
Principal Investigator	石井晃名古屋大学, 医学部, 助教授 (30252175)
Keywords	ガスクロマトグラフィー(GC) / 質量分析法(MS) / フェンザイクリジン(PCP) / ペチジン / 電子衝撃法(EI) / 化学イオン化法(CI) / タンデムMS(MS / MS)
Research Abstract	昨年度に行った、HPLC/タンデムMSによる利尿剤の高感度検出法の確立については、固相抽出による利尿剤の抽出に関する最適条件について現在も検討中である。昨年本学にGC/タンデムMS(GC/MS/MS)が導入されたため、一部ドーピング薬物の検出法を、本年はこのGC/MS/MSで試みた。GC/MS/MSについては、GC/MS部分でのイオン化の選択や、タンデムMS部分での親イオンの分解条件等、多数のパラメータを動かして最適条件を決定する必要がある。そのため、すでに我々が種々の方法で検出法を開発した幻覚剤のフェンサイクリジン(PCP)及び鎮痛剤のペチジンをモデルとして、GC/MS/MSの最適条件をより効率よく検索することを試みた。なお、ペチジンはIOCにおける禁止薬物のリストにも掲載されており、PCPも各国で法的に禁じられている。ペチジンについては、適切な条件を設定すれば、化学イオン化法(CI)でも、全イオンクロマトグラフィー(TIC)において、通常の電子衝撃法(EI)とほぼ同じイオン強度を得ることができた。CIでは、ペチジンのスペクトルは[M+H]^+のm/z248がベースピークであり、MS/MSでは、これを親イオンとしてさらに分解し、娘イオンをスキャンすることを試みた。得られた娘イオンはm/z220,174等があり、ベースピークはm/z174であった。この場合、MSでもMS/MSでもほぼ同じイオン強度(TICにおいて)が得られたが、MS/MSの利点は、娘イオンのパターンから化合物を同定することが可能であること(CIでは、[M]^+か[M+H]^+のどちらかしか得られないことが多い)や、夾雑物の多いサンプルではピークのs/n比がはるかに良いこと等があげられる。現在は、腐敗した血液からペチジンを同定しており、MS/MSに適した内部標準の選択を含め、さらに詳細な条件を設定を行っている。PCPについては、CIよりもEIの方が感度が高く、分子イオンの強度が低いため、既に開裂したイオンを親イオンとしてスキャンする条件を設定している。

Research Products
(20 results)

All Other

All Publications (20 results)

[Publications] Ishii,A.: "Ultrasensetive determination of phencyclidine in body fluids by surface ionization organic mass spectrometry"Analytical Chemistry. 72. 404-407 (2000)
[Publications] Seno,H.: "Determination of pentazocine in human whole blood and urine by gas chromatography / surface ionization organic mass spectrometry"Journal of Mass Spectrometry. 35. 33-38 (2000)
[Publications] 石井,晃: "シアンと類似化合物の分析"現代医学. 47. 15-21 (1999)
[Publications] 石井,晃: "向精神薬の分析"現代医学. 47. 7-13 (1999)
[Publications] Seno,H: "High performance liquid chromatography / electrospray tandem mass spectrometry for phenothiazines with heavy side chain in whole blood"Rapid Communications in Mass Spectrometry. 13. 2394-2398 (1999)
[Publications] Guan,F: "A method for simulataneous determination of five anticoagulant rodenticides in whole blood by high-performance liquid chromatography"Journal of Pharmaceutical and Biomedical Analysis. 21. 179-185 (1999)
[Publications] Ishii,A: "positive-ion,negative-ion and surface ionization mass spectra of MPTP and its derivatives"Japanese Journal of Forensic Toxicology. 17. 195-202 (1999)
[Publications] 石井,晃: "GC及びGC/MSを用いたシアンの高感度分析"日本医用マススペクトル学会サーキュラー. No.46. 4-9 (1999)
[Publications] 石井,晃他: "毒物検索システム"現代医学. 46. 467-470 (1999)
[Publications] Guan,F.: "Identification and quantification of cardiac giycosides in blood and urine samples by HPLC/MS/MS"Analtical Chemistry. 71. 4034-4043 (1999)
[Publications] Guan,F.: "Use of ion-pairing reagent for high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry determination of anionic anticoagulant rodenticides"Journal of Chromatography B. 731. 155-165 (1999)
[Publications] Seno,H.: "Positive-and negative-ion mass spectrometry of non-steroidal antiinflammatory agents and their clean-up with Bond Elut Glass C_<18> from biological samples"Forensic Science International. 100. 143-147 (1999)
[Publications] Kumazawa,T.: "Extraction of methylxanthines from human body fluids by solid-phase"Analytica Chimica Acta. 387. 53-60 (1999)
[Publications] Guan,F.: "Solid-phase microextraction and GC-ECD of benzophenones for detection of benzodiazepines in urine"Journal of Analytical Toxicology. 23. 54-61 (1999)
[Publications] Watanabe-Suzuki,K.: "Ultra-sensitive method for determination of ethanol in whole blood by headspace capillary gas chromatography with cryogenic oven trapping"Journal of Chromatography B. 727. 89-95 (1999)
[Publications] Ishii,A.: "Determination of cyanide in whole blood by capillary gas chromatography with cryogenic oven trapping"Analytical Chemistry. 70. 4873-4876 (1998)
[Publications] Hattori,H.: "Sensitive determination of xylenes in whole blood by capillary gas chromatography with cryogenic trapping"Journal of Chromatography B. 718. 285-289 (1998)
[Publications] Guan,F.: "Headspace solid-phase microextraction and gas chromatographic determination of dinitroaniline herbicides in human blood,urine and environmental water"Journal of Chromatography B. 714. 205-213 (1998)
[Publications] Kumazawa,T.: "Positive-and negative-ion mass spectra of alky1 ester derivatives of cocaine"Japanese Journal of Forensic Toxicology. 16. 221-227 (1998)
[Publications] Kumazawa,T.: "Monoamine oxidase activities in catfish(Paeasilurus Asotus) tissues"Journal of Enzyme Inhibition. 13. 377-384 (1998)

1999 Fiscal Year Annual Research Report

HPLC/タンデムMSによるドーピング薬物の迅速高感度検出法の確立

Principal Investigator

石井 晃 名古屋大学, 医学部, 助教授 (30252175)

Research Products

[Publications] Ishii,A.: "Ultrasensetive determination of phencyclidine in body fluids by surface ionization organic mass spectrometry"Analytical Chemistry. 72. 404-407 (2000)

[Publications] Seno,H.: "Determination of pentazocine in human whole blood and urine by gas chromatography / surface ionization organic mass spectrometry"Journal of Mass Spectrometry. 35. 33-38 (2000)

[Publications] 石井,晃: "シアンと類似化合物の分析"現代医学. 47. 15-21 (1999)

[Publications] 石井,晃: "向精神薬の分析"現代医学. 47. 7-13 (1999)

[Publications] Seno,H: "High performance liquid chromatography / electrospray tandem mass spectrometry for phenothiazines with heavy side chain in whole blood"Rapid Communications in Mass Spectrometry. 13. 2394-2398 (1999)

[Publications] Guan,F: "A method for simulataneous determination of five anticoagulant rodenticides in whole blood by high-performance liquid chromatography"Journal of Pharmaceutical and Biomedical Analysis. 21. 179-185 (1999)

[Publications] Ishii,A: "positive-ion,negative-ion and surface ionization mass spectra of MPTP and its derivatives"Japanese Journal of Forensic Toxicology. 17. 195-202 (1999)

[Publications] 石井,晃: "GC及びGC/MSを用いたシアンの高感度分析"日本医用マススペクトル学会サーキュラー. No.46. 4-9 (1999)

[Publications] 石井,晃他: "毒物検索システム"現代医学. 46. 467-470 (1999)

[Publications] Guan,F.: "Identification and quantification of cardiac giycosides in blood and urine samples by HPLC/MS/MS"Analtical Chemistry. 71. 4034-4043 (1999)

[Publications] Guan,F.: "Use of ion-pairing reagent for high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry determination of anionic anticoagulant rodenticides"Journal of Chromatography B. 731. 155-165 (1999)

[Publications] Seno,H.: "Positive-and negative-ion mass spectrometry of non-steroidal antiinflammatory agents and their clean-up with Bond Elut Glass C_<18> from biological samples"Forensic Science International. 100. 143-147 (1999)

[Publications] Kumazawa,T.: "Extraction of methylxanthines from human body fluids by solid-phase"Analytica Chimica Acta. 387. 53-60 (1999)

[Publications] Guan,F.: "Solid-phase microextraction and GC-ECD of benzophenones for detection of benzodiazepines in urine"Journal of Analytical Toxicology. 23. 54-61 (1999)

[Publications] Watanabe-Suzuki,K.: "Ultra-sensitive method for determination of ethanol in whole blood by headspace capillary gas chromatography with cryogenic oven trapping"Journal of Chromatography B. 727. 89-95 (1999)

[Publications] Ishii,A.: "Determination of cyanide in whole blood by capillary gas chromatography with cryogenic oven trapping"Analytical Chemistry. 70. 4873-4876 (1998)

[Publications] Hattori,H.: "Sensitive determination of xylenes in whole blood by capillary gas chromatography with cryogenic trapping"Journal of Chromatography B. 718. 285-289 (1998)

[Publications] Guan,F.: "Headspace solid-phase microextraction and gas chromatographic determination of dinitroaniline herbicides in human blood,urine and environmental water"Journal of Chromatography B. 714. 205-213 (1998)

[Publications] Kumazawa,T.: "Positive-and negative-ion mass spectra of alky1 ester derivatives of cocaine"Japanese Journal of Forensic Toxicology. 16. 221-227 (1998)

[Publications] Kumazawa,T.: "Monoamine oxidase activities in catfish(Paeasilurus Asotus) tissues"Journal of Enzyme Inhibition. 13. 377-384 (1998)

石井晃名古屋大学, 医学部, 助教授 (30252175)