1999 Fiscal Year Annual Research Report

法医学的応用のための表面電離型マススペクトロメータ(SIOMS)の開発

Research Project

Project/Area Number	09307008
Research Institution	Hamamatsu University School of Medicine
Principal Investigator	鈴木修浜松医科大学, 医学部, 教授 (70093044)
Co-Investigator(Kenkyū-buntansha)	石井晃名古屋大学, 医学部, 助教授 (30252175) 鈴木加奈子浜松医科大学, 医学部, 助手 (70288546) 妹尾洋浜松医科大学, 医学部, 助教授 (50236113) 服部秀樹愛知医科大学, 医学部, 助教授 (30107817) 藤井敏博国立環境研究所, 科学環境部, 室長 (60109907)
Keywords	フェンサイクリジン(PCP) / ペチジン / ペンタゾシン / MPTP / 表面電離 / 質量分析 / ガスクロマトグラフィー / 固相抽出
Research Abstract	本年は、まず体液中フェンサイクリジン(PCP)の超高感度分析法を完成させた。PCPのフラグメントイオンは、m/z242,230,206,180,156等で検出され、もっとも大きなフラグメントであったm/z156を用いて定量した。内部標準としては、鎮静剤であるペチジンを用い、そのフラグメントはほほ単一で、m/z170であった。この二つのピークで定量すると、マスクロマトグラフィー(MC)では感度限界は0.05ng/ml、選択的イオンモード(SIM)では0.01ng/mlで、従来のSIM法の25ないし1000倍の高感度で検出することができ、ラットに投与した場合で少量のサンプルから高感度にPCPを検出することができた。同様に、麻酔性鎮痛剤のペンタゾシンについてもSIOMSを用いた体液中からの定量法を確立した。ペンタゾシンもPCPと同様にC_<18>系のカラムで固相抽出により精製し、この場合はSIM法を用いて定量した。フラグメントパターンに関しては、ペンタゾシンも内部標準のデキストロメトルファンも、表面電離に特徴的である[M-1]^+イオンであるそれぞれm/z284および270が最も大きなピークであった。この感度限界は0.5ng/mlであり、従来法の60の高感度で、治療時の薬物モニタリングにも十分応用可能であった。これらの結果は、いずれも分析化学の国際誌に掲載された。PCPおよびぺチジンのフラグメントイオンであるm/z156および170の構造は、通常の電子衝撃法ではみられないものであるが、この解析に、神経毒のMPTPと類似化合物のフラグメンテーションパターンを比較したところ、サイクロヘキシル基やピペリジル基の水素が失われて芳香族化することが明らかになった。MPTPと類似化合物は電子衝撃法および正負化学イオン化法とフラグメンテーションパターンを比較した。感度はSIOMSはいずれの方法よりも高感度であった。現在は体液中ぺチジン及び三環系抗うつ剤の高感度分析法の条件を検討中である。

Research Products

(15 results)

All Other

All Publications (15 results)

[Publications] Seno,H.: "Analyses of butyrophenenes and their analogues in whole blood by high-perforamance liquid chromatography-electrosprey tandem mass spectrometry"Jornal of Chromatography B. in press
[Publications] Seno,H.: "Determination of pentazocine in human whole blood and urine by gas chromatography / surface ionization mass spectrometry"Joumal of Mass Spectrometry. 35. 33-38 (2000)
[Publications] Ishii,A.: "Ultrasensetive determination of phencylidine in boby fluids by surface ionization organic mass spectrometry"Analytical Chemsistry. 72. 404-407 (2000)
[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] Seno,H.: "Extraction of chloroform and methylene chloride in human whole blood and urine by headspace solid phase microextraction (SPME)"Medicine,Scinence and law. 39. 332-336 (1999)
[Publications] Guan,F: "A method for simulataneous detemination of anticoagulant rodenticides in whole blood by high-performance liquid chromatography"Joumal of pharmaceutical and Biomedical Analysis. 21. 179-185 (1999)
[Publications] Ishii,A: "positive-ino, negative-ion and surface ionization mass spectra of MPTP and its derivatives"Japanese Journal of forensic Toxicology. 17. 195-202 (1999)
[Publications] Guan,F: "Identification and quantification of caridiac glycosides in blood and urine samples by HPLC/MS/MS"Analytical Chemisitry. 71. 4034-4043 (1999)
[Publications] Guan.F: "Use of ion-pairing reagent for high-perfomance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry detemination of an ionic 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] Kamazawa,T: "Extraction of methylxanthines from human body fluids by solid-phase microextraction"Analytica Chimica Acta. 387. 53-60 (1999)
[Publications] Watanabe-Suzuki,K: "Ultra-sensitive method for determination of ethanol in whole blood by headspace capillary gas chromatography with cryogenis oven trapping"Journal of Chromatography B. 727. 89-94 (1999)
[Publications] Guan.F: "Solid-phase microextraction and GC-ECD of benzophenones for detection of benxzodiazepines in urine"Journal of Analytical Toxicology. 23. 54-61 (1999)
[Publications] Watanabe-Suzuki.K: "Sensitive detection of ethanol in human breath by headspase capilllary gas chromatography with cryogenic oven trapping"Japanese Journal of Forensic Toxicology. 17. 61-65 (1999)
[Publications] Fujii.T.: "Principle and applications of surface ionization in GC-MS In: Current Practice in GC-MS"Marcel Dekker (in press).

1999 Fiscal Year Annual Research Report

法医学的応用のための表面電離型マススペクトロメータ(SIOMS)の開発

Principal Investigator

鈴木 修 浜松医科大学, 医学部, 教授 (70093044)

Research Products

[Publications] Seno,H.: "Analyses of butyrophenenes and their analogues in whole blood by high-perforamance liquid chromatography-electrosprey tandem mass spectrometry"Jornal of Chromatography B. in press

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

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

[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] Seno,H.: "Extraction of chloroform and methylene chloride in human whole blood and urine by headspace solid phase microextraction (SPME)"Medicine,Scinence and law. 39. 332-336 (1999)

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

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

[Publications] Guan,F: "Identification and quantification of caridiac glycosides in blood and urine samples by HPLC/MS/MS"Analytical Chemisitry. 71. 4034-4043 (1999)

[Publications] Guan.F: "Use of ion-pairing reagent for high-perfomance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry detemination of an ionic 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] Kamazawa,T: "Extraction of methylxanthines from human body fluids by solid-phase microextraction"Analytica Chimica Acta. 387. 53-60 (1999)

[Publications] Watanabe-Suzuki,K: "Ultra-sensitive method for determination of ethanol in whole blood by headspace capillary gas chromatography with cryogenis oven trapping"Journal of Chromatography B. 727. 89-94 (1999)

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

[Publications] Watanabe-Suzuki.K: "Sensitive detection of ethanol in human breath by headspase capilllary gas chromatography with cryogenic oven trapping"Japanese Journal of Forensic Toxicology. 17. 61-65 (1999)

[Publications] Fujii.T.: "Principle and applications of surface ionization in GC-MS In: Current Practice in GC-MS"Marcel Dekker (in press).

鈴木修浜松医科大学, 医学部, 教授 (70093044)