42(1), 203 203 215 (2017) DOI: 10.1584/jpestics.W17-54 1, * 2, ** 3, *** 4, **** 4 1 2 3 4 2017 1 6 Recent data analysis technique in mass spectrometry Takaya Satoh, 1 Kentaro Takahara, 2 Tomoaki Kondo, 3 Ryo Ogasawara 4 and Chika Nogami 4 1 JEOL Ltd., Musashino, Akishima-shi, Tokyo 196 8558, Japan 2 Thermo Fisher Scientific K.K., Moriya-cho, Kanagawa-ku, Yokohama, Kanagawa 221 0022, Japan 3 Shimadzu Corporation, Kanda nishiki-cho, Chiyoda-ku, Tokyo 101 8448, Japan 4 Agilent Technologies Japan, Ltd., 9 1 Takakuramachi, Hachioji, Tokyo 192 8510, Japan Keywords: elemental composition analysis, Kendrick mass defect analysis, accurate mass library, MS/MS spectral database, standard-less analysis, simultaneous screening database. LC-MS GC-MS * 196 8558 3 1 2 E-mail: taksatoh@jeol.co.jp ** 221 0022 3 9 E-mail: kentaro.takanara@thermofisher.com *** 101 8448 1 3 E-mail: kon_tomo@shimadzu.co.jp **** 192 8510 9 1 E-mail: ryo_ogasawara@agilent.com 1. 3 4 m/z
204 1 m/z m/z m/z 2 m/z 202.04336 1 m/z ±20 ppm 35 ±5 ppm 9 2 1. m/z 202.04335 N 0 5 O 0 10 C 3 20 H 1 10 P 0 5 S 0 5 Cl 0 3 F 0 3 Br 0 3 2. m/z ±20 ppm ± 10 ppm ± 5 ppm 1. Dimethoate C 5 H 12 NO 3 PS 2, Dicryl C 10 H 9 Cl 2 NO 35 18 9 N S 1 6 2 1 Cl Br 2. 14 Thiabendazole m/z 202.04335
205 205 N S Cl Br 2 N S Cl Br ± 5 ppm 1 Kind Fiehn 1 2. CH 2 FT-ICR MS 1 1 KMD 2 3 12 C 12 u IUPAC 2 3 12 C 12 u IUPAC 12 C 1 H 2 14 M KM KM= M 14 /14.01565 ( 14.01565は, CH の IUPAC質量 ) (1) M CH 2 2 M=( 14.01565) n+ α (2) α Equation 1 KM= 14 n+ 14 /14.01565 α (3) KM KM NKM NKM KM Kendrick mass defect KMD Equation 3 1 KMD Eq. 3 2 3. KMD 3. IUPAC IUPAC u 1 H 1.00728 12 C 12.00000 14 N 14.00307 16 O 15.99491 32 S 31.97207 4. NKM KMD ΔM Δ KM Δ NKM Δ KMD 14 N 14.00307 13.98743 14 0.01257 16 O 15.99491 15.97705 16 0.02295 32 S 31.97207 31.93637 32 0.06363
206 n NKM 1 2 n 1 KM KMD NKM KMD CH 2 14 3 A Equation 3 NKM KMD 16 O, 32 S NKM, KMD ΔNKM, Δ KMD 4 Δ NKM, Δ KMD KMD 3 B KMD 4 4. KMD KMD FT-ICR MS TOF MS MALDI-TOF MS FT-ICR MS 3 KMD CH 2 C 2 H 4 O KMD 1 3. LC-QTOF GC-QTOF 3.1. GC-MS LC-MS MS time-flight-mass spectrometer: TOF MS quadrupole mass spectrometer: QMS Q-TOF MS TOF MS QTOF MS TOF MS QTOF MS 5.
207 207 MS/MS 5 MS/MS GC-MS EI LC-MS LC-MS QTOF MS LC-MS GC-MS 3.2. LC-QTOF LC-QTOF ESI GC- QTOF GC-QTOF 3.3 3.2.1. LC 6 EIC EIC EIC 7 EIC EIC 8 LC-QTOF TIC cyprodinil EIC 94.35 6. 7.
208 8. 9. Molecular Feature Extraction MFE 3.2.2. TIC Molecular Feature Extraction MFE S/N EIC 9 A 1 9 B TIC 10 LC- TOF MS TIC EIC TIC MFE245 TIC
209 209 10. TIC A MFE EIC B 11. 11 QTOF MS QTOF GC-MS 3.3. GC-QTOF GC-QTOF MS/MS LC-QTOF EI GC-MSCI CI TIC EICI LC-MS ESI ESI GC-QTOF LC-QTOF GC-QTOF 3.3.1. GC-QTOF Agilent GC-QTOF 740
210 EI 3 EI EI TOF CI LC-QTOF EIC LC-QTOF EI EIC LC-QTOF GC 12 GC-QTOF 12. GC-QTOF EIC EIC 3.3.2. GC-QTOF LC-QTOF MFE GC-MS EI CI GC-QTOF MFE GC-QTOF GC-MS m/z EICs TOF m/z EICs 13 GC- QTOF GC NIST EI NIST14 24EI GC-QTOF GC-MS 13. GC-QTOF
211 211 LC-QTOF GC-QTOF QTOF QTOF 4. MS/MS MS LC-MS/MS LC-MS/MSMS/MS Web MS/MS Massbank 4 METLIN 5 2013mzCloud mzcloud https://www.mzcloud.org/ Orbitrap MS/MS MS n MS/MS MS n 1 14. mzcloud 15. MS
212 100 2016 11 24 6091 155 1000 0 ppm 14 mzcloud MS MSn mzcloud 15MS3 mzcloud mzcloud Technique FAQs 5. GC-MS /MS 5.1. GC-MS /MS 5.2. GC-MS /MS n- ISTD 16 16.
213 213 17. 18. GC-MS /MS.. ISTD. 17. 17. False positive False negative 5.3. GC-MS /MS QA/QC QC 5.4. MRM SIM GC
214 19. 20. SIM MRM n- 18 SIM MRM 5.5. 2 19 20
215 215 20 5.6. 1) T. Kind and O. Fiehn: BMC Bioinformatics 8, 105 (2007). 2) E. Kendrick: Anal. Chem. 35, 2146 2154 (1963). 3) H. Sato, S. Nakamura, K. Teramoto and T. Sato: J. Am. Soc. Mass Spectrom. 25, 1346 1355 (2014). 4) H. Horai, M. Arita, S. Kanaya, Y. Nihei, T. Ikeda, K. Suwa, Y. Ojima, K. Tanaka, S. Tanaka, K. Aoshima, Y. Oda, Y. Kakazu, M. Kusano, T. Tohge, F. Matsuda, Y. Sawada, M. Y. Hirai, H. Naka nishi, K. Ikeda, N. Akimoto, T. Maoka, H. Takahashi, T. Ara, N. Sakurai, H. Suzuki, D. Shibata, S. Neumann, T. Iida, K. Tanaka, K. Funatsu, F. Matsuura, T. Soga, R. Taguchi, K. Saito and T. Nishi oka: J. Mass Spectrom. 45, 703 714 (2010). 5) C. A. Smith, G. O Maille, E. J. Want, C. Qin, S. A. Trauger, T. R. Brandon, D. E. Custodio, R. Abaqyan and G. Siuzdak: Ther. Drug Monit. 27, 747 751 (2005). 2002 4 1978 6 24 2007 2008 2010 1976 2 4 2004 GC-MS GC GC/MS LC LC/MS