Basic Knowledge of Chemistry and Mass Spectrometry

J. Mass Spectrom. Soc. Jpn. Vol. 56, No. 3, 2008 COMMENTARY Basic Knowledge of Chemistry and Mass Spectrometry Kazuo H>G6N6B6 Science Education Co., Inc., TOKYO, JAPAN Recently, rapid developments in mass spectrometry have enabled people who do not have adequate knowledge of chemistry to operate mass spectrometers. In addition, some sales engineers dealing with mass spectrometers have little knowledge of chemistry because they did not major in chemistry, when in university. However, basic knowledge of chemistry and mass spectrometry is necessary to obtain optimum results and to highlight the favorable points of their instruments. In this paper, we present some basic knowledge of chemistry and mass spectrometry as a short tutorial course for the abovementioned persons. (Received January 28, 2008; Accepted March 3, 2008) 1. 5 2. 1) 1 6 2 Correspondence to: Kazuo H>G6N6B6, Science Education Co., Inc., 2 13 16 Kamata, Ohta-ku, Tokyo 144 0052, JAPAN, e-mail: kazuo hirayama@science-education-jp.net Science Education Co., Inc., 144 0052 2 13 16 2. 1 1.1 1.2 1.3 1.4 1.5 2 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 2.10 2.11 2.12 2.13 2.14 2.15 (Electronvolt, ev) 2.16 3 3.1 3.2 3.3 163

K. Hirayama 4 4.1 4.2 5 5.1 (Electrospray ionization, ESI) 5.2 (Atmospheric pressure chemical ionization, APCI) 5.3 (Matrixassisted laser desorption/ionization, MALDI) 5.4 (Electron ionization, EI) (Chemical ionization, CI) 5.5 (Fast atom bombardment ionization, FAB ionization) 5.6 5.6.1 5.6.2 5.6.3 6 6.1 (Quadrupole mass spectrometer, QMS) 6.2 (Time-of-flight mass spectrometer, TOF-MS) 6.3 (Ion trap mass spectrometer, ITMS) 6.4 (Magnetic sector-type mass spectrometer) 6.5 (Fourier-transform ion cyclotron resonance mass spectrometer, FT-ICR-MS) 7 7.1 7.2 (Microchannel plate, MCP) 8 8.1 8.2 (Electrospray ionization, ESI) 8.3 (Matrixassisted laser desorption/ionization, MALDI) 8.4 (Electron ionization, EI) (Chemical ionization, CI) 8.5 (Fast atom bombardment ionization, FAB ionization) 9 9.1 (Quadrupole mass spectrometer, QMS) 9.2 (Ion trap mass spectrometer, ITMS) 9.3 (Time-of-flight mass spectrometer, TOF-MS) 9.3.1 MALDI-TOF-MS 9.3.2 ESI-TOF-MS 9.3.3 ESI-Q-TOF-MS 9.4 (Magnetic sector-type mass spectrometer) 9.5 (Fourier-transform ion cyclotron resonance mass spectrometer, FT-ICR-MS) 10 10.1 10.2 10.3 10.4 10.4.1 10.4.2 10.5 10.6 10.7 10.8 11 MS/MS 11.1 MS/MS 11.2 11.3 11.3.1 (Triple-quadrupole mass spectrometer) 11.3.2 (Ion trap mass spectrometer, ITMS) 11.3.3 Q-TOF-MS (Quadrupole-time-of-flight mass spectrometer) 11.3.4 11.3.5 (Fourier-transform ion cyclotron resonance mass spectrometer, FT-ICR-MS) 11.4 12 12.1 12.2 GC-MS 12.3 LC-MS 12.4 12.4.1 12.4.2 12.4.3 12.4.4 HPLC 12.4.5 12.4.6 12.4.7 12.4.8 12.5 12.6 MS 164

13 LC-MS 13.1 13.1.1 LC- (LC-quadrupole mass spectrometer, LC-QMS) 13.1.2 LC- (LC-triple quadrupole mass spectrometer) 13.1.3 LC- (LC-ion trap mass spectrometer, LC-ITMS) 13.1.4 LC- (LC-time-of-flight mass spectrometer, LC-TOF-MS) 13.1.5 LC- (LC-quadrupoletime-of-flight mass spectrometer, LC-Q-TOF- MS) 13.1.6 LC- (LC-magnetic sector-type mass spectrometer) 13.2 13.2.1 13.2.2 13.3 ESI APCI 13.4 LC-MS 13.5 LC-MS 13.5.1 HPLC 13.5.2 13.5.3 13.5.4 13.5.5 LC 14 GC-MS 14.1 14.1.1 GC- (GC-quadrupole mass spectrometer, GC-QMS) 14.1.2 GC- (GC-triple quadrupole mass spectrometer) 14.1.3 GC- (GC-ion trap mass spectrometer, GC-ITMS) 14.1.4 GC- (GC-time-of-flight mass spectrometer, GC-TOF-MS) 14.1.5 GC- (GC-magnetic sector-type mass spectrometer) 14.2 GC 14.3 GC-MS 14.4 14.5 14.5.1 14.5.2 14.6 15 15.1 MS 15.2 15.3 GC-MS LC-MS 15.4 Selected ion monitoring (SIM) 15.5 SIM 15.6 SIM SRM 2 1) 3. 3.1 8 (1) Fig. 1 n-butanol Diethyl ether n-pentane i-pentane 1-Pentene 2- Pentene n- i- normal Fig. 1. (a) n-butanol (b) Diethyl ether C 4 H 10 O O (c) n-pentane (d) i-pentane C 5 H 12 CH 3 (e) 1-Pentene (f) 2-Pentene C 5 H 10 165

K. Hirayama iso 1-Pentene 2-Pentene Pentene 1 5 1 2 2), 3) Fig. 4. (2) Fig. 2 trans-2-butene cis-2-butene Fig. 5. Fig. 2. trans-2-butene cis-2-butene (3) Fig. 3 2,3-Hexanediol OH H Fig. 3 3.2 Fig. 4 Fig. 4 (H 2 ) H:H HH H H CH 4 CH 4 CH 3 H CH 3 H (M) Fig. 5 Fig. 3. 2,3- I II III IV I III, I IV, II III, II IV 166

3.3 Fig. 6 Fig. 6. 3.4 Fig. 7 Methylamine p-aminotoluene Fig. 7. 3.5 1 2 Fig. 8 104.5 d d 1 q q d m qd m 2 Fig. 8. OH 2 3 3 1 Fig. 9 CH 3 OH CH 3 CH 2 OH CH 3 CH 2 CH 2 OH CH 3 CH 2 CH 2 - CH 2 OH CH 3 CH 2 CH 2 CH 2 CH 2 OH H 2 O CH 3 OH Fig. 10 OH Fig. 11 (R) R-SO 3 H R-COOH R-OH 32.6 24.3 3.6 Fig. 12 16 O 4 16 16 O, 17 17 O, 18 18 O 3 99.762, 0.038, 0.2 Fig. 12 16 O 8 8 8 16 O, 17 O, 18 O 8 8 16 O 8 17 O 9 18 O 10 16, 17, 18 8 16 O, 17 O, 18 O 8 Fig. 13 3.7 3 1 2 3 OH 4 12 C 12 167

K. Hirayama Fig. 9. 1 Fig. 10. OH Fig. 11. R-SO 3H R-COOH R-OH Fig. 12. 16 O 16 O 8 8 8 Fig. 13. 8 16 O 17 O 18 O 16 O, 17 O, 18 O 8 Fig. 14. (periodic law) (periodic table) 1 18 1 7 (periodic law) (periodic table) (Fig. 14) 1 18 1 7 1 17 18 3.8 16 O, 17 O, 18 O 99.757, 0.038, 0.205 16 O 15.9949 u 17 O, 18 O 1.0087 u 168

3.9 16 O, 17 O, 18 O Fig. 17 Fig. 15. 16 O, 17 O, 18 O 15.9949 u, 16.9991 u, 17.9992 u 99.757, 0.038, 0.205 EI 16 O, 17 O, 18 O 9.1093826 10 31 kg 1Da 1.66053886(28) 10 27 kg (u) 0.000548580 Fig. 17. Fig. 16. 16 O, 17 O, 18 O 17.0036 u, 18.0123 u 16.9991 u 17.9992 u 5 Fig. 15 16 O, 17 O, 18 O 16 O, 17 O, 18 O 16 O 17 O 18 O 15.9949 0.99757 16.9991 0.00038 17.9992 0.00205 15.9994 (Fig. 16) 16 O 16 O, 16 O 17 O, 16 O 18 O, 17 O 17 O, 17 O 18 O, 18 O 18 O 6 O 2 31.9988 3.10 17 (F) (Cl) (Br) (I) (At) 5 17.0036 u, 18.0123 u 16.9991 u 17.9992 u Fig. 18. p-chloroacetanilide (M ) p-chloroacetanilide (M ) m/z 169 m/z 171 3:1 35 Cl 37 Cl 75.78 24.22 169

K. Hirayama X 35 Cl 37 Cl 79 Br 81 Br Fig. 18 p-chloroacetanilide (M ) m/z 169 m/z 171 3:1 35 Cl 37 Cl 75.78 24.22 3.11 N, O, S, P (Fig. 19) Fig. 19. 3.12 (Unified atomic mass) u 12 12 C 1 12 1 (Da) (Fig. 20) Fig. 20. N, O, S, P. u 12 C 1/12 3.13 (Electronvolt, ev) (Electronvolt, ev) 1 1 (V) 1 (1 ev) (Fig. 21) Fig. 21. 3.14 kg 2 mol/l 10 3 1,000 g 1kg Fig. 22 g, mg, mg, ng, pg, fg, ag, zg (mg) (mg) (ng) (pg) (fg) (ag) (zg) 10 3 1zg 10 21 g (ev) 1 1 (V) 1 (1 Electronvolt, 1 ev) parts per cent 100 1 100 1 ppm (parts per million) 10 1 ppb (parts per billion) 1 1 ppt (parts per trillion) ppm, ppb, ppt 10 3 ppm 10 4 1ppm 0.0001, 1 ppm 1,000 ppb, 1 ppm 1,000,000 ppt (Fig. 23) mol mol H 2 O 18 CH 3 OH 32 mol 1 mol g 18 g 1 mol 32 g 18 g 32 g mol 1 mol H 2 O Fig. 22. 10 3 1zg 10 21 g 170

Fig. 23. ppm ppm 10 4 10 3 Fig. 24. mol 10 3 1zmol 10 21 mol 1 mol CH 3 OH 6.0221367 10 23 mol 1 mol, 2 mol mol mol mol, mmol, mmol, nmol, pmol, fmol, amol, zmol 10 3 (Fig. 24) mol 1 mol 1L 1 mol/l, 10 L 0.1 mol/l 100 mmol/l mol 4. 2007 3 2008 4 55 140 10 1 3 30 5 2007 5 55 2007 7 34 BMS 1), Mass Spectrometry Science Education Co., Inc., 2) 2 (1988). 3) 2 (1989). Keywords: Basic knowledge of mass spectrometry, Basic knowledge of chemistry 171