脱離エレクトロスプレーイオン化質量分析用イオン源 Title の試作と迅速分析への応用 芳本, 有史, 元木, 翔一, 森脇, 悠介, 川崎, 英也, Author(s) 荒川, 隆一 Journal of the Mass Spectrometry Citation n, 57(2): 109-115 Issue Date 2009 URL http://hdl.handle.net/10112/6001 Rights Type Journal Article Textversion publisher Kansai University http://kuir.jm.kansai-u.ac.jp/dspace/
J. Mass Spectrom. Soc. Jpn. Vol. 57, No. 2, 2009 Optimization of a Home-Built Desorption Electrospray Ionization Source and Its Application in Rapid Analysis 1 1 1 1 1, 2 Arifumi YDH=>BDID, 1 Shoichi MDID@>, 1 Yusuke MDG>L6@>, 1 Hideya K6L6H6@>, 1 and Ryuichi AG6@6L6 1, 2 1 Department of Chemistry and Materials Engineering, Kansai University, Suita, OSAKA, JAPAN 2 Research Center for Business Academia Collaboration, Kansai University, Suita, OSAKA, JAPAN High-performance liquid chromatography/mass spectrometry (LC/MS) is the most useful tool for qualitative and quantitative chemical analysis in the life sciences. However, sample preparation and LC separation demand an extraordinary amount of time and e#ort. Desorption electrospray ionization (DESI) and direct analysis in real time (DART) techniques that obtain mass spectra of samples without di$culty have been developed in recent years. We connected a home-built DESI ion source to an existing mass spectrometer and examined its performance. In this paper, we report the application of DESI to thin-layer chromatography (TLC)/ DESI-MS in rapid analysis of medicines in serum and concentrated analysis with a solid-phase extraction disk. (Received December 22, 2008; Accepted January 29, 2009) 1. (liquid chromatography/mass spectrometry; LC/MS) LC/MS (electrospray ionization; ESI) 1) (atmospheric pressure chemical ionization; APCI) 2) direct analysis in real time (DART) 3) 5) (desorption electrospray ionization; DESI) 6) 8) DART Correspondence to: Ryuichi AG6@6L6, Department of Chemistry and Materials Engineering, Kansai University, 3 3 35 Yamate-cho, Suita, Osaka 564 8680, JAPAN, e-mail: arak@ipcku.kansai-u.ac.jp 564 8680 3 3 35 DESI Cooks 2004 6) DESI ESI ESI DESI ESI Shiea (electrospray-assisted laser desorption ionization; ELDI) 9), 10) (matrix-assisted laser desorption/ionization; MALDI) DESI MALDI ESI Van Berkel (thinlayer chromatography; TLC) 109
A. Yoshimoto et al. TLC/DESI-MS aspirin, acetaminophen ca#eine TLC/DESI-MS 11) DESI-MS 12) 15) 16) DESI DESI ESI DESI DESI DESI TLC/DESI-MS 2. 2.1 6G I high-performance liquid chromatography; HPLC HPLC TLC 70F254 perfluorooctane sulfonate (PFOS) polytetrafluoroethylene (PTFE) 1.0 mm (ENVI TM - 18DSK 47 mm) RFD250NB, ADVANTEC, 2.2 Fig. 1 DESI TSQ 7000, ThermoFisher Scientific, DESI-MS 1/16 ESI DESI 50 mm, 150 mm 250 mm, 350 mm 0.5 1.0 mm d 1, d 2, a (Fig. 1) DESI 200 mm Fig. 1. Scheme of a DESI ion source and its parameters a, d 1,andd 2. 110
DESI 1/16 (high-voltage; HV) ESI d 1, d 2, a 1/16 2 2.3 TLC/DESI-MS / / / ( 40/20/6/3) TLC TLC TLC 1/16 8 mm/min SIM (selected ion monitoring) m/z 281, 455, 260 DESI-MS 2.4 3 PTFE TLC TLC DESI-MS TLC 2.5 6G 6G 6G DESI-MS PFOS 3. 3.1 DESI DESI DESI 6G 12 1 4 DESI Table 1 a d 1, d 2 (Fig. 1) (a) PTFE 4 kv 350 1,250 ml/min 0.5 5.0 ml/min Fig. 2a 800 ml/min Fig. 2b 2.0 ml/min PTFE 800 ml/min 2.0 ml/min DESI (b) Fig. 2c PTFE 6G 17) 6G [M H] 6kV 6G 4kV Fig. 2d 4kV 1 :1 6G 50 fmol 0.05 mm 1 ml S/N 3 (c) ph PTFE Table 1. Optimal Parameters in the DESI Operation Parameter Optimal setting Sample plate PTFE TLC plate Solid phase extraction disk Electrospray voltage 4 kv 4 kv 4 kv Electrospray solvent Acetonitrile Acetonitrile Methanol Electrospray flow rate 2 ml/min 10 ml/min 10 ml/min Nebulizing gas flow rate 800 ml/min 1,100 ml/min 1,250 ml/min Heated capillary temperature 250 250 250 Tip-to-sample distance (d 1 in Fig. 1) 1.5 mm 0.4 mm 1.2 mm Capillary inlet-to-tip distance (d 2 ) 3.5 mm 2.5 mm 5.5 mm Incident angle (a) 50 50 46 111
A. Yoshimoto et al. Fig. 2. Ion intensities vs. (a) electrospray flow rate, (b) nebulizing gas flow rate, (c) electrospray high voltage, and (d) types of spray solvents. ph DESI-MS 0.1 2.0 ESI (d) 6G I PTFE polymethyl methacrylate (PMMA), TLC, PTFE, PMMA m/z 1,296 m/z 649 PTFE PTFE I 1 ml 3mm 2 PTFE DESI-MS TLC PTFE I PTFE 2.0 ml/min 10 ml/min TLC PTFE PTFE Cooks 7) DESI DESI Table 1 3.2 TLC/DESI-MS 3 (12 pmol) TLC UV (ultraviolet) DESI-MS ([M H],[M Na] ) 1 pmol UV TLC 8mm/min SIM DESI-MS Fig. 3 TLC Fig. 3a c (1 pmol) TLC 3.3 Fig. 4 TLC PTFE 112
DESI Fig. 3. SIM chromatogram and mass spectra of the developed TLC plate. Fig. 4. DESI-MS spectra of the sample mixture of propranolol, imipramine, and verapamil obtained using TLC plates (a) in water and (b) in serum without preparation; and using a PTFE plate (c) in water. (1 mm) TLC DESI- PTFE PTFE DESI PTFE TLC TLC DESI-MS 5pmol 10 mm 0.5 ml S/N 3 (1 mm) DESI-MS [M H] (Fig. 5) 3.4 6G ESI-MS DESI-MS (500 pm) 113
A. Yoshimoto et al. Fig. 5. DESI-MS spectrum of creatinine in serum without preparation obtained using TLC plates. Fig. 6. Direct DESI-MS spectra of (a) rhodamine 6G, (b) PFOS trapped in a solid-phase extraction disk. 500 ml 8.5 cm 2 DESI-MS 6G (29 pmol/cm 2 ) (Fig. 6a) PFOS (1 nm) 500 ml DESI-MS PFOS (58 pmol/cm 2 ) (Fig. 6b) DESI-MS 4. PTFE DESI PTFE TLC DESI 3 1pmol TLC/ DESI- DESI-MS TLC 114
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