43 215 4 FENXI HUAXUE Chinese Journal of Analytical Chemistry 4 512 ~ 517 DI 1. 11895 /j. issn. 253-382. 14954 1 2 1 2 2 * 2 1 1 1 3313 2 33123 41 34 PCA CA 1 1 2 3 4 GC-MS EESI-MS 5 6 EESI-MS 6 EESI-MS 41 EESI-MS 2 2. 1 7 EESI 8 LTQ-XL Finnigan Xcalibur T2PV /L 5L- Tedlar SK Chemicals 2. 2 Tedlar 3 3 min 3 min 5L- Tedlar 214-1-27 215-1-18 No. IRT1354 Nos. 21225522 212652 No. 2124ACB7 * E-mail wuxiaoping2823@ aliyun. com
4 513 EESI-MS 3 h 2. 3 EESI-MS EESI α β a b 7 8 N 2 1. 2 MPa 1 5 ~ 8 Da 3. 5 kv 5 μl /min 3 3. 1 41 EESI-MS 1 1 41 m /z 5 ~ 4 EESI-MS m /z > 4 2 S /N > 1 m /z 56 74 89 15 157 21 279 318 1 a 5 74 32 33 42 x2 1 b 5 74 32 42 462 157 478 639 679 218 462 679 13 536 418 679 161 478 1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 8 1 1 d 1 e f x2 x2 x2 42 42 42 5 32 462 5 32 5 32 478 639 679 462 56 157 536 536 679 536 56 679 18 56 135 1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 8 x2 1 c 5 74 32 42 33 x2 1 EESI-MS a b c d e f Fig. 1 EESI-MS spectra of exhaled gas from patients and normal subjects a b c MS data of exhaled gas from patients d e f MS data of exhaled gas from normal subjects 3. 2 7 8 PCA 9 1 41 3 34 3 PCA
514 43 m /z 5 ~ 8 Excel Matlab Princomp PCA 2 PC3(7.%) 1-1 -2 a PC1(64.8%) -1 2-2 1 PC2(16.4%) 34 例正常人 34 cases of normal 41 例病人 41 cases of patient b 1 318-1 2 4 6 PC1 PC2 PC3.5 74 15 318 279 21 89 -.5 2 4 6 1 56 157 279-1 2 4 6 2 a PCA b Fig. 2 Principal component analysis PCA results a 3D plots of PCA score results b PCA loading results 2a PCA 225 PC1 PC2 PC3 3 64. 8% 16. 4% 7% 88. 2% PCA PC1 2b m /z 56 74 89 15 157 21 279 318 m /z 74 89 157 21 LTQ MS 3 m /z 74 C 3 H 7 N + 3a m /z 46 C CH 2 C m /z 32 3b m /z 157 2- C 3 H 6 3 S 2 2- CH 3 m /z 142 α- m /z 11 m /z 81 α- 11 12 2-2- 3c m /z 21 C 6 H 1 3 S + K + C 6 H 1 3 S 3c m /z 183 m /z 156 α- m /z 154 m /z 144 α- CCH m /z 89 van den Velde - GC-MS 13 14 15 CYP3A4 3- -2 m /z 89 3d m /z 89 3- -2 Qin 16 3- -2-83. 3% 91. 7% EESI-MS PCA
4 515 1 a 5 32 46 N H MW73 74 74 1 5 b 81 H3C 11 S S MW156 142 157 H 157 3 1 5 c 4 5 6 7 8 9 1 H3C S 89 46 MW162 144 H 169 156 183 21 1 5 8 1 12 14 16 18 2 d 47 89 47 H3C H MW88 89 6 8 1 12 14 16 18 2 22 24 3 4 5 6 7 8 18 2 3 EESI-LTQ MS a m /z 74 b m /z 157 c m /z 21 d m /z 89 Fig. 3 MS / MS spectrum and the proposed structure of different peak from the data of patients and normal subjects exhaled gassamples a MS /MS spectrum and the proposed structure of m /z 74 b MS /MS spectrum and the proposed structure of m /z 157 c MS /MS spectrum and the proposed structure of m /z 21 d MS /MS spectrum and the proposed structure of m /z 89 3. 3 CA 17 PCA Matlab 4 41 34 1 ~ 12 13 ~ 225 PCA 4 13 ~ 171 23 172 ~ 189 6 19 ~ 24 5 25 ~ 225 7 1 ~ 2 PCA CA
516 43 16 14 Euclidean distance 12 1 8 6 4 2 1-12 13-171 172-189 19-24 25-225 4 Fig. 4 data Clusber analysis CA results of patients and normal subjects exhaled gas samples obtained from MS 4 EESI-MS PCA CA References 1 Probert S J Ahmed I Khalid T Johnsn E Smith S Ratcliffe N. Gastrointestin Liver Dis. 29 18 3 337-343 2 Michael M Cullinane C Hatzimihalis A ' Kane C Milner A Booth R Schlicht S Clarke S J Francis P. Cancer Chemother. Pharmacol. 212 69 125-135 3 Schubert R Schwoebel H Mau-Moeller A Behrens M Fuchs P Sklorz M Schubert J K Bruhn S Miekisch W. Metabolomics 212 1-12 4 Li M Ding J H Gu H W Zhang Y Pan S S Xu N Chen H W Li H M. Scientific Reports 213 125 5 HU Bin YUE Hao HUANG Ke-Ke JIANG Cui-Cui LIU Shu-Ying FEI Qiang CHEN Huan-Wen. Chem. J. Chinese Universities 211 32 6 1289-1294. 211 32 1289-1294 6 Law W S Wang R Hu B Berchtold C Meier L Chen H W Zenobi R. Anal. Chem. 21 82 11 4494-45 7 Chen H W Wortmann A Zhang W H Zenobi R. Angew. Chem. Int. Ed. 27 46 58-583 8 Ding J H Yang S P Liang D P Chen H W Wu Z Z Zhang L L Ren Y L. Analyst 29 134 1 24-25 9 Wu Z C Chingin K Chen H W Zhu L Jia B Zenobi R. Anal. Bioanal. Chem. 21 397 4 1549-1556 1 ZHU Zhi-Qiang YAN Jian-Ping WANG Yu CHEN Shun-Zong CHEN Huan-Wen. Chinese J. Anal. Chem. 213 41 6 95-91. 213 41 6 95-91 11 Khalid T Y Costello B D L Ewen R White P Stevens S Gordon F Collins P McCune A Shenoy A Shetty S Ratcliffe N M Probert C S. Metabolomics 213 9 938-948 12 Alkhouri N Cikach F Eng K Moses J Patel N Yan C Hanouneh I Grove D Lopez Rocio Dweik R. Eur. J. Gastroent. Hepat. 214 26 1 82-87 13 van den Velde S Nevens F Van hee P van Steenberghe D Quirynen M. J. Chromatogr. B 28 875 2 344-348 14 tsuka M Mine T huchi K hmori S. J. Biochem. 1996 119 2-251 15 V lkel W Wolf N Derelanko M Dekant W. Toxicol. Sci. 1999 47 2 144-15
4 517 16 Qin T Liu H Song Q Song G Wang H Z Pan Y Y Xiong F X Gu K S Sun G P Chen Z D. Cancer Epidemiology Biomar. Prev. 21 19 2247-2253 17 Chen H W Liang H Z Ding J H Lai J H Huan Y F Qiao X L. J. Agric. Food Chem. 27 55 193-11 Direct Analysis of Exhaled Breath of Chronic Hepatitis B Patients by Extractive Electrospray Ionization Mass Spectrometry WANG Hai-Dong 1 LU Jiao 2 LI Peng-Hui 1 ZHU Lan-Lan 2 ZHANG Wei 2 WU Xiao-Ping * 2 ZENG Qian 1 DING Jian-Hua 1 1 Jiangxi Key Labor Atory for Mass Spectrometry and Instrumentation East China Institute of Technology Nanchang Jianxi 3313 China 2 The First Affiliated Hospital of NanChang University Nanchang Jianxi 33123 China Abstract The exhaled breath samples of patients with chronic hepatitis B 41 cases and healthy volunteers 34 cases were detected by extractive electrospray ionization mass spectrometry EESI-MS. After the process of MS data using principal component analysis PCA methods the patients and normal subjects were distinguished effectively and the PCA results were also validated for cluster analysis CA. The results are helpful to the analysis of progression of chronic hepatitis B and may provide bases for the development of a simple rapid and noninvasive chnical diagnosis method for chronic hepatitis B. Keywords Chronic hepatitis B Exhaled breath Extractive electrospray ionization mass spectrometry Principal component analysis Cluster analysis This work was supported by the National Natural Science Foundation of China Nos. 21225522 212652 Received 27 ctober 214 accepted 18 January 215 櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫 478 SmartFlow - Thermo Scientific TM Dionex TM Chromeleon TM eworkflow Cobra Smart Link Chromeleon Thermo Scientific TM Vanquish TM Charger Vanquish UHPLC VanquishCharger 9 2 / 2 Vanquish 1 mm 6 mm LightPipe 1 2Hz 3D 4 1 nm 8 nm