33 4 Vol. 33 Iss. 4 2016 4 CHINESE JOURNAL OF APPLIED CHEMISTRY Apr. 2016 a a b a* a 330013 b 342400 Asparagus Officinalis L ieesi-ms CH 3 OH m /z 50 ~ 1000 CID 1 min O652 A DOI10. 11944 /j. issn. 1000-0518. 2016. 04. 150315 1000-0518201604-481-08 Asparagus Officinalis L 1-2 24 h 3 β 2 4-7 P 8 ambient ionization mass spectrometry 9 MPT 10 2015-08-31 2015-10-05 2015-11-20 21565004 IRT13054 20142BCB24005 KJLD13051 Tel /Fax0791-83896370E-mailchw8868@ gmail. com
482 33 LTP 11 DART 12 SDAPCI 13 LAESI 14 DESI 15 AFAI 16 EESI 17 paper spray 18 ieesi-ms 19-20 ieesi- MS ieesi- MS 1 1. 1 ieesi LTQ-XL Xcalibur Thermo Scientific 0. 10 mm 0. 19 mm Agilent Technologies ROE m /z 50 ~ 1000 3. 5 kv 150 80 V 65 V 1. 5 Da 10% ~ 30% 30 ~ 50 ms LTQ-Tune 1. 2 A B C D 4 ieesi-ms 1 min 1. 3 ieesi-ms ieesi-ms CH 3 OH 3 ~ 5 μl /min 2 mm 5 mm 1 1 Fig. 1 ieesi-ms Schematic diagram of ieesi-ms
4 483 2 2. 1 ieesi-ms ieesi-ms 2 2A 2B 2C2D A B C D ieesi-ms K + Na + M + K + M + Na + 20 / CID ieesi-ms / glucose /fructose MW180 sucrose MW342 m /z 219 glucose / fructose + K + m /z 381 sucrose + K + m /z 399 sucrose + K + H 2 O + m /z 561 glucose / fructose + sucrose + K + m /z 707 2sucrose + Na + 21 m /z 175 arginine + H + m /z 104 choline + MW170m /z 171 undecanal + H + MW184m /z 185 lauraldehyde + H +3 2 A A B B C CD D ieesi-ms Fig. 2 ieesi-ms spectra of fresh asparagus tubers subcutaneous tissue of AA BB CCand DDsegments which were cut out subsequently from the bottom to the top of asparegus ieesi-ms / glucose /fructose MW180 sucrose MW342 m /z 219 glucose /fructose + K + m /z 381 sucrose + K + m /z 399 sucrose + K + H 2 O + m /z 561 glucose /fructose + sucrose + K + m /z 104 choline + m /z 171undecanal + H + m /z 185 lauraldehyde + H + 2. 2 ieesi-ms 3 ieesi-ms 3A 3B 3C3D A B C D ieesi-ms m /z 219 glucose /fructose + K + m /z 381 sucrose + K + m /z 399 sucrose + K + H 2 O + m /z 175 arginine + H + m /z 104 choline + m /z 171 undecanal + H + m /z 185 lauraldehyde + H + m /z 649 814
484 33 3 A A B B C CD D ieesi-ms Fig. 3 ieesi-ms spectra of fresh asparagus epidermal tissue of AA BB CCand DDsegments which were cut out subsequently from the bottom to the top of asparegus m /z 976 CID m /z 814-162Da m /z 976 m /z 649 rutin MW610M + K + 5 P 2. 3 ieesi-ms ieesi-ms 4 4A 4B 1 2 m /z 104 171 185 219 381 399 797 821 976 m /z 219 glucose /fructose + K + m /z 399 sucrose + K + H 2 O + m /z 399 sucrose + K + H 2 O + m /z 381 sucrose + K + H 2 O m /z 700 ~ 900 m /z 797 821 CID PC34 2+ K + PC36 4+ K +22 2 m /z 175 arginine + 4 ieesi-ms Fig. 4 ieesi-ms spectra of two types of dry asparagus H + 1 tubers m /z 116 proline + H + A. rhizomeb. stem tip m /z 104 choline +
4 485 m /z 104 m /z 171 undecanal + H + m /z 185 lauraldehyde + H + 2. 4 CID 5 A B C DMS 2 CID m / z 104 choline + m /z 87 60 OH CHOHCH 2 5A m /z 171 undecanal + H + m /z 154 127 OH CH 2 CH 2 O 5B m /z 175 arginine + H + m /z 158 157 130 116 60 NH 3 17 H 2 O 18 COOH 45 NH CNH 2 2 59 5C 23 m /z 219 glucose + K + m /z 201 130 H 2 O18 C 3 H 5 O 3 5D MS 2 CID 1 1 5 m /z 104 A m /z 171 B m /z 175 C / m /z 219 DMS /MS Fig. 5 The MS 2 spectra of cholinem /z 104 A undecanalm /z 171 B argininem /z 175 Cand glucose m /z 219 Dfrom asparagus tissue 1 Table 1 ieesi-ms /MS The characteristic product ions of ieesi-ms / MS from asparagus tissue Cmpound Molecular structure Observed m /z Ion formation FragmentsMS /MS Undecanal Continued on next page O 154M + H - OH + 171 M + H + CH 3 CH 2 8 CH 2 H 127M + H - CH 2 CH 2 O +
486 33 continued from previous page Cmpound Molecular structure Observed m /z Ion formation FragmentsMS /MS Proline 116 M + H + 70M + H - H 2 O - CO + + 87M - OH + Choline 104 M 60M - CH 2 CH 2 O + Sucrose 342 M + K + 363M + K - H 2 O + 345M + K - 2H 2 O + 219M + K - Glu + 201M + K - Glucose + Serine H 2 O NCHCOH CH2 OH + 88M + H - H 2 O + 106 M + H 60M + H - H 2 O - CO + 158M + H - NH 3 + Arginine 175 M + H + 157M + H - H 2 O + 130M + H - COOH + 116M + H - NH = CCNH 2 2 + Glucose 219 M + K + 201M + K - H 2 O + 130M + K - C 3 H 5 O 3 + 2. 5 ieesi-ms SDAPCI-MS 13 LAESI-MS 14 Leaf spray- MS 21 ieesi-ms ieesi DESI SDAPCI 23-24 ieesi-ms ieesi-ms 19 4 ieesi-ms 1 min 1LI Cuixia MAO Ruoqing LI Zhizhong et al. Composition Analysis and Nutritional Evaluation of the Asparagus J. Mod
4 487 Food Sci Technol 2011 2710 1260-1263in Chinese.. J. 2011 2710 1260-1263. 2SUN Chunyan ZHAO Botao YU Zhifang et al. The Development of Chemical Components in Asparagus Officinalis and Their Medical Effects J. Chinese Wild Plant Resour 2004 235 1-5in Chinese.. J. 2004 235 1-5. 3KANG Xu YUAN Jianglan DENG Chuan et al. Analysis of Volatile Flavour Components in Green Asparagus Tea by GC- MS J. Farm Prod Process 2010 1256-58in Chinese.. GC-MS J. 2010 1256-58. 4Kim B Y Cui Z G Lee S R et al. Effects of Asparagus Officinalis Extracts on Liver Cell Toxicity and Ethanol Metabolism J. J Food Sci 2009 747 H204-208. 5Wang M F Tadmor Y Wu Q L et al. Quantification of Protodioscin and Rutin in Asparagus Shoots by LC / MS and HPLC methods J. J Agric Food Chem 2003 5121 6132-6136. 6Zhong C Jiang C Xia X et al. Antihepatic Fibrosis Effect of Active Components Isolated from Green AsparagusAsparagus Officinalis L. Involves the Inactivation of Hepatic Stellate Cells J. J Agric Food Chem 2015 6326 6027-6034. 7Hafizur R M Kabir N and Chishti S. Asparagus Officinalis Extract Controls Blood Glucose by Improving Insulin Secretion and Beta-Cell Function in Streptozotocin-Induced Type 2 Diabetic Rats J. Br J Nutr 2012 1089 1586-1595. 8Chua L S. A Review on Plant-Based Rutin Extraction Methods and its Pharmacological Activities J. J Ethnopharmacol 2013 1503 805-817. 9ZHANG Xie HU Bin CHEN Huanwen. Fundamental Principles and Practical Applications of Ambient Ionization Mass Spectrometry for Direct Analysis of Complex Samples J. Chinese J Anal Chem 2010 388 1069-1088in Chinese.. J. 2010 388 1069-1088. 10Zhang T Q Zhou W Jin W et al. Direct Desorption / Ionization of Analytes by Microwave Plasma Torch for Ambient Mass Spectrometric Analysis J. J Mass Spectrom 2013 486 669-676. 11Wiley J S Shelley J T Cooks R G. HandheldLow-Temperature Plasma Probe for Portable Point-and-Shoot Ambient Ionization Mass Spectrometry J. Anal Chem 2013 8514 6545-6552. 12Nah T Chan M Leone S R et al. RealTime in Situ Chemical Characterization of Submicrometer Organic Particles Using Direct Analysis in Real Time-Mass Spectrometry J. Anal Chem 2013 854 2087-2095. 13ZHU ZhiqiangYAN JianpingWANG Yu et al. Surface Desorption Atmospheric Pressure Chemical Ionization Mass Spectrometry for Rapid Analysis of Capmhor Wood ProductsJ. Chinese J Anal Chem 2013 41 6 905-910 in Chinese.. J. 2013 416 905-910. 14Shrestha B and Vertes A. High-throughput Cell and Tissue Analysis with Enhanced Molecular Coverage by Laser Ablation Electrospray Ionization Mass Spectrometry Using Ion Mobility Separation J. Anal Chem 2014 869 4308-4315. 15David Calligaris D C Xiaohui Liu Isaiah Norton et al. Application of Desorption Electrospray Ionization Mass Spectrometry Imaging in Breast Cancer Margin Analysis J. Proc Natl Acad Sci USA 2014 11142 15184-15189. 16Luo Z G He J M Chen Y et al. Air Flow-Assisted Ionization Imaging Mass Spectrometry Method for Easy Whole-body Molecular Imaging under Ambient Conditions J. Anal Chem 2013 855 2977-2982. 17Chen H W Sun Y P Arno Wortmann et al. Differentiation of Maturity and Quality of Fruit Using Noninvasive Extractive Electrospray Ionization Quadrupole Time-of-flight Mass Spectrometry J. Anal Chem 2007 794 1447-1455. 18Zhang C Manicke N E. Development of a Paper Spray Mass Spectrometry Cartridge with Integrated Solid Phase Extraction for Bioanalysis J. Anal Chem 2015 8712 6212-6219. 19Zhang H Gu H Yan F et al. Direct Characterization of Bulk Samples by Internal Extractive Electrospray Ionization Mass Spectrometry J. Sci Rep 2013 32495. 20Zhang H Chingin K Zhu L et al. Molecular Characterization of Ongoing Enzymatic Reactions in Raw Garlic Cloves Using Extractive Electrospray Ionization Mass Spectrometry J. Anal Chem 2015 875 2878-2883. 21Liu J Wang H Cooks R G et al. Leaf SprayDirect Chemical Analysis of Plant Material and Living Plants by Mass Spectrometry J. Anal Chem 2011 8320 7608-7613. 22Guo SWang Y Zhou D et al. Significantly Increased Monounsaturated Lipids Relative to Polyunsaturated Lipids in Six Types of Cancer Microenvironment are Observed by Mass Spectrometry Imaging J. Sci Rep 2014 45959. 23ZHANG Hua ZHU Liang CHEN Huanwen. Direct Molecular Analysis of Garlic Using Internal Extractive Electrospray Ionization Mass Spectrometry J. Chinese J Anal Chem 2014 4211 1634-1638in Chinese.. J. 2014 4211 1634-1639. 24Zhang H Zhu L Luo L et al. Direct Assessment of Phytochemicals Inherent in Plant Tissues Using Extractive Electrospray
488 33 Ionization Mass Spectrometry J. J Agric Food Chem 2013 6145 10691-10698. Rapid Analysis of Chemical Composition in Asparagus Using Internal Extractive Electrospray Ionization Mass Spectrometry LU Haiyan a ZHANG Hua a PENG Xiaoming b CHEN Huanwen a* a Jiangxi Key Laboratory for Mass Spectrometry and Instrumentation East China Institute of Techonolgy Nanchang 330013 China b Xingguo Xian Boyuan Agricultural Development Co. Ltd. Xingguo Jiangxi 342400 China Abstract Rapid analysis chemical composition of plant samples was achieved using internal extractive electrospray ionization mass spectrometryieesi-mswithout any sample pretreatment. In this studyfresh asparagus tubers together with two kinds of dry asparagus tubers were treated as representative samples for the ieesi-ms analysis. Choosing methanol as an ieesi extractantvarious chemical composition in asparagus tissue samples was profiled in mass scan range of m /z 50 ~ 1000 under the positive ion detection modeand through collision-induced dissociation CID experimentsnutrient and medicinal components including sugarsamino acidsalkaloidsand rutin were identifiedwhich play an significant role in development of pharmaceutical drugsnatural product research and understanding of primary and secondary metabolites. Our experimental results demonstrate that ieesi-ms makes rapid recognition of chemical composition differences in different asparagus. Such information renders the nutritious and medicinal assessment of plant natural products possible. The merits of ieesi-ms include no sample pretreatmenthigh-throughput less than 1 min per sample low sample consumptionsimplicityas well as good specificityshowing potential applications in phytochemicals analysis. Keywords asparagusinternal extractive electrospray ionizationmass spectrometrydirect analysis Received 2015-08-21Revised 2015-10-05Accepted 2015-11-20 Supported by the National Natural Science Foundation of ChinaNo. 21565004 Program for Changjiang Scholars and Innovative Research Team in UniversityPCSIRT No. IRT13054 Science and Technology Planning Project at the Department of Science and Technology of Jiangxi ProvinceChinaNo. 20142BCB24005 Jiangxi Province Program for the support of Science and Technology in UniversitiesNo. KJLD13051 Corresponding authorchen HuanwenprofessiorTel /Fax0791-83896370E-mailchw8868@ gmail. comresearch interestsmass spectrometry