芦笋中化学成分的内部萃取电喷雾电离质谱检测

doi:10.11944/j.issn.1000-0518.2016.04.150315

摘要/Abstract

摘要：

选择芦笋(Asparagus Officinalis L)新鲜茎块和两种干燥茎块为代表性植物组织样品,建立了一种直接检测芦笋中多种化学成分的内部萃取电喷雾电离质谱(iEESI-MS)分析方法。在正离子检测模式下,选择甲醇(CH₃OH)作萃取溶剂,在无需样品预处理的条件下对芦笋组织样品进行直接质谱分析,获得了组织样品在m/z 50~1000范围内的化学指纹谱图,并通过目标离子的碰撞诱导解离(CID)实验,鉴定了对药物和自然产品研发具有重要意义的糖类、氨基酸、生物碱以及芦丁等多种代表性的营养成分。本方法具有无需样品预处理、样品耗量少、操作简便、分析速度快(单个样品的分析时间少于1 min)等优点,为食源性植物组织样品的快速分析提供了一种质谱分析新方法。

关键词: 芦笋, 内部电喷雾萃取电离, 质谱, 直接分析

Abstract:

Rapid analysis chemical composition of plant samples was achieved using internal extractive electrospray ionization mass spectrometry(iEESI-MS) without any sample pretreatment. In this study, fresh 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 extractant, various chemical composition in asparagus tissue samples was profiled in mass scan range of m/z 50~1000 under the positive ion detection mode, and through collision-induced dissociation(CID) experiments, nutrient and medicinal components including sugars, amino acids, alkaloids, and rutin were identified, which play an significant role in development of pharmaceutical drugs, natural 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 pretreatment, high-throughput(less than 1 min per sample), low sample consumption, simplicity, as well as good specificity, showing potential applications in phytochemicals analysis.

Key words: asparagus, internal extractive electrospray ionization, mass spectrometry, direct analysis

卢海艳, 张华, 彭小明, 陈焕文. 芦笋中化学成分的内部萃取电喷雾电离质谱检测[J]. 应用化学, 2016, 33(4): 481-488.

LU Haiyan, ZHANG Hua, PENG Xiaoming, CHEN Huanwen. Rapid Analysis of Chemical Composition in Asparagus Using Internal Extractive Electrospray Ionization Mass Spectrometry[J]. Chinese Journal of Applied Chemistry, 2016, 33(4): 481-488.

参考文献

[1]	LI Cuixia,MAO Ruoqing,LI Zhizhong,et al.Composition Analysis and Nutritional Evaluation of the Asparagus[J]. Mod Food Sci Technol,2011,27(10):1260-1263(in Chinese). 李翠霞,毛箬青,李志忠,等. 芦笋营养成分的分析评价[J]. 现代食品科技,2011,27(10):1260-1263.
[2]	SUN Chunyan,ZHAO Botao,YU Zhifang,et al.The Development of Chemical Components in Asparagus Officinalis and Their Medical Effects[J]. Chinese Wild Plant Resour,2004,23(5):1-5(in Chinese). 孙春艳, 赵伯涛,郁志芳,等. 芦笋的化学成分及药理作用研究进展[J]. 中国野生植物资源,2004,23(5):1-5.
[3]	KANG Xu,YUAN Jianglan,DENG Chuan,et al.Analysis of Volatile Flavour Components in Green Asparagus Tea by GC-MS[J]. Farm Prod Process,2010,(12):56-58(in Chinese). 康旭, 袁江兰,邓川,等. 绿芦笋茶挥发性风味成分的GC-MS分析[J]. 农产品加工学刊,2010,(12):56-58.
[4]	Kim 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,2009,74(7):H204-208.
[5]	Wang 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,2003,51(21):6132-6136.
[6]	Zhong C,Jiang C,Xia X,et al.Antihepatic Fibrosis Effect of Active Components Isolated from Green Asparagus(Asparagus Officinalis L.) Involves the Inactivation of Hepatic Stellate Cells[J]. J Agric Food Chem,2015,63(26):6027-6034.
[7]	Hafizur 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,2012,108(9):1586-1595.
[8]	Chua L S. A Review on Plant-Based Rutin Extraction Methods and its Pharmacological Activities[J]. J Ethnopharmacol,2013,150(3):805-817.
[9]	ZHANG 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,2010,38(8):1069-1088(in Chinese). 张燮,胡斌,陈焕文. 复杂样品质谱分析技术的原理与应用[J]. 分析化学,2010,38(8):1069-1088.
[10]	Zhang 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,2013,48(6):669-676.
[11]	Wiley J S,Shelley J T,Cooks R G. HandheldLow-Temperature Plasma Probe for Portable “Point-and-Shoot” Ambient Ionization Mass Spectrometry[J]. Anal Chem,2013,85(14):6545-6552.
[12]	Nah 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,2013,85(4):2087-2095.
[13]	ZHU Zhiqiang,YAN Jianping,WANG Yu,et al.Surface Desorption Atmospheric Pressure Chemical Ionization Mass Spectrometry for Rapid Analysis of Capmhor Wood Products[J]. Chinese J Anal Chem,2013,41(6):905-910(in Chinese). 朱志强,闫建平,汪雨,等. 表面解吸常压化学电离质谱快速鉴别樟木制品[J]. 分析化学,2013,41(6):905-910.
[14]	Shrestha 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,2014,86(9):4308-4315.
[15]	David 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,2014,111(42):15184-15189.
[16]	Luo 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,2013,85(5):2977-2982.
[17]	Chen 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,2007,79(4):1447-1455.
[18]	Zhang C,Manicke N E. Development of a Paper Spray Mass Spectrometry Cartridge with Integrated Solid Phase Extraction for Bioanalysis[J]. Anal Chem,2015,87(12):6212-6219.
[19]	Zhang H,Gu H,Yan F,et al.Direct Characterization of Bulk Samples by Internal Extractive Electrospray Ionization Mass Spectrometry[J]. Sci Rep,2013,3:2495.
[20]	Zhang 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,2015,87(5):2878-2883.
[21]	Liu J,Wang H,Cooks R G,et al.Leaf Spray:Direct Chemical Analysis of Plant Material and Living Plants by Mass Spectrometry[J]. Anal Chem,2011,83(20):7608-7613.
[22]	Guo S,Wang 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,2014,4:5959.
[23]	ZHANG Hua,ZHU Liang,CHEN Huanwen. Direct Molecular Analysis of Garlic Using Internal Extractive Electrospray Ionization Mass Spectrometry[J]. Chinese J Anal Chem,2014,42(11):1634-1638(in Chinese). 张华,朱亮,陈焕文. 电喷雾内部萃取电离质谱直接分析蒜瓣组织的研究[J]. 分析化学,2014,42(11):1634-1639.
[24]	Zhang H,Zhu L,Luo L,et al.Direct Assessment of Phytochemicals Inherent in Plant Tissues Using Extractive Electrospray Ionization Mass Spectrometry[J]. J Agric Food Chem,2013,61(45):10691-10698.