Complementary Mass Spectrometry Imaging and Discovery of Quality Characters-Related Markers of Isatidis Radix Based on AP-MALDI-IT-TOF/MS and DESI-Q-TOF/MS
NIE Li-xing1, HUANG Lie-yan1, QIAN Xiu-yu2, KANG Shuai1, YAO Ling-wen1, DAI Zhong1, MA Shuang-cheng1*
1. National Institutes for Food and Drug Control, Beijing 100050, China; 2. Chinese Pharmaceutical Association, Beijing 100050, China
摘要目的 采用大气压基质辅助激光解吸电离-离子阱-飞行时间质谱(atmospheric pressure matrix assisted laser desorption combined with ion trap-time of flight mass spectrometry,AP-MALDI-IT-TOF/MS)和解吸电喷雾电离-四级杆-飞行时间质谱(desorption electrospray ionization combined with quadrupole-time of flight mass spectrometry,DESI-Q-TOF/MS)两种技术,实现板蓝根的全质谱成像分析,揭示多种成分的组织原位可视化分布,寻找品质特征相关指标群。方法 不同商品规格的板蓝根,分别喷涂2,5-二羟基苯乙酮(2,5-DHAP)和1,5-二氨基萘(1,5-DAN)基质,在正、负离子模式下进行AP-MALDI-IT-TOF/MS质谱成像、成分鉴定和偏最小二乘回归(partial least squares regression,PLSR)分析。不同品质特征的板蓝根,在正、负离子模式下进行DESI-Q-TOF/MS质谱成像、成分鉴定和正交偏最小二乘判别分析(orthogonal partial least squares discrimination analysis,OPLS-DA)分析。结果 板蓝根经质谱成像分析,初步鉴别得到多个类别约100余个化合物,AP-MALDI-IT-TOF/MS和DESI-Q-TOF/MS均可揭示板蓝根化合物的空间分布,并可区分不同规格、品质样品,3-醛基吲哚、前告依春/表前告依春、isatithioetherin C/isatithioetherin E、松柏苷、紫丁香酚苷、直铁线莲宁B、腺苷、腺嘌呤、尿苷、精氨酸、2-羟基丁二酸、顺丁烯二酸/富马酸、枸橼酸、大黄素-8-O-β-D-葡萄糖苷、异牡荆素在高商品规格/品质样品中特定空间分布信号更强,对分类影响显著,组成品质特征相关指标群。结论 质谱成像可将中药材的品质与化学信息建立连接,为其质量评价和进一步开发利用提供实验基础和新的手段。
Abstract：OBJECTIVE To reveal the spatial locations of components in Isatidis Radix and discover the markers relating to its quality characters by conducting mass spectrometry imaging(MSI)employing atmospheric pressure matrix assisted laser desorption combined with ion trap-time of flight mass spectrometry(AP-MALDI-IT-TOF/MS)and desorption electrospray ionization combined with quadrupole-time of flight mass spectrometry(DESI-Q-TOF/MS). METHODS After spraying with matrices of2′, 5′-dihydroxyacetophenone(2,5-DHAP) and 1, 5-Diaminonaphthalene(1,5-DAN), MSI of Isatidis Radix with different specifications was conducted by AP-MALDI-IT-TOF/MS in positive and negative modes, the components were identified, and the data was analyzed with partial least squares regression(PLSR). MSI of Isatidis Radix with different quality characters were conducted by DESI-Q-TOF/MS in positive and negative modes, the components were identified, and the data was analyzed with orthogonal partial least squares discrimination analysis(OPLS-DA). RESULTS As a result of MSI, above 100 ions in Isatidis Radix were assigned as several classes of components. AP-MALDI-IT-TOF/MS and DESI-Q-TOF/MS both could reveal the distribution of chemicals in Isatidis Radix and distinguish samples with different specifications and quality characters. Markers relating to the quality characters were 3-formylindole, epiprogoitrin/progoitrin, isatithioetherin C/isatithioetherin E, coniferin, syringing, clemastanin B, adenosine, adenine, uridine, arginine, malic acid, maleic acid/fumaric acid, citric acid, emodin-8-O-β-D-glucoside and isovitexin, which had stronger spatial signals in samples with higher specifications/quality characters and showed significant influence on differentiation. CONCLUSION MSI can link the quality characters and the chemical information of Chinese material medica, offering experimental basis and novel approach for quality evaluation and further development.
聂黎行, 黄烈岩, 钱秀玉, 康帅, 姚令文, 戴忠, 马双成. 基于AP-MALDI-IT-TOF/MS和DESI-Q-TOF/MS的板蓝根全质谱成像及品质相关指标成分群的研究[J]. 中国药学杂志, 2023, 58(9): 823-830.
NIE Li-xing, HUANG Lie-yan, QIAN Xiu-yu, KANG Shuai, YAO Ling-wen, DAI Zhong, MA Shuang-cheng. Complementary Mass Spectrometry Imaging and Discovery of Quality Characters-Related Markers of Isatidis Radix Based on AP-MALDI-IT-TOF/MS and DESI-Q-TOF/MS. Chinese Pharmaceutical Journal, 2023, 58(9): 823-830.
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2023, Vol. 58 
