目的 基于气相色谱-离子迁移谱(GC-IMS)技术建立白及饮片和黄花白及饮片的挥发性有机物指纹图谱,对比两者挥发性有机物的差异。方法 基于GC-IMS检测白及饮片和黄花白及饮片的挥发性有机物,采用直观法和指纹图谱法对比两者挥发性有机物的差异,并对其进行定性和定量分析;借助主成分分析(PCA)和正交偏最小二乘-判别分析(OPLS-DA)方法对指纹图谱筛选出的差异峰进行分析,并结合变量重要性投影值(VIP值)和P值筛选两者的差异标志物。结果 基于软件内置的NIST数据库和IMS数据库,在两种饮片中共定性出60种挥发性有机物,其以醇类、醛类、酮类为主;通过初步分析可观察到两种饮片部分挥发性有机物的峰强度存在较明显的差异,进一步通过对比指纹图谱和峰体积发现两种饮片共有65种含量差异较大的挥发性有机物,其中,白及有41种含量较高的成分,黄花白及有24种。最后结合VIP值和P值还确定了4-甲基-2-戊酮(二聚体)、樟脑(单体)、5-甲基-2-呋喃甲醇(二聚体)等12种差异标志物。结论 GC-IMS技术可用于白及饮片与黄花白及饮片挥发性有机物的快速分析和对比,为后期开展两者的整体差异研究提供重要的参考。
Abstract
OBJECTIVE To establish the fingerprints of volatile organic compounds (VOCs) in Bletilla striata decoction pieces and Bletilla ochracea decoction pieces based on gas chromatography-ion mobility spectrometry (GC-IMS) technology, and to compare the differences of VOCs between the two decoction pieces. METHODS The VOCs in Bletilla striata decoction pieces and Bletilla ochracea decoction pieces were detected by GC-IMS, and the differences of VOCs in the two kinds of decoction pieces were compared by two methods, the intuitive method and fingerprinting method, and at the same time, the qualitative and quantitative analysis were carried out to identify these volatile organic compounds. Principal component analysis (PCA) and orthogonal partial least squares-discriminant analysis (OPLS-DA) were used to analyze the differential peaks screened by fingerprints, and the differential marker were screened by combining the variable importance in the projection(VIP) and P-value. RESULTS Based on the built-in NIST database and IMS database in the software, a total of 60 VOCs were identified in two kinds of decoction pieces, most of which were alcohols, aldehydes, and ketones. Through preliminary analysis, it can be observed that the peak intensity of VOCs in two kinds of decoction pieces has obvious differences. Further comparison of fingerprint and peak volume shows that there are 65 kinds of VOCs whose content were quite different in the two kinds of decoction pieces, including 41 components with high contents in Bletilla striata and 24 components in Bletilla ochracea. Finally, combined with VIP and P-value, 12 kinds of differential markers such as the 4-methyl-2-pentanone dimer, alcanfor monomer, 5-methyl-2-furanmethanol dimer and other components were determined. CONCLUSION GC-IMS technology can be used for rapid analysis and comparison of VOCs in Bletilla striata decoction pieces and Bletilla ochracea decoction pieces, which can provide an important reference for the later study of the overall difference between Bletilla striata and Bletilla ochracea.
关键词
白及 /
黄花白及 /
气相色谱-离子迁移谱 /
挥发性有机物
{{custom_keyword}} /
Key words
Bletilla striata /
Bletilla ochracea /
gas chromatography-ion mobility spectroscopy(GC-IMS) /
volatile organic compound
{{custom_keyword}} /
{{custom_sec.title}}
{{custom_sec.title}}
{{custom_sec.content}}
参考文献
[1] Ch.P(2020)Vol Ⅱ(中国药典2020年版.一部)[S]. 2020:106-107.
[2] LIU J M, AN L L, LIU G, et al. Research progress on chemical composition and pharmacological effects of Bletilla Striate and predictive analysis on quality marker [J]. Chin Arch Tradit Chin Med(中华中医药学刊),2021, 39(6):28-37.
[3] LIU G, DING Z S, LIU Y C, et al. Establishment on HPLC fingerprint of Bletilla striata and their cluster analysis [J]. J China Pharm(中国药房),2018, 29(22):3050-3053.
[4] DONG Y X, LIU X X, DONG L, et al. Study on hemostatic effect and mechanism of polysaccharides from Bletilla striata in blood heat and hemorrhage model rats [J]. J China Pharm(中国药房),2016, 27(31):4347-4350.
[5] XU D, PAN Y, CHEN J. Chemical constituents, pharmacologic properties, and clinical applications of Bletilla striata [J]. Front Pharmacol,2019, 10:1168. Doi:10.3389.fphar.2019.01168.
[6] SUN A J, PANG S Q, WANG G Q. Chemical constituents from Bletilla striata and their anti-tumor activities [J]. Chin Pharm J(中国药学杂志),2016, 51(2):101-104.
[7] ZHANG M, HAN T T, HU C F, et al. Industrialization condition and sustainable development strategies of Bletillae Rhizoma [J]. Chin Tradit Herb Drugs(中草药),2019, 50(20):5103-5108.
[8] LIU J H, ZHOU L, ZHONG X H, et al. Research progress in Bletilla striata resource and development strategy for long industry chain [J]. Mod Chin Med(中国现代中药),2017, 19(10):1485-1494,1504.
[9] ZHANG M, SHAO Q, XU E, et al. Bletilla striata: a review of seedling propagation and cultivation modes [J]. Physiol Mol Biol Plants,2019, 25(3):601-609.
[10] ADMINISTRATION FOR MARKET REGULATION OF SICHUAN PROVINCE. Standard for Chinese Medicinal Materials in Sichuan Province(2010 Edition)(四川省中药材标准2010版)[M]. Chengdu:Sichuan Science and Technology Press, 2011:583.
[11] GANSU MEDICAL PRODUCT ADMINISTRATION. Standard for Chinese Medicinal Materials in Gansu Province(2020 Edition)(甘肃省中药材标准2020版)[M]. Lanzhou: Lanzhou University Press, 2020:13.
[12] CHEN M J, LI F Q, LYU M, et al. Comparison and identification of secondary structure of ITS2 sequence in Bletillae Rhizoma and its counterfeits [J]. Chin J Exp Tradit Med Form(中国实验方剂学杂志),2017, 23(15):46-52.
[13] CHEN M J. Study on quality evaluation of Bletilla Rhizoma[D]. Chengdu:Chengdu University of Traditional Chinese Medicine, 2017.
[14] SU T, LI X F, QIU B, et al. Pharmacognostical Study on Bletilla Produced in Yunnan Province [J]. Res Pract Chin Med(现代中药研究与实践),2015, 29(6):18-21.
[15] CHEN M J, LI F Q, CHEN H P, et al. Study on UPLC fingerprints of Rhizoma Bletillae and Bletilla ochracea [J]. Pharm Clin Chin Mater Med(中药与临床),2017, 8(5):8-14.
[16] JIN L, GUO F Q, FU M M, et al. Progresses on molecular authentication of Bletilla striata[EB/OL]. [2023-05-16]. http://kns.cnki.net/kems/detail/46.1068.5.20210713.1319.003.html.
[17] XIONG G H, ZHOU X G, XIAO F. Identification of the volatile oil components from the tuber of Bletilla Striata by GC-MS analysis [J]. J Jinggangshan Univ-Nat Sci(井冈山大学学报-自然科学版),2020, 41(6):46-50.
[18] CHEN T, GU H, CHEN M J, et al. Measurement of the refining degree of sunflower oil based on Gas Chromatography-Ion Mobility Spectrometry [J]. Food Sci(食品科学),2019, 40(18):312-316.
[19] Baumbach J I. Process analysis using ion mobility spectrometry [J]. Anal Bioanal Chem,2006, 384(5):1059-1070.
[20] TANG Y Q N, LI L, LIN L M, et al. Differences of flavor compounds in lonicerae japonicae flos and lonicerae flos based on headspace gas chromatography-ion mobility spectroscopy [J]. China J Chin Mater Med(中国中药杂志) ,2022,47(14):3798-3805.
[21] VAUTZ W, FRANZKE J, ZAMPOLLI S, et al. On the potential of ion mobility spectrometry coupled to GC pre-separation – A tutorial [J]. Anal Chim Acta, 2018 Sep 18;1024:52-64.
[22] DING X L, WANG G Y, ZOU Y L, et al. Influence of partial replacement of NaCl with KCl on the volatile compounds of Xuanwei ham investigated by Gas Chromatography-Ion Mobility Spectrometry combined with multivariate statistical analysis [J]. Food Sci(食品科学),2020, 41(24):190-198.
[23] CHEN Y J, YU J N, JING G X, et al. Application of gas chromatography-ion mobility spectrometry in agriculture [J]. Chin J Anal Lab(分析试验室),2020, 39(12):1480-1488.
[24] LI Q, LI X J, REN Z Y, et al. Physicochemical properties and antioxidant activity of Maillard reaction products derived from Dioscorea opposita polysaccharides [J]. LWT-Food Sci Technol,2021, 149:111833. Doi:10.1016.j.lwt.2021.111833.
[25] DAULTON E, WICAKSONO A N, TIELE A, et al. Volatile organic compounds(VOCs) for the non-invasive detection of pancreatic cancer from urine [J]. Talanta,2020, 221:121604. Doi:10.1016.j.talanta.2020.121604.
[26] BUDZYNSKA E, SIELEMANN S, PUTON J, et al. Analysis of e-liquids for electronic cigarettes using GC-IMS/MS with headspace sampling [J]. Talanta, 2020, 209:120594.
[27] LIANG T Y, YANG J, DONG H, et al. Identification of volatile flavor substances in Xinhui tangerine peel in different years based on GC-IMS technology [J]. China Cond(中国调味品),2020, 45(4):168-173.
[28] ZHOU Q, DAI Y P, GUO W, et al. Analysis of volatile organic compounds(VOCs)fingerprint of raw and honey-fried licorice based on headspace-gas-chromatography ion-mobility spectrometry(HS-GC-IMS) [J]. China J Chin Mater Med(中国中药杂志),2020, 45(16):3857-3862.
[29] ZHOU M, ZHOU Q, JIANG H Q, et al. A kind of quality evaluation method of traditional Chinese medicine licorice and its application:China,201911132222.8[P]. 2022-01-07.
[30] SHI D H, DAI Y P, LU Q, et al. Primary study on identification of carbonizing degree of Platycladi Cacumen based on odor detection by GC-IMS [J]. Chin Tradit Herb Drugs(中草药),2021, 52(21):6510-6517.
[31] FENG J W, GUO X H, ZHANG Y, et al. GC-IMS Analysis of Volatile Components in Rhododendri Mollis Flos at Different Flowering Stages [J]. Chin J Exp Tradit Med Form(中国实验方剂学杂志),2021, 27(10):85-92.
[32] HE J, HUANG W K, MA X F, et al. Geoherbalism and grand evaluation of Zhejiang Ophiopogon japonicas based on PCA and PLS-DA [J]. Chin Pharm J(中国药学杂志),2021, 56(4):285-292.
[33] ARROYO-MANZANARES N, MARTIN GOMEZ A, JURADO-CAMPOS N, et al. Target vs spectral fingerprint data analysis of Iberian ham samples for avoiding labelling fraud using headspace-gas chromatography-ion mobility spectrometry [J]. Food Chem,2018, 246:65-73.
[34] WANG Y C, ZHANG M M, MA W Y, et al. Effect of different drying methods on volatile components in pseudostellariae Radix based on GC-IMS [J]. Chin J Exp Tradit Med Form(中国实验方剂学杂志), 2022,28(20):100-107.
[35] GE S, CHEN Y Y, PENG Z G, et al. Application of Headspace-gas Chromatography-ion Mobility Spectrometry to Investigate the Influence of Drying Method on Volatile Substances of Capsicum frutescens [J]. Acta Laser Biol Sin(激光生物学报),2020, 29(4):368-378.
[36] RODRIGUEZ-MAECKER R, VYHMEISTER E, MEISEN S, et al. Identification of terpenes and essential oils by means of static headspace gas chromatography-ion mobility spectrometry [J]. Anal Bioanal Chem, 2017, 409(28):6595-6603.
[37] CHEN J, ZHANG Q, ZHAO S, et al. Quality evaluation of Glycyrrhiza uralensis Fisch. in different harvest periods based on combinative methods of HPLC specific chromatogram, Multi-Component Assay, and Chemometrics [J]. Chin Pharm J(中国药学杂志),2020, 55(18):1540-1547.
[38] LI J E, NIE S P, QIU Z H, et al. Antimicrobial and antioxidant activities of the essential oil from Herba Moslae [J]. J Sci Food Agric,2010, 90(8):1347-1352.
[39] GU C A, GU H J. Prduction of isovaleraldehyde and isovaleril acid. 2006 Proceedings of the Seminar on Fragrance and Flavor China(2006年中国香料香精学术研讨会论文集)[C]. Beijing:China Association of Fragrance Flavour and Cosmetic Industries, 2006:154-155.
{{custom_fnGroup.title_cn}}
脚注
{{custom_fn.content}}
基金
国家自然科学基金项目资助(81773892);国家重点研发计划中医药现代化重点专项资助(2017YFC1703400,2017YFC1703401,2017YFC1703402);河南省中医药拔尖人才培养项目资助(2019ZYBJ07);河南省高层次人才特殊支持“中原千人计划”-“中原青年拔尖人才”项目资助(ZYQR201912158);河南省卫生健康中青年学科带头人专项资助(HNSWJW-2020014);河南省科技攻关项目资助(222102310377);河南省卫生健康委员会国家中医临床研究基地科研专项课题资助(2021JDZY104);2022年协同创新中心研究生科研创新基金项目资助(协同中心[2022]002)
{{custom_fund}}
PDF(2512 KB)
