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Article(id=1239238142952272593, tenantId=1146029695717560320, journalId=1205117023404326918, issueId=1239238136711139764, articleNumber=null, orderNo=null, doi=10.16155/j.0254-1793.2023-0616, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1695139200000, receivedDateStr=2023-09-20, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773386997211, onlineDateStr=2026-03-13, pubDate=1722355200000, pubDateStr=2024-07-31, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773386997211, onlineIssueDateStr=2026-03-13, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773386997211, creator=13701087609, updateTime=1773386997211, updator=13701087609, issue=Issue{id=1239238136711139764, tenantId=1146029695717560320, journalId=1205117023404326918, year='2024', volume='44', issue='7', pageStart='1105', pageEnd='1284', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773386995723, creator=13701087609, updateTime=1773387118529, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1239238651851370909, tenantId=1146029695717560320, journalId=1205117023404326918, issueId=1239238136711139764, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1239238651851370910, tenantId=1146029695717560320, journalId=1205117023404326918, issueId=1239238136711139764, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=1222, endPage=1232, ext={EN=ArticleExt(id=1239238143250068202, articleId=1239238142952272593, tenantId=1146029695717560320, journalId=1205117023404326918, language=EN, title=Establishment of identification method for Fritillariae Cirrhosae Bulbus and its adulterant Fritillariae Ussuriensis Bulbus based on chemometrics, columnId=1206272757852074373, journalTitle=Chinese Journal of Pharmaceutical Analysis, columnName=Safety Monitoring, runingTitle=null, highlight=null, articleAbstract=
Objective:

To establish a method for identifying Fritillariae Cirrhosae Bulbus and its adulterant Fritillariae Ussuriensis Bulbus.

Methods:

Chemometrics techniques were used for the analysis of the sample data from determination with Q TOF MS, and characteristic ion pairs were selected as m/z 578.3→164.14 and m/z 578.3→398.31 with triple quadrupole mass spectrometry applied, respectively. Then a specific approach was developed which used Waters Acquisition UPLC CSH (75 mm×2.1 mm, 1.7 μm) as column, and with acetonitrile and 0.1% formic acid solution as the mobile phase, and a flow rate of 0.4 mL·min-1. Two ion pairs: m/z 578.3→164.14 and m/z 578.3→398.31 were detected by triple quadrupole mass spectrometer with MRM mode.

Results:

The validation results through 108 batches of samples indicated that the two characteristic ion pairs, m/z 578.3→164.14 and m/z 578.3→398.31, could effectively distinguish between Fritillariae Cirrhosae Bulbus and its adulterant Fritillariae Ussuriensis Bulbus.

Conclusion:

The method had good specificity and sensitivity, and could be used for the detection of adulterated Fritillariae Cirrhosae Bulbus with Fritillariae Ussuriensis Bulbus.

, correspAuthors=Feng WEI, Shuang-cheng MA, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, authorCompany=null, fund=null, authors=null, authorsList=Yan SHI, Wei LIU, Feng WEI, Shuang-cheng MA), CN=ArticleExt(id=1239238147440178107, articleId=1239238142952272593, tenantId=1146029695717560320, journalId=1205117023404326918, language=CN, title=基于化学计量学的川贝母药材及其混伪品平贝母的鉴别方法的建立, columnId=1206272758036623764, journalTitle=药物分析杂志, columnName=安全监测, runingTitle=null, highlight=null, articleAbstract=
目的：

建立能够鉴别川贝母及其混伪品平贝母的方法。

方法：

使用化学计量学技术对样品四极杆串联飞行时间（Q TOF）质谱仪测定数据进行分析，并结合三重四极杆质谱筛选出特征离子对为m/z 578.3→164.14和m/z 578.3→398.31。采用Waters Acquity UPLC CSH（75 mm×2.1 mm，1.7 μm）色谱柱，以乙腈-0.1%甲酸溶液为流动相，流速0.4 mL·min-1。三重四极杆质谱仪MRM模式检测m/z 578.3→164.14和m/z 578.3→398.31 2个离子对。

结果：

108批样品的验证结果表明，m/z 578.3→164.14和m/z 578.3→398.31 2个特征离子对能够有效区分川贝母及其混伪品平贝母。

结论：

方法有较好的专属性和灵敏度，可用于平贝母掺伪川贝母的检测。

, correspAuthors=魏锋, 马双成, authorNote=null, correspAuthorsNote=
* 马双成　Tel：(010)53852076；E-mail：；
魏锋　Tel：(010)53852020；E-mail：
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Tel：（010）53852081；E-mail：

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Vol Ⅰ[S]. 2020： 38, articleTitle=null, refAbstract=null), Reference(id=1239238156613120280, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, doi=null, pmid=null, pmcid=null, year=2001, volume=935, issue=1-2, pageStart=321, pageEnd=null, url=null, language=null, rfNumber=[3], rfOrder=4, authorNames=LIN G, LI P, LI S, journalName=J Chromatogr A, refType=null, unstructuredReference=LIN G， LI P， LI S， et al. Chromatographic analysis of Fritillaria isosteroidal alkaloids， the active ingredients of beimu， the antitussive traditional Chinese medicinal herb[J]. J Chromatogr A， 2001， 935(1-2)： 321, articleTitle=Chromatographic analysis of Fritillaria isosteroidal alkaloids， the active ingredients of beimu， the antitussive traditional Chinese medicinal herb, refAbstract=null), Reference(id=1239238156697006363, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, doi=null, pmid=null, pmcid=null, year=2014, volume=null, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[4], rfOrder=5, authorNames=WANG D, WANG S, DU Q, journalName=BioMed Res Int, refType=null, unstructuredReference=WANG D， WANG S， DU Q， et al. Optimization of extraction and enrichment of steroidal alkaloids from bulbs of cultivated Fritillaria cirrhosa[J]. BioMed Res Int， 2014： 258402, articleTitle=Optimization of extraction and enrichment of steroidal alkaloids from bulbs of cultivated Fritillaria cirrhosa, refAbstract=null), Reference(id=1239238156814446878, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, doi=null, pmid=null, pmcid=null, year=2009, volume=40, issue=1, pageStart=15, pageEnd=null, url=null, language=null, rfNumber=[5], rfOrder=6, authorNames=曹新伟, 张萌, 李军, journalName=中草药, refType=null, unstructuredReference=曹新伟， 张萌， 李军， 等. 川贝母生物碱类成分的研究[J]. 中草药， 2009， 40(1)： 15, articleTitle=川贝母生物碱类成分的研究, refAbstract=null), Reference(id=1239238156948664614, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, doi=null, pmid=null, pmcid=null, year=2009, volume=40, issue=1, pageStart=15, pageEnd=null, url=null, language=null, rfNumber=[5], rfOrder=7, authorNames=CAO XW, ZHANG M, LI J, journalName=Chin Tradit Herb Drugs, refType=null, unstructuredReference=CAO XW， ZHANG M， LI J， et al. Alkaloid constituents of Fritillaria cirrhosa [J]. Chin Tradit Herb Drugs， 2009， 40(1)： 15, articleTitle=Alkaloid constituents of Fritillaria cirrhosa, refAbstract=null), Reference(id=1239238157057716521, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, doi=null, pmid=null, pmcid=null, year=2014, volume=36, issue=7, pageStart=1477, pageEnd=null, url=null, language=null, rfNumber=[6], rfOrder=8, authorNames=雷艳辉, 李会军, 李萍, journalName=中成药, refType=null, unstructuredReference=雷艳辉， 李会军， 李萍. 川贝母药材生物碱成分HPLC-ELSD特征图谱的研究[J]. 中成药， 2014， 36(7)： 1477, articleTitle=川贝母药材生物碱成分HPLC-ELSD特征图谱的研究, refAbstract=null), Reference(id=1239238157137408301, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, doi=null, pmid=null, pmcid=null, year=2014, volume=36, issue=7, pageStart=1477, pageEnd=null, url=null, language=null, rfNumber=[6], rfOrder=9, authorNames=LEI YH, LI HJ, LI P, journalName=Chin Tradit Pat Med, refType=null, unstructuredReference=LEI YH， LI HJ， LI P. HPLC-ELSD specific chromatograms of alkaloid components in Fritillariae Cirrhosae Bulbus[J]. Chin Tradit Pat Med， 2014， 36(7)： 1477, articleTitle=HPLC-ELSD specific chromatograms of alkaloid components in Fritillariae Cirrhosae Bulbus, refAbstract=null), Reference(id=1239238157246460210, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, doi=null, pmid=null, pmcid=null, year=2019, volume=34, issue=5, pageStart=463, pageEnd=null, url=null, language=null, rfNumber=[7], rfOrder=10, authorNames=李成容, 李冬连, 李玲蕊, journalName=华西药学杂志, refType=null, unstructuredReference=李成容， 李冬连， 李玲蕊， 等. 栽培瓦布贝母中生物碱类成分的研究[J]. 华西药学杂志， 2019， 34(5)： 463, articleTitle=栽培瓦布贝母中生物碱类成分的研究, refAbstract=null), Reference(id=1239238157359706423, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, doi=null, pmid=null, pmcid=null, year=2019, volume=34, issue=5, pageStart=463, pageEnd=null, url=null, language=null, rfNumber=[7], rfOrder=11, authorNames=LI CR, LI DL, LI LR, journalName=West China J Pharm Sci, refType=null, unstructuredReference=LI CR， LI DL， LI LR， et al. Study on alkaloid constituents from the bulbus of cultivated Fritillaria wabuensis [J]. West China J Pharm Sci， 2019， 34(5)： 463, articleTitle=Study on alkaloid constituents from the bulbus of cultivated Fritillaria wabuensis, refAbstract=null), Reference(id=1239238157468758329, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, doi=null, pmid=null, pmcid=null, year=2019, volume=54, issue=12, pageStart=1012, pageEnd=null, url=null, language=null, rfNumber=[8], rfOrder=12, authorNames=李冬连, 李成容, 黎萍, journalName=中国药学杂志, refType=null, unstructuredReference=李冬连， 李成容， 黎萍， 等. HPLC-ELSD同时测定瓦布贝母药材中7种异甾体生物碱[J]. 中国药学杂志， 2019， 54(12)： 1012, articleTitle=HPLC-ELSD同时测定瓦布贝母药材中7种异甾体生物碱, refAbstract=null), Reference(id=1239238157556838715, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, doi=null, pmid=null, pmcid=null, year=2019, volume=54, issue=12, pageStart=1012, pageEnd=null, url=null, language=null, rfNumber=[8], rfOrder=13, authorNames=LI DL, LI CR, LI P, journalName=Chin Pharm J, refType=null, unstructuredReference=LI DL， LI CR， LI P， et al. Simultaneous determination of seven isosteroidal alkaloids in Fritillaria wabuensis by HPLC-ELSD method [J]. Chin Pharm J， 2019， 54(12)： 1012, articleTitle=Simultaneous determination of seven isosteroidal alkaloids in Fritillaria wabuensis by HPLC-ELSD method, refAbstract=null), Reference(id=1239238159159062847, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, doi=null, pmid=null, pmcid=null, year=2016, volume=151, issue=null, pageStart=239, pageEnd=null, url=null, language=null, rfNumber=[9], rfOrder=14, authorNames=LONG Z, GUO Z, ACWORTH IN, journalName=Talanta, refType=null, unstructuredReference=LONG Z， GUO Z， ACWORTH IN， et al. A non-derivative method for the quantitative analysis of isosteroidal alkaloids from Fritillaria by high performance liquid chromatography combined with charged aerosol detection[J]. Talanta， 2016， 151： 239, articleTitle=A non-derivative method for the quantitative analysis of isosteroidal alkaloids from Fritillaria by high performance liquid chromatography combined with charged aerosol detection, refAbstract=null), Reference(id=1239238159272309058, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, doi=null, pmid=null, pmcid=null, year=2009, volume=1216, issue=11, pageStart=2142, pageEnd=null, url=null, language=null, rfNumber=[10], rfOrder=15, authorNames=LI H, JIANG Y, LI P, journalName=J Chromatogr A, refType=null, unstructuredReference=LI H， JIANG Y， LI P. Characterizing distribution of steroidal alkaloids in Fritillaria spp. and related compound formulas by liquid chromatography-mass spectrometry combined with hierarchial cluster analysis[J]. J Chromatogr A， 2009， 1216(11)： 2142, articleTitle=Characterizing distribution of steroidal alkaloids in Fritillaria spp. and related compound formulas by liquid chromatography-mass spectrometry combined with hierarchial cluster analysis, refAbstract=null), Reference(id=1239238159414915397, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, doi=null, pmid=null, pmcid=null, year=1998, volume=44, issue=1, pageStart=175, pageEnd=null, url=null, language=null, rfNumber=[11], rfOrder=16, authorNames=WOLD S, ANTTI H, LINDGREN F, journalName=Chemometr Intell Lab, refType=null, unstructuredReference=WOLD S， ANTTI H， LINDGREN F， et al. Orthogonal signal correction of near-infrared spectra[J]. Chemometr Intell Lab， 1998， 44(1)： 175, articleTitle=Orthogonal signal correction of near-infrared spectra, refAbstract=null), Reference(id=1239238159549133128, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, doi=null, pmid=null, pmcid=null, year=2002, volume=16, issue=3, pageStart=119, pageEnd=null, url=null, language=null, rfNumber=[12], rfOrder=17, authorNames=TRYGG J, WOLD S, journalName=J Chemometr, refType=null, unstructuredReference=TRYGG J， WOLD S. Orthogonal projections to latent structures(O-PLS)[J]. J Chemometr， 2002， 16(3)： 119, articleTitle=Orthogonal projections to latent structures(O-PLS), refAbstract=null), Reference(id=1239238159658185035, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, doi=null, pmid=null, pmcid=null, year=2011, volume=25, issue=9, pageStart=514, pageEnd=null, url=null, language=null, rfNumber=[13], rfOrder=18, authorNames=BIAGIONI JD, ASTLING PD, GRAF P, journalName=J Chemometr, refType=null, unstructuredReference=BIAGIONI JD， ASTLING PD， GRAF P， et al. Orthogonal projection to latent structures solution properties for chemometrics and systems biology data[J]. J Chemometr， 2011， 25(9)： 514, articleTitle=Orthogonal projection to latent structures solution properties for chemometrics and systems biology data, refAbstract=null), Reference(id=1239238159767236944, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, doi=null, pmid=null, pmcid=null, year=2016, volume=24, issue=4, pageStart=1480, pageEnd=null, url=null, language=null, rfNumber=[14], rfOrder=19, authorNames=YIN S, WANG G, GAO H, journalName=IEEE Trans Control Syst Technol, refType=null, unstructuredReference=YIN S， WANG G， GAO H. Data-driven process monitoring based on modified orthogonal projections to latent structures[J]. IEEE Trans Control Syst Technol， 2016， 24(4)：1480, articleTitle=Data-driven process monitoring based on modified orthogonal projections to latent structures, refAbstract=null), Reference(id=1239238159859511633, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, doi=null, pmid=null, pmcid=null, year=2014, volume=28, issue=8, pageStart=623, pageEnd=null, url=null, language=null, rfNumber=[15], rfOrder=20, authorNames=GALINDO-PRIETO B, ERIKEEON L, TRYGG J, journalName=J Chemometr, refType=null, unstructuredReference=GALINDO-PRIETO B， ERIKEEON L， TRYGG J. Variable influence on projection (VIP) for orthogonal projections to latent structures(OPLS)[J]. J Chemometr， 2014， 28(8)：623, articleTitle=Variable influence on projection (VIP) for orthogonal projections to latent structures(OPLS), refAbstract=null)], funds=null, companyList=[AuthorCompany(id=1239238147679253452, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, xref=null, ext=[AuthorCompanyExt(id=1239238147683447757, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, companyId=1239238147679253452, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=National Institutes for Food and Drug Control, Beijing 102629, China), AuthorCompanyExt(id=1239238147691836367, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, companyId=1239238147679253452, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=中国食品药品检定研究院，北京 102629)])], figs=[ArticleFig(id=1239238152326541463, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, language=EN, label=Fig.1, caption=Total ion chromatograms of Fritillariae　Cirrhosae Bulbus samples from different origins and Fritillariae Ussuriensis Bulbus sample with UPLC-Q TOF MS, figureFileSmall=7u/2LhfLkFBJsMrYuRsVqA==, figureFileBig=o8dwww99RioW9dDXbkY7Zg==, tableContent=null), ArticleFig(id=1239238152427204761, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, language=CN, label=图1, caption=不同基原川贝母与平贝母UPLC-Q TOF MS测定总离子流图, figureFileSmall=7u/2LhfLkFBJsMrYuRsVqA==, figureFileBig=o8dwww99RioW9dDXbkY7Zg==, tableContent=null), ArticleFig(id=1239238152645308577, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, language=EN, label=Fig.2, caption=Cluster analysis dendrogram of samples, figureFileSmall=5XHRUAEyfT0+bvX3N7nFcQ==, figureFileBig=Sa7pavieUsh4yYeSlOuAvw==, tableContent=null), ArticleFig(id=1239238152750166184, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, language=CN, label=图2, caption=样品聚类分析树状图, figureFileSmall=5XHRUAEyfT0+bvX3N7nFcQ==, figureFileBig=Sa7pavieUsh4yYeSlOuAvw==, tableContent=null), ArticleFig(id=1239238152922132655, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, language=EN, label=Fig.3, caption=Correlation hot map of samples, figureFileSmall=WXAC1fKTIbBd7NXVvTcXMg==, figureFileBig=nc5gy7pXa4mRL0Bb9+f8Gw==, tableContent=null), ArticleFig(id=1239238153022795956, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, language=CN, label=图3, caption=样品相关性热图, figureFileSmall=WXAC1fKTIbBd7NXVvTcXMg==, figureFileBig=nc5gy7pXa4mRL0Bb9+f8Gw==, tableContent=null), ArticleFig(id=1239238153123459258, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, language=EN, label=Fig.4, caption=Principal component analysis of samples, figureFileSmall=8xDhK6+dWRu+oZ3/gNSOtw==, figureFileBig=ajHxoBmLiegoHJq1qbL0aw==, tableContent=null), ArticleFig(id=1239238154625020098, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, language=CN, label=图4, caption=样品主成分分析

A.样品得分分布散点图(score scatter plot of samples)　B.主成分累计方差折线图(principal component cumulative variance line chart)

, figureFileSmall=8xDhK6+dWRu+oZ3/gNSOtw==, figureFileBig=ajHxoBmLiegoHJq1qbL0aw==, tableContent=null), ArticleFig(id=1239238154780209348, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, language=EN, label=Fig.5, caption=Scatter plot of samples with OPLS-DA, figureFileSmall=T0F82k23ojVptApOl5oOww==, figureFileBig=awk9EKo0S6Pk2x8NbMs27w==, tableContent=null), ArticleFig(id=1239238154939592907, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, language=CN, label=图5, caption=样品OPLS-DA分布散点图, figureFileSmall=T0F82k23ojVptApOl5oOww==, figureFileBig=awk9EKo0S6Pk2x8NbMs27w==, tableContent=null), ArticleFig(id=1239238155065422032, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, language=EN, label=Fig.6, caption=S-plot(A) and VIP (B) of OPLS-DA method, figureFileSmall=nrl5ALpmZKxPFDsA/sAnwA==, figureFileBig=ks+Fm4tmxXl8TRRTe8nLBg==, tableContent=null), ArticleFig(id=1239238155166085331, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, language=CN, label=图6, caption=OPLS-DA法的S-plot图(A)和VIP图(B), figureFileSmall=nrl5ALpmZKxPFDsA/sAnwA==, figureFileBig=ks+Fm4tmxXl8TRRTe8nLBg==, tableContent=null), ArticleFig(id=1239238155275137239, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, language=EN, label=Fig.7, caption=Fragment ion mass spectrometry of characteristic ion of m/z 578.3, figureFileSmall=l6GTS9WcEvlkhDGV/4o5+w==, figureFileBig=fmxjUuEk5vQSvGly+y6fBQ==, tableContent=null), ArticleFig(id=1239238155367411932, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, language=CN, label=图7, caption=m/z 578.3特征离子碎片离子质谱图, figureFileSmall=l6GTS9WcEvlkhDGV/4o5+w==, figureFileBig=fmxjUuEk5vQSvGly+y6fBQ==, tableContent=null), ArticleFig(id=1239238155484852448, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, language=EN, label=Fig.8, caption=Chromatograms of blank，Fritillariae Cirrhosae Bulbus samples from different origins and Fritillariae Ussuriensis Bulbus sample with MRM model, figureFileSmall=7vzdBuRMhkzMTHLZCXfmZg==, figureFileBig=urCeOt5TowiyyNxXNE98NQ==, tableContent=null), ArticleFig(id=1239238155568738534, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, language=CN, label=图8, caption=空白与不同基原川贝母与平贝母样品MRM模式色谱图, figureFileSmall=7vzdBuRMhkzMTHLZCXfmZg==, figureFileBig=urCeOt5TowiyyNxXNE98NQ==, tableContent=null), ArticleFig(id=1239238155648430314, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, language=EN, label=Fig.9, caption=Chromatograms of sample with 1% adulteration ratio with Fritillariae Ussuriensis Bulbus using MRM model, figureFileSmall=pkxj6scDIPlps2fzdm1/pg==, figureFileBig=LXgiYTGFefAQQ/1v5UzCjQ==, tableContent=null), ArticleFig(id=1239238155799425264, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, language=CN, label=图9, caption=平贝母1%比例掺伪样品的MRM模式检测色谱图, figureFileSmall=pkxj6scDIPlps2fzdm1/pg==, figureFileBig=LXgiYTGFefAQQ/1v5UzCjQ==, tableContent=null), ArticleFig(id=1239238155908477171, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, language=EN, label=Tab.1, caption=

Information of samples

, figureFileSmall=null, figureFileBig=null, tableContent=
序号
(serial number)		编号
(sample No.)		植物来源或商品规格
(plant source or product specification)		产地或来源
(origin or source)
1AZ_1暗紫贝母(F. unibracteata)四川(Sichuan)
2AZ_2四川(Sichuan)
3AZ_3四川(Sichuan)
4AZ_4四川(Sichuan)
5AZ_5四川(Sichuan)
6AZ_6四川(Sichuan)
7AZ_7青海(Qinghai)
8AZ_8青海(Qinghai)
9AZ_9-
10AZ_10西藏(Tibet)
11CB_1川贝母(F. cirrhosa)青海(Qinghai)
12CB_2青海(Qinghai)
13CB_3青海(Qinghai)
14CB_4青海(Qinghai)
15CB_5青海(Qinghai)
16CB_6青海(Qinghai)
17CB_7-
18CB_8四川(Sichuan)
19CB_9-
20CB_10四川(Sichuan)
21WB_1瓦布贝母(F. unibracteata var. wabuensis)四川(Sichuan)
22WB_2-
23WB_3-
24WB_4四川(Sichuan)
25WB_5四川(Sichuan)
26WB_6四川(Sichuan)
27WB_7四川(Sichuan)
28SS_1梭砂贝母(F. delavayi)青海(Qinghai)
29SS_2四川(Sichuan)
30SS_3四川(Sichuan)
31SS_4四川(Sichuan)
32GS_1甘肃贝母(F. przewalskii)青海(Qinghai)
33GS_2甘肃(Gansu)
34GS_3甘肃(Gansu)
35GS_4甘肃(Gansu)
36TB_1太白贝母(F. taipaiensis)青海(Qinghai)
37TB_2陕西(Shaanxi)
38TB_3陕西(Shaanxi)
39TB_4陕西(Shaanxi)
40PB_1平贝母(F. ussuriensis)黑龙江(Heilongjiang)
41PB_2黑龙江(Heilongjiang)
42PB_3黑龙江(Heilongjiang)
43PB_4-
44PB_5-
45PB_6-
46PB_7-
47PB_8-
48PB_9黑龙江(Heilongjiang)
49PB_10黑龙江(Heilongjiang)
50PB_11吉林(Jilin)
51PB_12吉林(Jilin)
52PB_13吉林(Jilin)
53PB_14吉林(Jilin)
54PB_15黑龙江(Heilongjiang)
55PB_16吉林(Jilin)
56PB_17黑龙江(Heilongjiang)
57PB_18黑龙江(Heilongjiang)
58PB_19黑龙江(Heilongjiang)
59PB_20黑龙江(Heilongjiang)
60SB_1松贝(Songbei)国家专项抽验(sample drawing for national special item)
61SB_2
62SB_3
63SB_4
64SB_5
65SB_6
66SB_7
67SB_8
68SB_9
69SB_10
70QB_1青贝(Qingbei)国家专项抽验(sample drawing for national special item)
71QB_2
72QB_3
73QB_4
74QB_5
75QB_6
76QB_7
77QB_8
78QB_9
79QB_10
80LB_1炉贝(Lubei)国家专项抽验(sample drawing for national special item)
81LB_2
82LB_3
83LB_4
84LB_5
85LB_6
86LB_7
87LB_8
88LB_9
89LB_10
90CBM_sp_1统装(unified packaging)质量监测抽样(sample drawing for quality monitoring)
91CBM_sp_2
92CBM_sp_3
93CBM_sp_4
94CBM_sp_5
95CBM_sp_6
96CBM_sp_7
97CBM_sp_8
98CBM_sp_9
99CBM_sp_10
100CBM_sp_11
101CBM_sp_12
102CBM_sp_13
103CBM_sp_14
104CBM_sp_15
105CBM_sp_16
106CBM_sp_17
107CBM_sp_18
108CBM_sp_19
), ArticleFig(id=1239238156059472123, tenantId=1146029695717560320, journalId=1205117023404326918, articleId=1239238142952272593, language=CN, label=表1, caption=

样品信息表

, figureFileSmall=null, figureFileBig=null, tableContent=
序号
(serial number)		编号
(sample No.)		植物来源或商品规格
(plant source or product specification)		产地或来源
(origin or source)
1AZ_1暗紫贝母(F. unibracteata)四川(Sichuan)
2AZ_2四川(Sichuan)
3AZ_3四川(Sichuan)
4AZ_4四川(Sichuan)
5AZ_5四川(Sichuan)
6AZ_6四川(Sichuan)
7AZ_7青海(Qinghai)
8AZ_8青海(Qinghai)
9AZ_9-
10AZ_10西藏(Tibet)
11CB_1川贝母(F. cirrhosa)青海(Qinghai)
12CB_2青海(Qinghai)
13CB_3青海(Qinghai)
14CB_4青海(Qinghai)
15CB_5青海(Qinghai)
16CB_6青海(Qinghai)
17CB_7-
18CB_8四川(Sichuan)
19CB_9-
20CB_10四川(Sichuan)
21WB_1瓦布贝母(F. unibracteata var. wabuensis)四川(Sichuan)
22WB_2-
23WB_3-
24WB_4四川(Sichuan)
25WB_5四川(Sichuan)
26WB_6四川(Sichuan)
27WB_7四川(Sichuan)
28SS_1梭砂贝母(F. delavayi)青海(Qinghai)
29SS_2四川(Sichuan)
30SS_3四川(Sichuan)
31SS_4四川(Sichuan)
32GS_1甘肃贝母(F. przewalskii)青海(Qinghai)
33GS_2甘肃(Gansu)
34GS_3甘肃(Gansu)
35GS_4甘肃(Gansu)
36TB_1太白贝母(F. taipaiensis)青海(Qinghai)
37TB_2陕西(Shaanxi)
38TB_3陕西(Shaanxi)
39TB_4陕西(Shaanxi)
40PB_1平贝母(F. ussuriensis)黑龙江(Heilongjiang)
41PB_2黑龙江(Heilongjiang)
42PB_3黑龙江(Heilongjiang)
43PB_4-
44PB_5-
45PB_6-
46PB_7-
47PB_8-
48PB_9黑龙江(Heilongjiang)
49PB_10黑龙江(Heilongjiang)
50PB_11吉林(Jilin)
51PB_12吉林(Jilin)
52PB_13吉林(Jilin)
53PB_14吉林(Jilin)
54PB_15黑龙江(Heilongjiang)
55PB_16吉林(Jilin)
56PB_17黑龙江(Heilongjiang)
57PB_18黑龙江(Heilongjiang)
58PB_19黑龙江(Heilongjiang)
59PB_20黑龙江(Heilongjiang)
60SB_1松贝(Songbei)国家专项抽验(sample drawing for national special item)
61SB_2
62SB_3
63SB_4
64SB_5
65SB_6
66SB_7
67SB_8
68SB_9
69SB_10
70QB_1青贝(Qingbei)国家专项抽验(sample drawing for national special item)
71QB_2
72QB_3
73QB_4
74QB_5
75QB_6
76QB_7
77QB_8
78QB_9
79QB_10
80LB_1炉贝(Lubei)国家专项抽验(sample drawing for national special item)
81LB_2
82LB_3
83LB_4
84LB_5
85LB_6
86LB_7
87LB_8
88LB_9
89LB_10
90CBM_sp_1统装(unified packaging)质量监测抽样(sample drawing for quality monitoring)
91CBM_sp_2
92CBM_sp_3
93CBM_sp_4
94CBM_sp_5
95CBM_sp_6
96CBM_sp_7
97CBM_sp_8
98CBM_sp_9
99CBM_sp_10
100CBM_sp_11
101CBM_sp_12
102CBM_sp_13
103CBM_sp_14
104CBM_sp_15
105CBM_sp_16
106CBM_sp_17
107CBM_sp_18
108CBM_sp_19
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基于化学计量学的川贝母药材及其混伪品平贝母的鉴别方法的建立
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石岩 , 刘薇 , 魏锋 * , 马双成 *
药物分析杂志 | 安全监测 2024,44(7): 1222-1232
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药物分析杂志 | 安全监测 2024, 44(7): 1222-1232
基于化学计量学的川贝母药材及其混伪品平贝母的鉴别方法的建立
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石岩 , 刘薇, 魏锋* , 马双成*
作者信息
  • 中国食品药品检定研究院，北京 102629

    • Tel：（010）53852081；E-mail：

通讯作者:

* 马双成　Tel：(010)53852076；E-mail：；
魏锋　Tel：(010)53852020；E-mail：
Establishment of identification method for Fritillariae Cirrhosae Bulbus and its adulterant Fritillariae Ussuriensis Bulbus based on chemometrics
Yan SHI , Wei LIU, Feng WEI* , Shuang-cheng MA*
Affiliations
  • National Institutes for Food and Drug Control, Beijing 102629, China
出版时间: 2024-07-31 doi: 10.16155/j.0254-1793.2023-0616
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摘要
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目的：

建立能够鉴别川贝母及其混伪品平贝母的方法。

方法：

使用化学计量学技术对样品四极杆串联飞行时间（Q TOF）质谱仪测定数据进行分析，并结合三重四极杆质谱筛选出特征离子对为m/z 578.3→164.14和m/z 578.3→398.31。采用Waters Acquity UPLC CSH（75 mm×2.1 mm，1.7 μm）色谱柱，以乙腈-0.1%甲酸溶液为流动相，流速0.4 mL·min-1。三重四极杆质谱仪MRM模式检测m/z 578.3→164.14和m/z 578.3→398.31 2个离子对。

结果：

108批样品的验证结果表明，m/z 578.3→164.14和m/z 578.3→398.31 2个特征离子对能够有效区分川贝母及其混伪品平贝母。

结论：

方法有较好的专属性和灵敏度，可用于平贝母掺伪川贝母的检测。

川贝母  /  平贝母  /  化学计量学  /  正交偏最小二乘判别分析  /  伪品鉴别  /  液质联用法  /  数据分析  /  特征筛选  /  特征离子
Objective:

To establish a method for identifying Fritillariae Cirrhosae Bulbus and its adulterant Fritillariae Ussuriensis Bulbus.

Methods:

Chemometrics techniques were used for the analysis of the sample data from determination with Q TOF MS, and characteristic ion pairs were selected as m/z 578.3→164.14 and m/z 578.3→398.31 with triple quadrupole mass spectrometry applied, respectively. Then a specific approach was developed which used Waters Acquisition UPLC CSH (75 mm×2.1 mm, 1.7 μm) as column, and with acetonitrile and 0.1% formic acid solution as the mobile phase, and a flow rate of 0.4 mL·min-1. Two ion pairs: m/z 578.3→164.14 and m/z 578.3→398.31 were detected by triple quadrupole mass spectrometer with MRM mode.

Results:

The validation results through 108 batches of samples indicated that the two characteristic ion pairs, m/z 578.3→164.14 and m/z 578.3→398.31, could effectively distinguish between Fritillariae Cirrhosae Bulbus and its adulterant Fritillariae Ussuriensis Bulbus.

Conclusion:

The method had good specificity and sensitivity, and could be used for the detection of adulterated Fritillariae Cirrhosae Bulbus with Fritillariae Ussuriensis Bulbus.

Fritillariae Cirrhosae Bulbus  /  Fritillariae Ussuriensis Bulbus  /  chemometrics  /  OPLS-DA  /  counterfeit identification  /  LC-MS method  /  data analysis  /  feature screening  /  characteristic ion
石岩, 刘薇, 魏锋, 马双成. 基于化学计量学的川贝母药材及其混伪品平贝母的鉴别方法的建立. 药物分析杂志, 2024 , 44 (7) : 1222 -1232 . DOI: 10.16155/j.0254-1793.2023-0616
Yan SHI, Wei LIU, Feng WEI, Shuang-cheng MA. Establishment of identification method for Fritillariae Cirrhosae Bulbus and its adulterant Fritillariae Ussuriensis Bulbus based on chemometrics[J]. Chinese Journal of Pharmaceutical Analysis, 2024 , 44 (7) : 1222 -1232 . DOI: 10.16155/j.0254-1793.2023-0616
正文
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贝母类药材是贝母属植物的鳞茎，自古以来就是我国传统的中药材，有着悠久的药用历史，有止咳平喘等功效[1]。而该类药材中的川贝母更是我国名贵的重要中药材，从1963年版开始，此后被历版《中华人民共和国药典》(以下简称《中国药典》)收载，其来源植物也有多次改变，前期研究文献[1]中已有详细叙述，在此不再赘述。在现行2020年版《中国药典》一部中明确规定了川贝母的6种植物来源，分别为百合科贝母属植物川贝母Fritillaria cirrhosa D. Don、暗紫贝母F. unibracteata Hsiao et K. C. Hsia、甘肃贝母F. przewalskii Maxim.、梭砂贝母F. delavayi Franch.、太白贝母F. taipaiensis P. Y. Li或瓦布贝母F. unibracteata Hsiao et K. C. Hsia var. wabuensis (S. Y. Tang et S. C. Yue) Z. D. Liu，S. Wang et S. C. Chen的干燥鳞茎[2]。川贝母药材价格高，存在严重的过度采挖现象，随着人类生活范围的不断扩大，野生川贝母的生长环境常常受到较大的破坏，造成川贝母药材资源紧缺不断加剧，市场上出现了越来越多的以假充真的情况。川贝母药材有来源多，资源少，需求量大的特点，导致了川贝母药材市场混乱，以假乱真，监管困难的局面，对人民群众的用药安全有效形成了威胁。
平贝母药材是百合科植物平贝母F. ussuriensis Maxim.的干燥鳞茎，植物来源与川贝母同科同属。平贝母的价格比川贝母低，且小平贝的外观性状与川贝母中价格最高的商品规格松贝非常相近，因此市场常有以平贝母掺伪川贝母的现象发生。由于川贝母药材有6种同属不同种(变种)的植物来源，正品药材的组内差异已经较大，与作为同科同属的平贝母差异有限，其中的化学成分也都是以生物碱类成分为主，目前除分子生物学手段外，很难以化学成分，尤其是以主要活性成分甾体类生物碱作为差异特征对川贝母药材进行正品与伪品的鉴别。
本研究对使用LC-MS法对多批次的6种植物来源的川贝母药材及平贝母药材进行测定，使用代谢组学研究中常用的化学计量学技术对川贝母药材和平贝母药材的差异性特征离子进行研究，取得了一定的成果。
1　仪器与试药
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Waters Synapt G2-S型Q TOF MS液相色谱质谱联用仪(Waters公司)；Waters Xevo TQ-XS型三重四极杆液相色谱质谱联用仪(Waters公司)；XPE105型电子天平(Mettler-Toledo公司，万分之一精度)；KQ-500DE数控超声波清洗器(昆山市超声仪器有限公司)。甲醇、二氯甲烷、氨水均为分析纯，乙腈、甲酸为质谱级。
平贝母对照药材(批号120924-201711)与川贝母(暗紫贝母)对照药材(批号121000-201609)均来自中国食品药品检定研究院。
共收集样品108批，其中川贝母药材共88批，平贝母药材共20批。88批川贝母药材中，基地或产地收集，能够明确植物来源的样品有39批，分别为暗紫贝母10批，川贝母10批，瓦布贝母7批，梭砂贝母、甘肃贝母以及太白贝母各4批；此外49批川贝母药材为按照2020年版《中国药典》检验全部合格的国家专项抽验或质量检测的商品川贝母，分别为松贝、青贝及炉贝各10批，川贝母统装商品药材19批。样品信息详见表1，以已知确切植物来源的川贝母药材样品(AZ_1~AZ_10，CB_1~CB_10，WB1~WB_7，SS_1~SS_4，GS_1~GS4，TB_1~TB_4)和平贝母药材样品(PB_1~PB_10)用于方法建立及川贝母药材和平贝母药材差异特征离子的筛查发现(即表1中序号1~49的样品)，其余样品用于特征离子的验证(即表1中序号50~108的样品)。
研究涉及数据处理与分析所使用的软件或编程语言为Progenesis QI(Waters公司)、SIMCA多元变量统计分析软件(Umetrics公司，version 14.1)、Python计算机编程语言(Python Software Foundation，version 3.8.8)。
2　方法与结果
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2.1　溶液的制备
2.1.1　供试品溶液
取各样品粉末(过4号筛)约1.0 g，精密称定，置具塞锥形瓶中，精密加入氨水2 mL浸润过夜，精密加入甲醇-二氯甲烷(2∶1)6 mL，称量，超声(功率300 W，频率40 kHz)处理1 h，放冷，再称量，用甲醇-二氯甲烷(2∶1)补足减失的量，混匀，离心(5 000 r·min-1)10 min，取上清液过滤，取续滤液，即得。
2.1.2　空白溶液
除不称取样品粉末外，其他操作同“2.1.1”项。
2.1.3　参比溶液
取平贝母对照药材粉末约30 mg，精密称定，其他操作同“2.1.1”项。
2.1.4　不同比例掺伪的供试溶液
将平贝母对照药材分别按照1%、3%、5%、10%、20%、30%、40%、50%、60%和70%的比例与川贝母(暗紫贝母)对照药材混合均匀，制得掺伪样品，然后其他操作同“2.1.1”项，制备得到一系列不同比例平贝母掺伪的供试溶液。
2.2　色谱与质谱条件
采用Waters Acquity UPLC CSH(75 mm×2.1 mm，1.7 μm)色谱柱，以乙腈(A)-0.1%甲酸水溶液(B)为流动相，梯度洗脱(0~5 min，2%A→13%A；5~13 min，13%A→17%A；13~15 min，17%A→65%A；15~15.1 min，65%A→95%A；15.1~18 min，95%A)，流速0.4 mL·min-1，柱温35 ℃，进样量为1 μL。
差异特征离子筛选与发现研究，使用Waters Synapt G2-S型Q TOF MS液相色谱质谱联用仪，依据特征离子建立平贝母掺伪川贝母的方法，使用Waters Xevo TQ-XS型三重四极杆液相色谱质谱联用仪。选用电喷雾离子源，正离子模式，离子源温度为120 ℃，毛细管电压为3 kV，锥孔电压为20 V，去溶剂温度为450 ℃，去溶剂气体流速为600 L·h-1。以特征离子建立的平贝母掺伪川贝母的检验方法使用多反应监测(MRM)，以m/z 578.3→398.31和m/z 578.3→164.14检测离子对进行检测。
2.3　数据采集
按照上述色谱和质谱条件对各批样品进样测定，有确切生物种属信息的代表性样品总离子流图见图1。
2.4　数据分析
首先使用Waters数据分析软件Progenesis QI先将各批样品的液质图谱数据进行色谱峰校准并转换成精确质量-保留时间表示的数据对变量形式，然后导出为CSV文件格式，导入SIMCA数据分析软件或使用python语言进行数据处理和分析。
2.4.1　聚类分析
对测得的液质数据进行l2范数归一化预处理，然后使用ward法根据样品间欧氏距离进行聚类分析，树状图见图2。
2.4.2　相关性分析
将液质测定数据转置后，进行pearson相关系数分析，可以得到各批样品之间的相关性，按照相关性分析结果绘制热图，见图3。
2.4.3　主成分分析
对测得的液质数据进行l2范数归一化预处理，然后以累计方差达到95%为指标进行主成分分析，各批样品在第一和第二主成分二维平面的分布图见图4-A，主成分累计方差折线图见图4-B。
2.4.4　正交偏最小二乘判别分析
将液质测定数据做帕累托(Pareto)预处理，然后将样品分类标签代入数据进行正交偏最小二乘判别分析(OPLS-DA)，样品分布图见图5。
绘制数据变量的S-plot及平贝母相关性与变量投影重要性(VIP)分布图，结果见图6。从图6结果可得出m/z分别为441.346 1和578.371 3的2个离子为相对于川贝母药材的平贝母中特征离子，由于m/z 441.346 1离子保留时间<1 min，不宜作为川贝母药材与平贝母的差异特征离子，因此初步确定m/z 578.371 3离子作为特征离子进行进一步的研究与验证。
2.5　基于特征离子的平贝母掺伪川贝母的方法建立
2.5.1　特征子离子的确定
使用液相色谱与三重四极杆质谱联用子离子扫描模式，对m/z 578.3离子的碎片离子进行研究，质谱图见图7。该图显示，m/z 578.3离子有3个子离子，m/z分别为560.36、m/z 398.31和m/z 164.14，其中m/z 560.36离子应为母离子失去1个水分子产生的离子，因此选取m/z 398.31和m/z 164.14的离子作为m/z 578.3离子的特征子离子。
基于以上研究，在使用液相色谱与三重四极杆质谱联用方式检测平贝母掺伪川贝母样品时，采用MRM模式对m/z 578.3→164.14和m/z 578.3→398.31的离子进行检测，各种植物来源的川贝母药材样品、各商品规格川贝母药材样品以及平贝母样品的MRM模式检测色谱图见图8。
2.5.2　平贝母掺伪样品判定原则的确立
判定原则：(1)供试品溶液的2个检测离子对色谱中，未同时检出与参比溶液相应的色谱峰，视为未检出；(2)供试品溶液的2个检测离子对色谱中，同时检出与参比溶液相应的色谱峰，且m/z 578.3→164.14检测离子对色谱峰面积不大于参比溶液相应色谱峰峰面积，视为未检出；(3)供试品溶液的2个检测离子对色谱中，同时检出与参比溶液相应的色谱峰，且m/z 578.3→164.14检测离子对色谱峰面积大于参比溶液相应色谱峰峰面积，视为检出。
2.5.3　精密度
将PB_8供试品溶液，连续进样6次，结果在MRM模式下m/z 578.3→164.14和m/z 578.3→398.31色谱图中主要色谱峰峰面积的RSD分别为0.89%和6.7%。
2.5.4　专属性
将空白溶液、川贝母和平贝母的供试品溶液进样测定，结果如图8所示，可见在空白溶液和川贝母供试品溶液色谱图中与平贝母供试品色谱图中主色谱峰对应位置未检测到色谱峰，方法专属性良好。
2.5.5　检测限
将PB_8样品的供试品溶液，用甲醇-二氯甲烷(2∶1)逐级稀释，以色谱图中主要色谱峰信噪比3∶1时进样溶液稀释百分比作为检测限，结果MRM检测m/z 578.3→164.14和m/z 578.3→398.31的仪器检测限分别为0.01%和0.1%。
将平贝母1%比例掺伪样品的供试溶液进样测定，该比例掺伪样品的供试溶液MRM检测m/z 578.3→164.14和m/z 578.3→398.31结果见图9，色谱峰信噪比符合3∶1要求，为本研究方法的检测限。
2.5.6　线性关系考察
将平贝母不同比例掺伪样品的供试溶液依次进样测定，以主要色谱峰峰面积(Y)与对应的掺入平贝母的比例(X)进行线性回归，结果m/z 578.3→164.14和m/z 578.3→398.31的线性方程及相关系数平方分别为
2.5.7　样品测定
将各样品按照以上方法进行溶液制备及测定，结果除所有平贝母样品以及平贝母按照3%、5%、10%、20%、30%、40%、50%、60%和70%的比例掺伪的样品呈阳性外，其余样品测定结果均为未检出。
3　讨论
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3.1　供试品溶液制备
贝母类药材中的甾体生物碱类成分是主要的活性成分，如西贝母碱、西贝母碱苷、贝母辛、贝母素甲、贝母素乙、川贝酮碱、异浙贝甲素等[3-9]，这些化学成分不仅是各种贝母类药材的重点研究对象，也是各相关质量标准的指标性成分，因此本研究以甾体生物碱类成分作为川贝母药材和掺伪品平贝母的区分特征变量。供试品溶液的制备方法参考了2020年版《中国药典》一部川贝母药材品种项下的总生物碱类成分的测定。但《中国药典》中的提取方法在实际的试验操作过程有2个问题，首先该法使用到了重点管控的三氯甲烷试剂，该试剂不仅具有一定毒性，目前在购买、领用及使用等环节程序也十分烦琐复杂；其次该法须水浴加热回流提取2 h，还需要将提取液于具塞试管中水浴蒸干，过程过于复杂且费时，并不适合大量样品的快速测定。在充分借鉴相关研究文献[9-10]的基础上，遵循《中国药典》方法的思路，本研究对提取方法进行了改进，不仅使用二氯甲烷替代三氯甲烷，还考察了甲醇-二氯甲烷的比例，以达到与加入的氨水不会产生分层，利于使用更加简便易操作的超声提取方式。
3.2　数据分析实验
3.2.1　关于数据预处理
由于质谱检测器检测到的离子数据与取样量、样品测定条件等密切相关，而且不同变量之间的数据取值范围往往也会存在一定的差异，这种差异有时是巨大的，这些都会对分析试验的结果造成影响。因此，在大部分情况下，测得的试验数据须在进行各种分析试验前首先进行预处理。
一般来说，数据预处理方法可分为归一化法和标准化法，归一化法是将数据缩小至[0，1]或[-1，1]区间，这种方法损失了数据分布，保留了数据的权重；标准化法则为数据分布的归一保留了数据的分布情况，但损失了数据权重。本研究在数据分析实验阶段应用了3种数据预处理方式，即无预处理、归一化法和标准化法。在相关性分析时，由于分析目标仅为揭示无监督分析情况下样品数据的远近关系，因此并未进行预处理，但是若要求得到更加强烈的相关性信息，仍建议进行数据预处理。在聚类分析和主成分分析时，本研究采用了l2范数归一化预处理，这种处理方法可以使预处理后的同一批样品数据平方和归一化，在机器学习等数据科学研究中有较多的应用[11-13]。OPLS-DA作为代谢组学中寻找差异性代谢组分常用的分析方法，在中药分析中也多应用于差异性化学成分的研究，其中帕累托数据标准化方法也多有应用[14-15]。帕累托数据标准化方法是在对数据进行中心化处理后，再除以数据标准差的平方和，对于OPLS-DA来说，正如上述本研究所描述的，在进行这种数据预处理之后，一般多使用S-plot图筛选差异性化学成分。数据预处理可以减少或消除数据变异、量纲差异等因素对分析实验的影响，在多数情况下是十分必要的，不同的处理方法对分析结果也会有影响，因此选择合适的预处理方法十分重要且必要。
3.2.2　无监督分析
本研究使用了聚类分析法、相关性分析法及主成分分析法，对样品的测定数据进行了非监督分析，旨在揭示样品数据之间关系。在聚类分析树状图中，平贝母与川贝母药材是完全各自聚为一类的，6种植物来源的川贝母药材也基本按照不同植物来源各自聚类。相关性分析结果表明，相同植物来源的贝母相关性最高，反映在热图上颜色最深；除此之外，在相关性热图上颜色略深的部分表示了除了自身植物来源的样品有强相关性外，还与其他一些样品具有一定的相关性，比如来源于暗紫贝母的川贝母药材与来源于甘肃贝母、梭砂贝母和太白贝母的川贝母药材有一定相关性。需要指出的是，pearson相关系数一般只是衡量随机变量之间的线性相关程度，并不代表变量间所有相关信息。尽管如此，本研究的相关性分析结果也可以提供许多有意义的信息，值得进一步地深入研究。
3.2.3　OPLS-DA法
基于研究目的，在监督分析时，选择使用了代谢组学中常用OPLS-DA，将来自不同类别样品的数据进行进一步的变量特征解构，按照类别关系差异找出其中的特征性变量。OPLS-DA是偏最小二乘法的一种变化形式，基于偏最小二乘法每个组件所解释的变异，借鉴正交信号校正法的思想，移除与X轴无相关性的系统变异，使得最小二乘法模型的分析结果更具解释性，而且非相关变异可得到进一步的研究[11-14]。
OPLS-DA法筛选差异化合物通常通过S-plot或VIP计算。其中S-plot是通过计算绘制变量对于主成分的相关系数和协方差的分布散点图而得，越是靠近右上角或者左下角的变量点，代表该变量的组间差异性越显著。VIP在偏最小二乘法模型中是反映变量对于模型的重要性的既定参数，在OPLS-DA模型中该参数随着正交处理的步骤进行相应地变化[15]。由于VIP有正则化处理，若所有变量对模型的重要性完全一样，则VIP为1。这就意味着当VIP>1时，变量可能对模型具有重要意义。在本研究中，离子数据(变量)较多，按照常规绘制VIP棒状图无法清晰呈现特征离子，因此采用了离子在分组相关系数和VIP的二维空间散点分布图的形式，并且同时也使用S-plot图的方法，使得差异特征离子的选择结果能够通过2种方法互相佐证。图6显示了分别通过S-plot和VIP 2种方式筛选得到2个差异特征离子的情况。
3.3　鉴别方法判定原则的制定
本研究在判定原则的制定时，考虑到避免假阳性的出现，规定须有m/z 578.3→164.14和m/z 578.3→398.31 2个离子对检出，而且考虑到一般情况下，中药饮片中杂质不得过3%的规定，规定了参比溶液的取样量与制法。由于m/z 578.3→164.14离子对相较于m/z 578.3→398.31离子对来说，灵敏度更高，因此使用该离子对作为与参比溶液相比较的检测离子对。
4　总结
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正品川贝母药材来源较多，给该药材正伪品的鉴别研究带来了挑战。本研究是在充分比较6种川贝母药材来源与平贝母差别的基础上，开展的差异特征离子的研究，这些来源植物属于同科同属，所含成分极其相似，因此平贝母相对于川贝母药材的特征离子并不多。借助质谱检测器极高的灵敏度与专属性，以及先进的化学计量学分析算法，筛选出能够表征川贝母和平贝母差异的特征离子，进而建立了通过m/z 578.3→164.14和m/z 578.3→398.31 2个特征离子对进行鉴别的方法，并经过了108批产地或市场收集的样品验证。由于贝母属药材中存在多种甾体生物碱类成分，且不乏同分异构体，目前还未确定m/z 578.3离子为何种成分产生的离子，有待进一步深入研究。
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doi: 10.16155/j.0254-1793.2023-0616
  • 接收时间：2023-09-20
  • 首发时间：2026-03-13
  • 出版时间：2024-07-31
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  • 收稿日期：2023-09-20
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    中国食品药品检定研究院，北京 102629

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2种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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