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Article(id=1210148025142473466, tenantId=1146029695717560320, journalId=1189982191388893191, issueId=1210148010437243088, articleNumber=null, orderNo=null, doi=10.16438/j.0513-4870.2022-0757, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1654963200000, receivedDateStr=2022-06-12, revisedDate=1655481600000, revisedDateStr=2022-06-18, acceptedDate=null, acceptedDateStr=null, onlineDate=1766451372656, onlineDateStr=2025-12-23, pubDate=1660233600000, pubDateStr=2022-08-12, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1766451372656, onlineIssueDateStr=2025-12-23, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1766451372656, creator=13701087609, updateTime=1766451372656, updator=13701087609, issue=Issue{id=1210148010437243088, tenantId=1146029695717560320, journalId=1189982191388893191, year='2022', volume='57', issue='8', pageStart='2245', pageEnd='2556', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1766451369151, creator=13701087609, updateTime=1766451533022, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210148697808179705, tenantId=1146029695717560320, journalId=1189982191388893191, issueId=1210148010437243088, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210148697808179706, tenantId=1146029695717560320, journalId=1189982191388893191, issueId=1210148010437243088, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=2405, endPage=2415, ext={EN=ArticleExt(id=1210148026241381172, articleId=1210148025142473466, tenantId=1146029695717560320, journalId=1189982191388893191, language=EN, title=Monoterpene glucosides from an aqueous extract of Monochasma savatieri, columnId=1190335348761793317, journalTitle=Acta Pharmaceutica Sinica, columnName=Original Articles, runingTitle=null, highlight=null, articleAbstract=

Eleven monoterpene glucosides were isolated from a water decoction of Monochasma savatieri by column chromatography over macroporous adsorbent resin, MCI resin, Sephadex LH-20, and HW-40C, combined with preparative TLC, reversed phase HPLC, and flash column chromatographic techniques. Their structures were elucidated by comprehensive analysis of spectroscopic data, along with acidic and enzymatic hydrolysis as well as electronic circular dichroism (ECD) and NMR calculations, including six new compounds (1-4, 7 and 8), named monochasides A-D, G and H, respectively. Comparing the reported data of 9-hydroxylinaloyl 3-O-β-D-glucoside (5), (6Z)-9-hydroxylinaloyl 3-O-β-D-glucoside (6), and kankanoside D1 (9) with those obtained in this study, the absolute configurations of 6 and 9 were proved for the first time. Other two compounds were identified as 8-hydroxygeraniol 1-O-β-D-glucopyranoside (10) and 8-hydroxygeraniol 8-O-β-D-glucopyranoside (11), respectively.

, correspAuthors=Qing-lan GUO, Jian-gong SHI, authorNote=null, correspAuthorsNote=null, copyrightStatement=Copyright ©2022 Acta Pharmaceutica Sinica. All rights reserved., 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=Chen LIU, Cheng-gen ZHU, Cheng-bo XU, Bin MU, Qing-lan GUO, Jian-gong SHI), CN=ArticleExt(id=1210148030007866367, articleId=1210148025142473466, tenantId=1146029695717560320, journalId=1189982191388893191, language=CN, title=鹿茸草水提取物中的单萜苷类成分, columnId=1190335348896011050, journalTitle=药学学报, columnName=研究论文, runingTitle=null, highlight=null, articleAbstract=

通过大孔吸附树脂、MCI树脂、Sephadex LH-20和HW-40C柱色谱, 结合制备薄层色谱、反相HPLC和Flash等色谱分离技术, 从鹿茸草水煎煮提取物中分离得到11个单萜苷类化合物。借助波谱数据解析、酸或酶水解以及电子圆二色谱(ECD) 和NMR计算综合分析, 确定了它们的结构(1~11), 包括6个新结构化合物, 分别命名为鹿茸草苷A~D (1~4)、G和H (7和8)。通过9-羟基芳樟醇3-O-β-D-葡萄糖苷(5)、(6Z)-9-羟基芳樟醇-3-O-β-D-葡萄糖苷(6) 和kankanoside D1 (9) 的文献报道数据与本实验数据比较, 首次确证了6和9的绝对构型。另外两个化合物分别鉴定为8-羟基香叶醇1-O-β-D-葡萄糖苷(10) 和8-羟基香叶醇8-O-β-D-葡萄糖苷(11)。

, correspAuthors=郭庆兰, 石建功, authorNote=null, correspAuthorsNote=
*郭庆兰, Tel: 86-10-83154789, E-mail: ;
石建功, Tel: 86-10-63025166, Fax: 86-10-63017757, E-mail:
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J Chem Ecol, 1994, 20: 2089-2097., articleTitle=Isolation of 8-hydroxygeraniol-8-O-β-D-glucoside, a probable intermediate in biosynthesis of iridoid monoterpenes, from defensive secretions of Plagiodera versicolora and Gastrophysa viridula (Coleoptera: Chrysomelidae), refAbstract=null), Reference(id=1210148041143742885, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1210148025142473466, doi=10.1248/yakushi1947.103.5_508, pmid=null, pmcid=null, year=1983, volume=103, issue=null, pageStart=508, pageEnd=511, url=null, language=null, rfNumber=[28], rfOrder=27, authorNames=null, journalName=Yakugaku Zasshi, refType=null, unstructuredReference=Kabayashi H, Komatsu J. Study on constituents of Cistanchis herba. I.[J]. Yakugaku Zasshi, 1983, 103: 508-511., articleTitle=Study on constituents of Cistanchis herba. I., refAbstract=null), Reference(id=1210148041236017576, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1210148025142473466, doi=null, pmid=null, pmcid=null, year=1991, volume=95, issue=null, pageStart=2595, pageEnd=2601, url=null, language=null, rfNumber=[29], rfOrder=28, authorNames=null, journalName=J Chem Phys, refType=null, unstructuredReference=Helgaker T, Jørgensen P. An electronic Hamiltonian for origin independent calculations of magnetic properties[J]. J Chem Phys, 1991, 95: 2595-2601., articleTitle=An electronic Hamiltonian for origin independent calculations of magnetic properties, refAbstract=null), Reference(id=1210148041315709354, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1210148025142473466, doi=10.1021/cr200106v, pmid=null, pmcid=null, year=2012, volume=112, issue=null, pageStart=1839, pageEnd=1862, url=null, language=null, rfNumber=[30], rfOrder=29, authorNames=null, journalName=Chem Rev, refType=null, unstructuredReference=Lodewyk MW, Siebert MR, Tantillo DJ, et al. Computational prediction of 1H and 13C chemical shifts: a useful tool for natural product, mechanistic, and synthetic organic chemistry[J]. Chem Rev, 2012, 112: 1839-1862., articleTitle=Computational prediction of 1H and 13C chemical shifts: a useful tool for natural product, mechanistic, and synthetic organic chemistry, refAbstract=null)], funds=[Fund(id=1210148037599555920, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1210148025142473466, awardId=81630094, language=CN, fundingSource=国家自然科学基金资助项目(81630094), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1210148030280495126, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1210148025142473466, xref=null, ext=[AuthorCompanyExt(id=1210148030284689431, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1210148025142473466, companyId=1210148030280495126, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1. 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(b) The overlaid experimental UV of 1 and calculated UV spectra of 1 (red dash) and (3<i>S</i>)-1 (blue dash). (Blue-shifted by 16.5 nm) , figureFileSmall=iNDR581omwMu2OnmMF3xnQ==, figureFileBig=pasVL6zHeOC+9r3gqBPsSw==, tableContent=null), ArticleFig(id=1210148035791810832, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1210148025142473466, language=EN, label=null, caption=null, figureFileSmall=wO8WdGAqYeAwBS0lBKaZ7w==, figureFileBig=YUFYNrHDd1zhXwNHbqcoxg==, tableContent=null), ArticleFig(id=1210148035888279830, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1210148025142473466, language=CN, label=Figure 5, caption= (a) The overlaid experimental CD (red line) of 2 and calculated ECD spectra of 2 (red dash) and (3<i>S</i>)-2 (blue dash). (b) The overlaid experimental UV of 2 and calculated UV spectra of 2 (red dash) and (3<i>S</i>)-2 (blue dash). 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(Blue-shifted by 5.0 nm) , figureFileSmall=g9v/AzP++nJNmlbXN8sywg==, figureFileBig=1+YS6o8f9e4/IBCZyCORCw==, tableContent=null), ArticleFig(id=1210148036194464030, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1210148025142473466, language=EN, label=null, caption=null, figureFileSmall=CMSwV8EePAHzkNfvLkJwVA==, figureFileBig=YwEMsAfgu9klqLimBXGLIw==, tableContent=null), ArticleFig(id=1210148036303515940, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1210148025142473466, language=CN, label=Figure 7, caption= (a) The overlaid experimental CD (red line) of 9 and calculated ECD spectra of 9 (red dash) and its stereoisomer with the enantiomeric aglycone (blue dash). (b) The overlaid experimental UV of 9 and calculated UV spectra of 9 (red dash) and its stereoisomer with the enantiomeric aglycone (blue dash). (Red-shifted by 4.0 nm) , figureFileSmall=CMSwV8EePAHzkNfvLkJwVA==, figureFileBig=YwEMsAfgu9klqLimBXGLIw==, tableContent=null), ArticleFig(id=1210148036408373547, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1210148025142473466, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
No.123
δHδCδHδCδHδC
1a5.20 dd (17.4, 1.8)115.85.36 dd (18.0, 1.8)117.54.30 dd (12.0, 7.2)66.2
1b5.15 dd (10.8, 1.8)5.34 dd (10.8, 1.8)4.21 dd (12.0, 7.2)
25.86 dd (17.4, 10.8)144.35.92 brdd (18.0, 10.8)141.85.39 dd (6.6, 7.2)122.7
381.481.9140.2
41.56 m42.31.86 brt (7.2)39.02.21 t (7.2)38.8
52.04 m23.32.48 brq (7.2)24.52.49 q (7.2)28.1
65.32 dt (7.2, 1.2)126.96.80 tq (7.2, 1.2)160.26.56 t (7.2)156.1
7135.9139.3140.7
83.84 brs69.09.29 d (1.2)200.39.30 brd (2.4)197.2
91.57 s13.71.72 s8.91.67 s9.1
101.30 s23.31.43 s22.51.67 s16.4
1′4.30 d (7.8)99.54.56 d (7.8)97.94.21 d (7.8)102.8
2′3.11 dd (9.6, 7.8)75.23.25 dd (9.6, 7.8)73.93.11 dd (9.0, 7.8)75.1
3′3.27 dd (10.2, 9.6)78.13.47 dd (10.2, 9.6)76.53.27 t (9.0)78.2
4′3.18 dd (10.2, 9.6)71.93.36 dd (10.2, 9.6)70.53.21 t (9.0)71.7
5′3.31 ddd (9.6, 6.6, 2.4)74.93.41 m76.33.17 m78.1
6′a4.27 dd (12.0, 2.4)65.03.88 dd (12.0, 2.4)61.53.81 dd (12.0, 1.8)62.8
6′b4.10 dd (12.0, 6.6)3.68 dd (12.0, 6.0)3.60 dd (12.0, 5.4)
1ʺ172.7
2ʺ1.99 s20.8
), ArticleFig(id=1210148036525814060, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1210148025142473466, language=CN, label=Table 1, caption=

NMR spectroscopic data of compounds 1-3. δ were measured in CD3OD for 1 and 3 (references: δHCD2OD = 3.250 for 1H and δCCDH2OD = 49.000 for 13C) and in D2O for 2 (references: δHDO = 4.800 for 1H and δCH3OH = 49.50 for 13C) at 600 MHz for 1H and 150 MHz for 13C. Proton coupling constants (J) in Hz are given in parentheses. The assignments were based on 1H-1H COSY, HSQC, and HMBC experiments

, figureFileSmall=null, figureFileBig=null, tableContent=
No.123
δHδCδHδCδHδC
1a5.20 dd (17.4, 1.8)115.85.36 dd (18.0, 1.8)117.54.30 dd (12.0, 7.2)66.2
1b5.15 dd (10.8, 1.8)5.34 dd (10.8, 1.8)4.21 dd (12.0, 7.2)
25.86 dd (17.4, 10.8)144.35.92 brdd (18.0, 10.8)141.85.39 dd (6.6, 7.2)122.7
381.481.9140.2
41.56 m42.31.86 brt (7.2)39.02.21 t (7.2)38.8
52.04 m23.32.48 brq (7.2)24.52.49 q (7.2)28.1
65.32 dt (7.2, 1.2)126.96.80 tq (7.2, 1.2)160.26.56 t (7.2)156.1
7135.9139.3140.7
83.84 brs69.09.29 d (1.2)200.39.30 brd (2.4)197.2
91.57 s13.71.72 s8.91.67 s9.1
101.30 s23.31.43 s22.51.67 s16.4
1′4.30 d (7.8)99.54.56 d (7.8)97.94.21 d (7.8)102.8
2′3.11 dd (9.6, 7.8)75.23.25 dd (9.6, 7.8)73.93.11 dd (9.0, 7.8)75.1
3′3.27 dd (10.2, 9.6)78.13.47 dd (10.2, 9.6)76.53.27 t (9.0)78.2
4′3.18 dd (10.2, 9.6)71.93.36 dd (10.2, 9.6)70.53.21 t (9.0)71.7
5′3.31 ddd (9.6, 6.6, 2.4)74.93.41 m76.33.17 m78.1
6′a4.27 dd (12.0, 2.4)65.03.88 dd (12.0, 2.4)61.53.81 dd (12.0, 1.8)62.8
6′b4.10 dd (12.0, 6.6)3.68 dd (12.0, 6.0)3.60 dd (12.0, 5.4)
1ʺ172.7
2ʺ1.99 s20.8
), ArticleFig(id=1210148036634865970, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1210148025142473466, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
No.456
δHδCδHδCδHδC
1a5.22 dd (17.4, 1.2)112.65.33 dd (10.8, 1.2)117.25.32 dd (10.8, 1.2)117.2
1b5.14 dd (10.8, 1.2)5.31 dd (17.4, 1.2)5.30 dd (17.4, 1.2)
26.00 dd (17.4, 10.8)144.75.91 brdd (17.4, 10.8)142.15.89 ddd (17.4, 10.8, 1.8)142.1
374.482.382.2
41.64 t (7.2)41.41.69 t (7.2)40.51.66 t (7.2)41.1
52.11 m22.82.09 m22.62.09 m22.5
65.91 t (7.2)131.55.46 t (7.2)127.65.41 t (7.2)129.5
7131.7135.0134.5
8a4.25 d (12.0)76.13.97 s68.34.10 s60.7
8b4.15 d (12.0)3.97 s4.10 s
91.69 s13.81.65 s13.61.75 s21.1
101.32 s26.61.41 s22.41.39 s22.4
1′4.44 d (7.8)100.84.54 d (7.8)97.94.53 d (7.8)97.9
2′3.30 dd (9.0, 7.8)73.73.24 dd (9.0, 7.8)73.93.23 dd (9.0, 7.8)73.9
3′3.48 t (9.0)76.53.47 t (9.0)76.53.46 t (9.0)76.5
4′3.40 dd (9.6, 9.0)70.33.36 dd (9.6, 9.0)70.53.35 t (9.0)70.5
5′3.42 m76.53.40 m76.23.40 m76.2
6′a3.90 dd (12.6, 1.8)61.33.88 dd (12.0, 2.4)61.53.87 dd (12.6, 1.8)61.5
6′b3.74 dd (12.6, 6.0)3.69 dd (12.0, 6.0)3.68 dd (12.6, 6.6)
), ArticleFig(id=1210148036748112182, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1210148025142473466, language=CN, label=Table 2, caption=

NMR spectroscopic data of compounds 4-6. δ were measured in D2O at 600 MHz for 1H and 150 MHz for 13C (references δHDO = 4.800 for 1H and δCH3OH = 49.50 for 13C). Proton coupling constants (J) in Hz are given in parentheses. The assignments were based on 1H-1H COSY, HSQC, and HMBC experiments

, figureFileSmall=null, figureFileBig=null, tableContent=
No.456
δHδCδHδCδHδC
1a5.22 dd (17.4, 1.2)112.65.33 dd (10.8, 1.2)117.25.32 dd (10.8, 1.2)117.2
1b5.14 dd (10.8, 1.2)5.31 dd (17.4, 1.2)5.30 dd (17.4, 1.2)
26.00 dd (17.4, 10.8)144.75.91 brdd (17.4, 10.8)142.15.89 ddd (17.4, 10.8, 1.8)142.1
374.482.382.2
41.64 t (7.2)41.41.69 t (7.2)40.51.66 t (7.2)41.1
52.11 m22.82.09 m22.62.09 m22.5
65.91 t (7.2)131.55.46 t (7.2)127.65.41 t (7.2)129.5
7131.7135.0134.5
8a4.25 d (12.0)76.13.97 s68.34.10 s60.7
8b4.15 d (12.0)3.97 s4.10 s
91.69 s13.81.65 s13.61.75 s21.1
101.32 s26.61.41 s22.41.39 s22.4
1′4.44 d (7.8)100.84.54 d (7.8)97.94.53 d (7.8)97.9
2′3.30 dd (9.0, 7.8)73.73.24 dd (9.0, 7.8)73.93.23 dd (9.0, 7.8)73.9
3′3.48 t (9.0)76.53.47 t (9.0)76.53.46 t (9.0)76.5
4′3.40 dd (9.6, 9.0)70.33.36 dd (9.6, 9.0)70.53.35 t (9.0)70.5
5′3.42 m76.53.40 m76.23.40 m76.2
6′a3.90 dd (12.6, 1.8)61.33.88 dd (12.0, 2.4)61.53.87 dd (12.6, 1.8)61.5
6′b3.74 dd (12.6, 6.0)3.69 dd (12.0, 6.0)3.68 dd (12.6, 6.6)
), ArticleFig(id=1210148036857164091, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1210148025142473466, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
Parameter4(3S)-48(4S, 5S, 8R, 9S)-8(4R, 5R, 8S, 9R)-8(4S, 5R, 8S, 9R)-8
DP4+(H data)100.00%00.00%100.00%00.00%0.00%0.00%
DP4+(C data)94.09%5.91%79.50%0.04%0.01%20.46%
DP4+(all data)100.00%00.00%100.00%00.00%0.00%0.00%
), ArticleFig(id=1210148036966215994, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1210148025142473466, language=CN, label=Table 3, caption=

DP4+ analysis of the measured and calculated NMR data of 4, 8, and their stereoisomers

, figureFileSmall=null, figureFileBig=null, tableContent=
Parameter4(3S)-48(4S, 5S, 8R, 9S)-8(4R, 5R, 8S, 9R)-8(4S, 5R, 8S, 9R)-8
DP4+(H data)100.00%00.00%100.00%00.00%0.00%0.00%
DP4+(C data)94.09%5.91%79.50%0.04%0.01%20.46%
DP4+(all data)100.00%00.00%100.00%00.00%0.00%0.00%
), ArticleFig(id=1210148037079462204, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1210148025142473466, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
No.789
δHδCδHδCδHδC
1a185.53.57 dd (11.5, 4.5)65.54.48 dd (11.5)64.7
1b3.42 dd (11.5, 3.0)4.20 dd (11.5)
3a4.00 d (11.4)76.93.95 dd (10.0, 4.5)75.43.63 m61.1
3b3.71 d (11.4)3.36 dd (10.0, 6.0)3.59 m
4a88.81.75 m38.11.92 m36.2
4b1.34 m
52.93 q (9.6)46.61.55 m44.42.77 m43.6
6a1.86 m28.01.62 m28.51.99 m28.7
6b1.67 m1.42 m1.43 m
7a1.86 m35.41.64 m33.82.33 m37.2
7b1.28 m1.20 m2.40 m
82.23 m39.81.75 m37.5142.5
93.04 dd (9.6, 4.8)55.11.40 m51.9133.1
101.13 d (6.6)20.50.94 d (6.5)20.41.70 s14.0
111.40 s18.50.96 d (6.5)16.0
1′4.44 d (7.8)103.44.39 d (7.5)103.74.41 d (8.0)101.9
2′3.28 dd (9.6, 7.8)73.73.22 dd (9.5, 7.5)73.93.21 dd (9.5, 8.0)73.8
3′3.48 dd (9.6, 9.0)76.43.43 dd (9.5, 9.0)76.53.43 dd (9.5, 9.0)76.6
4′3.38 t (9.0)70.33.35 t (9.0)70.33.35 t (9.0)70.3
5′3.45 m76.63.38 m76.43.38 m76.5
6′a3.92 dd (12.0, 2.4)61.43.87 dd (12.5, 2.0)61.43.88 dd (12.5, 2.0)61.4
6′b3.72 dd (12.0, 6.0)3.68 dd (12.5, 6.0)3.69 dd (12.5, 6.6)
), ArticleFig(id=1210148037209485632, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1210148025142473466, language=CN, label=Table 4, caption=

NMR spectroscopic data of compounds 7-9. δ were measured in D2O for 7 at 600 MHz for 1H and 150 MHz for 13C and for 8 and 9 at 500 MHz for 1H and 125 MHz for 13C (references δHDO = 4.800 for 1H and δCH3OH = 49.50 for 13C). Proton coupling constants (J) in Hz are given in parentheses. The assignments were based on 1H-1H COSY, HSQC, and HMBC experiments

, figureFileSmall=null, figureFileBig=null, tableContent=
No.789
δHδCδHδCδHδC
1a185.53.57 dd (11.5, 4.5)65.54.48 dd (11.5)64.7
1b3.42 dd (11.5, 3.0)4.20 dd (11.5)
3a4.00 d (11.4)76.93.95 dd (10.0, 4.5)75.43.63 m61.1
3b3.71 d (11.4)3.36 dd (10.0, 6.0)3.59 m
4a88.81.75 m38.11.92 m36.2
4b1.34 m
52.93 q (9.6)46.61.55 m44.42.77 m43.6
6a1.86 m28.01.62 m28.51.99 m28.7
6b1.67 m1.42 m1.43 m
7a1.86 m35.41.64 m33.82.33 m37.2
7b1.28 m1.20 m2.40 m
82.23 m39.81.75 m37.5142.5
93.04 dd (9.6, 4.8)55.11.40 m51.9133.1
101.13 d (6.6)20.50.94 d (6.5)20.41.70 s14.0
111.40 s18.50.96 d (6.5)16.0
1′4.44 d (7.8)103.44.39 d (7.5)103.74.41 d (8.0)101.9
2′3.28 dd (9.6, 7.8)73.73.22 dd (9.5, 7.5)73.93.21 dd (9.5, 8.0)73.8
3′3.48 dd (9.6, 9.0)76.43.43 dd (9.5, 9.0)76.53.43 dd (9.5, 9.0)76.6
4′3.38 t (9.0)70.33.35 t (9.0)70.33.35 t (9.0)70.3
5′3.45 m76.63.38 m76.43.38 m76.5
6′a3.92 dd (12.0, 2.4)61.43.87 dd (12.5, 2.0)61.43.88 dd (12.5, 2.0)61.4
6′b3.72 dd (12.0, 6.0)3.68 dd (12.5, 6.0)3.69 dd (12.5, 6.6)
), ArticleFig(id=1210148037377257800, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1210148025142473466, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
No.1011
δHδCδHδC
14.31 d (7.5)66.14.09 d (7.0)58.5
25.36 t (7.5)119.35.38 t (7.0)122.6
3144.7141.8
42.12 t (7.5)39.12.10 t (7.0)38.9
52.20 dt (7.0, 7.5)25.82.21 quint (7.0)26.0
65.41 t (7.0)127.25.51 t (7.0)131.5
7135.2131.7
8a3.94 s68.34.19 d (11.5)76.0
8b4.10 d (11.5)
91.62 s13.61.65 s13.9
101.68 s16.11.66 s15.9
1′4.42 d (8.0)100.94.38 d (8.0)100.6
2′3.23 dd (9.0, 8.0)73.73.24 dd (9.0, 8.0)73.7
3′3.43 t (9.0)76.63.42 t (9.0)76.5
4′3.35 t (9.0)70.33.34 t (9.0)70.3
5′3.36 m76.73.35 m76.5
6′a3.88 dd (12.5, 2.0)61.43.87 dd (12.5, 1.0)61.4
6′b3.69 dd (12.5, 5.0)3.68 dd (12.5, 5.0)
), ArticleFig(id=1210148037469532491, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1210148025142473466, language=CN, label=Table 5, caption=

NMR spectroscopic data of compounds 10 and 11. δ were measured in D2O at 500 MHz for 1H and 125 MHz for 13C (references δHDO = 4.800 for 1H and δCH3OH = 49.50 for 13C). Proton coupling constants (J) in Hz are given in parentheses. The assignments were based on 1H-1H COSY, HSQC, and HMBC experiments

, figureFileSmall=null, figureFileBig=null, tableContent=
No.1011
δHδCδHδC
14.31 d (7.5)66.14.09 d (7.0)58.5
25.36 t (7.5)119.35.38 t (7.0)122.6
3144.7141.8
42.12 t (7.5)39.12.10 t (7.0)38.9
52.20 dt (7.0, 7.5)25.82.21 quint (7.0)26.0
65.41 t (7.0)127.25.51 t (7.0)131.5
7135.2131.7
8a3.94 s68.34.19 d (11.5)76.0
8b4.10 d (11.5)
91.62 s13.61.65 s13.9
101.68 s16.11.66 s15.9
1′4.42 d (8.0)100.94.38 d (8.0)100.6
2′3.23 dd (9.0, 8.0)73.73.24 dd (9.0, 8.0)73.7
3′3.43 t (9.0)76.63.42 t (9.0)76.5
4′3.35 t (9.0)70.33.34 t (9.0)70.3
5′3.36 m76.73.35 m76.5
6′a3.88 dd (12.5, 2.0)61.43.87 dd (12.5, 1.0)61.4
6′b3.69 dd (12.5, 5.0)3.68 dd (12.5, 5.0)
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鹿茸草水提取物中的单萜苷类成分
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刘琛 1 , 朱承根 1 , 徐成博 1 , 穆滨 2 , 郭庆兰 1, * , 石建功 1, *
药学学报 | 研究论文 2022,57(8): 2405-2415
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药学学报 | 研究论文 2022, 57(8): 2405-2415
鹿茸草水提取物中的单萜苷类成分
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刘琛1, 朱承根1, 徐成博1, 穆滨2, 郭庆兰1, * , 石建功1, *
作者信息
  • 1.中国医学科学院、北京协和医学院药物研究所, 天然药物活性物质与功能国家重点实验室, 北京 100050
  • 2.哈尔滨市康隆药业有限责任公司, 黑龙江 哈尔滨 150025

通讯作者:

*郭庆兰, Tel: 86-10-83154789, E-mail: ;
石建功, Tel: 86-10-63025166, Fax: 86-10-63017757, E-mail:
Monoterpene glucosides from an aqueous extract of Monochasma savatieri
Chen LIU1, Cheng-gen ZHU1, Cheng-bo XU1, Bin MU2, Qing-lan GUO1, * , Jian-gong SHI1, *
Affiliations
  • 1. Key Laboratory of Bioactive Substance and Function of Natural Medicines, Institute of Materia Medica, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100050, China
  • 2. Harbin Kanglong Pharmaceutical Co., Ltd., Harbin 150025, China
出版时间: 2022-08-12 doi: 10.16438/j.0513-4870.2022-0757
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摘要
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通过大孔吸附树脂、MCI树脂、Sephadex LH-20和HW-40C柱色谱, 结合制备薄层色谱、反相HPLC和Flash等色谱分离技术, 从鹿茸草水煎煮提取物中分离得到11个单萜苷类化合物。借助波谱数据解析、酸或酶水解以及电子圆二色谱(ECD) 和NMR计算综合分析, 确定了它们的结构(1~11), 包括6个新结构化合物, 分别命名为鹿茸草苷A~D (1~4)、G和H (7和8)。通过9-羟基芳樟醇3-O-β-D-葡萄糖苷(5)、(6Z)-9-羟基芳樟醇-3-O-β-D-葡萄糖苷(6) 和kankanoside D1 (9) 的文献报道数据与本实验数据比较, 首次确证了6和9的绝对构型。另外两个化合物分别鉴定为8-羟基香叶醇1-O-β-D-葡萄糖苷(10) 和8-羟基香叶醇8-O-β-D-葡萄糖苷(11)。

玄参科  /  鹿茸草  /  水提取物  /  单萜葡萄糖苷  /  鹿茸草苷

Eleven monoterpene glucosides were isolated from a water decoction of Monochasma savatieri by column chromatography over macroporous adsorbent resin, MCI resin, Sephadex LH-20, and HW-40C, combined with preparative TLC, reversed phase HPLC, and flash column chromatographic techniques. Their structures were elucidated by comprehensive analysis of spectroscopic data, along with acidic and enzymatic hydrolysis as well as electronic circular dichroism (ECD) and NMR calculations, including six new compounds (1-4, 7 and 8), named monochasides A-D, G and H, respectively. Comparing the reported data of 9-hydroxylinaloyl 3-O-β-D-glucoside (5), (6Z)-9-hydroxylinaloyl 3-O-β-D-glucoside (6), and kankanoside D1 (9) with those obtained in this study, the absolute configurations of 6 and 9 were proved for the first time. Other two compounds were identified as 8-hydroxygeraniol 1-O-β-D-glucopyranoside (10) and 8-hydroxygeraniol 8-O-β-D-glucopyranoside (11), respectively.

Scrophulariaceae  /  Monochasma savatieri  /  aqueous extract  /  monoterpene glucosides  /  monochasides
刘琛, 朱承根, 徐成博, 穆滨, 郭庆兰, 石建功. 鹿茸草水提取物中的单萜苷类成分. 药学学报, 2022 , 57 (8) : 2405 -2415 . DOI: 10.16438/j.0513-4870.2022-0757
Chen LIU, Cheng-gen ZHU, Cheng-bo XU, Bin MU, Qing-lan GUO, Jian-gong SHI. Monoterpene glucosides from an aqueous extract of Monochasma savatieri[J]. Acta Pharmaceutica Sinica, 2022 , 57 (8) : 2405 -2415 . DOI: 10.16438/j.0513-4870.2022-0757
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鹿茸草为玄参科(Scrophulariaceae) 鹿茸草属(Monochasma) 植物棉毛鹿茸草(Monochasma savatieri Franch.) 的干燥全草, 主要分布在浙江、江苏、福建及江西等地, 全草入药, 具有清热解毒、凉血止血、祛湿止痛等功效[1]。由鹿茸草、白花蛇舌草、鸭跖草制成的中成药炎宁糖浆, 用于治疗上呼吸道感染、扁桃体炎、尿路感染、急性菌痢和肠炎等疾病[2]。然而, 关于鹿茸草化学成分的研究相对较少, 到目前为止从其丙酮、水或乙醇提取物中, 仅报道了包括苯乙醇苷、环烯醚萜苷、黄酮和有机酸等结构类型的30余个化合物[3-6]。作为对中草药化学成分及其药理活性多样性系统研究的内容之一[7-14], 结合鹿茸草及其制剂以水煎煮使用的实际情况[15], 作者对鹿茸草水提物的化学成分进行了研究, 重点从微量成分入手, 为阐明鹿茸草水提物化学成分的多样性特点和进一步深入研究奠定基础。本文报道11个单萜苷类成分(1~11) 的分离纯化和结构鉴定(图 1)。其中, 1~4、7和8为新结构化合物, 6和9的苷元绝对构型为首次确定。
结果和讨论
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化合物1为无色胶状物, [α]$ {}_{\mathrm{D}}^{20} $ -19.8 (c 0.10, CH3OH)。红外光谱显示其分子结构中存在羟基(3 396 cm-1) 和羰基(1 741 cm-1)。根据(+)-HR-ESI-MS m/z 397.183 2 [M+Na]+ (C18H30O8Na计算值, 397.183 3) 和NMR谱数据(表 1), 确定其分子组成为C18H30O8, 不饱和度为4。在甲醇-d4中, 该化合物的1H NMR谱显示可归属于1个三取代乙烯基[δH 5.32 (1H, dt, J = 7.2, 1.2 Hz, H-6)]; 1个乙烯基[δH 5.86 (1H, dd, J = 17.4, 10.8 Hz, H-2), 5.20 (1H, dd, J = 17.4, 1.8 Hz, H-1a), 5.15 (1H, dd, J = 10.8, 1.8 Hz, H-1b)]; 1个连氧亚甲基[δH 3.84 (2H, s, H2-8)]; 两个亚甲基[δH 1.56 (2H, m, H2-4), 2.04 (2H, m, H2-5)]; 1个与双键相连的甲基[δH 1.57 (3H, s, H3-9)]; 1个与氧同碳的叔甲基[δH 1.30 (3H, s, H3-10)] 和1个典型的乙酰甲基[δH 1.99 (3H, s, H3-2ʺ)] 的氢共振信号。此外, 还显示1个β-葡萄糖基的特征氢信号[δH 4.30 (1H, d, J = 7.8 Hz, H-1ʹ), 3.11 (1H, dd, J = 9.6, 7.8 Hz, H-2ʹ), 3.27 (1H, dd, J = 10.2, 9.6 Hz, H-3ʹ), 3.18 (1H, dd, J = 10.2, 9.6 Hz, H-4ʹ), 3.31 (1H, ddd, J = 9.6, 6.6, 2.4 Hz, H-5ʹ), 4.27 (1H, dd, J = 12.0, 2.4 Hz, H-6ʹa), 4.10 (1H, dd, J = 12.0, 6.6 Hz, H-6ʹb)]。13C NMR和DEPT给出以上单元对应的碳共振信号(表 1)。根据H2-6ʹ和C-6ʹ的化学位移, 推定β-葡萄糖基单元的6ʹ-羟基与乙酰基形成酯; 同时, 根据上述可归属于苷元的NMR数据, 结合分子组成和不饱和度, 推测1的苷元为一个开链单萜-二烯-二醇。通过2D NMR谱数据解析, 对1的结构进行了进一步确定。首先, 通过HSQC谱数据分析, 对NMR谱中氢和连氢的碳共振信号进行了准确归属(表 1)。在1H-1H COSY谱中, 除显示β-葡萄糖基的氢依次偶合相关的交叉峰外(图 2), 交叉峰H2-1/H-2和H2-4/H2-5/H-6及其化学位移, 表明1的结构中存在1个乙烯基和1个三取代双键的次甲基(CH-6) 与两个亚甲基(H2-5和H2-4) 依次连接的结构单元。在1的HMBC谱中, H3-9与C-6、C-7和C-8的交叉峰, 结合它们的化学位移, 表明三取代双键的季碳C-7同时与1个甲基和1个羟甲基连接。同时, 依据H3-10与C-2、C-3和C-4的HMBC交叉峰, 结合它们的化学位移, 确定连氧的季碳C-3与CH-2、CH2-4和CH3-10相连。另外, H-1′与C-3的HMBC交叉峰证明β-吡喃葡萄糖氧基连接在C-3上; H2-6ʹ和H3-2ʺ与C-1ʺ的HMBC交叉峰确证葡萄糖基的6-羟基与乙酸脱水形成酯。因此, 化合物1的平面结构确定为如图 2所示。在化合物1的NOESY谱中, 交叉峰H-6/H2-8和H2-5/H3-9 (图 3) 表明三取代双键为反式(E)。化合物1用2 mol·L-1盐酸水解后, 从水解液中分离得到糖, 经衍生化后, 与D-和L-葡萄糖对照品的衍生物进行GC比较分析, 确定1中的葡萄糖单元具有D-构型。在1的圆二色谱(CD) 中, 显示苷元双键π-π*跃迁末端吸收的(-)-Cotton效应, 实测CD谱与1的计算电子圆二色(ECD) 谱曲线能够很好吻合(图 4), 据此确定1具有R构型。因此, 化合物1的结构得到确定, 命名为鹿茸草苷A (monochaside A)。
化合物2为无色胶状物, [α]$ {}_{\mathrm{D}}^{20} $ -10.5 (c 0.15, CH3OH), 红外光谱显示羟基(3 365 cm-1) 和共轭羰基(1 681 cm-1) 的特征吸收峰。由(+)-HR-ESI-MS m/z 353.156 8 [M+Na]+确定其分子式为C16H26O7。化合物2与1的NMR谱数据相似, 进一步比较发现二者结构的主要区别是2的1个共轭醛基[δH 9.29 (1H, d, J = 1.2 Hz, H-8) 和δC 200.3 (C-8)] 替代了1的羟甲基, 同时2的β-葡萄糖基上无乙酰化取代。因此, 初步推断2为1的苷元8-羟基氧化为醛且葡萄糖基上去乙酰化的衍生物, 并得到2的2D NMR数据分析以及酶水解实验的确证。尤其是, 在2的HMBC谱中, H3-9与C-6、C-7和C-8的交叉峰(图 2), 结合它们的化学位移, 确证结构中存在7-甲基-6-烯-8-醛共轭单元; 同时, H-1′与C-3的交叉峰, 确证β-D-吡喃葡萄糖氧基位移苷元的C-3上。另外, 在2的NOESY谱中, 交叉峰H-6/H-8 (图 3) 确证共轭烯醛为反式(E)。同样, 采用实验CD与计算ECD比较(图 5) 的方法确定2拥有3R构型。因此, 化合物2的结构得以确定, 命名为鹿茸草苷B (monochaside B)。
化合物3为无色胶状物, [α]$ {}_{\mathrm{D}}^{20} $ -14.9 (c 0.09, CH3OH)。通过IR、(+)-HR-ESI-MS和NMR波谱数据分析, 推定3为2的同分异构体。比较二者的NMR数据(表 1) 显示3的1个三取代双键[δH 5.39 (1H, dd, J = 6.6, 7.2 Hz, H-2), δC 122.7 (C-2) 和140.2 (C-3)] 替代了2的乙烯基; 同时, 3的1个连氧亚甲基[δH 4.30 (1H, dd, J = 12.6, 6.6 Hz, H-1a) 和4.21 (1H, dd, J = 12.6, 7.2 Hz, H-1b) 及δC 66.2 (C-1)] 替代了2的连氧季碳。由此推断3是2的1-β-D-吡喃葡萄糖氧基-2-烯异构体, 并进一步得到3的2D NMR谱数据解析的证实; 特别是得到1H-1H COSY谱交叉峰H2-1/H-2和HMBC谱交叉峰H3-10/C-2、C-3和C-4及H-1′/C-1 (图 2) 的确证。根据3的NOESY谱中NOE交叉峰H-2/H-4和H-6/H-8 (图 3), 确定其结构中的两个三取代双键均为反式(E)。用蜗牛酶水解3后, 从水解物中分离得到糖, 经衍生化后的GC分析, 确证为D-葡萄糖。因此, 化合物3的结构确定为如图 1所示, 命名为鹿茸草苷C (monochaside C)。
化合物4为无色胶状物, [α]$ {}_{\mathrm{D}}^{20} $为-8.2 (c 0.21, CH3OH)。经包括2D NMR的波谱数据(表 2、图 2和实验部分) 分析, 确定其平面结构与文献[16-19]报道的betulalbuside A相同。尽管文献[16, 19]中通过酶水解和衍生物制备确定了betulalbuside A的结构, 然而文献中先后报道betulalbuside A经酶水解得到苷元的比旋光数据{[α]$ {}_{\mathrm{D}}^{20} $ -1.5 (c 0.1, CH3OH)[16]; [α]$ {}_{\mathrm{D}}^{23} $ +7.59 (c 0.76, CH3OH)[19]} 相反。化合物4经酶水解后, 得到苷元4a和糖。其中, 糖与D-和L-葡萄糖对照品分别衍生化后, 经GC分析比较, 确证为β-D-吡喃葡萄; 苷元4a在CD3OD中的1H NMR数据与文献[19]报道betulalbuside A的苷元在相同溶剂中的一致, 4a的[α]$ {}_{\mathrm{D}}^{20} $为-8.33 (c 0.01, CH3OH), 与(+)-(S)-tobacodiol的相反, 而与(-)-(R)-芳樟醇氧化产物的一致[20, 21]。据此, 确定4具有R构型, 并得到计算NMR和DP4+概率分析(表 3) 的支持。尽管文献[16-19]报道从不同植物中分离得到具有相同平面结构的betulalbuside A, 但较早的文献[16-18]中均未确定苷元的构型, 而随后文献[19]中报道betulalbuside A的苷元为S。特别需要指出, 最初文献[16]报道betulalbuside A的苷化和羟基化位置以及糖单元端基碳(C-8、C-3和C-1′) 的化学位移分别为δC 67.2、75.2和99.1, 而随后文献[16, 17]中均为δC 76.0、73.8和102.7, 先后差异显著, 超出溶剂效应和实验误差范围。因此, 认为早期文献[16]与后期文献[17-19]报道的并非同一化合物, 为了避免与苷元构型确定为S的betulalbuside A混淆, 此处将化合物4命名为鹿茸草苷D (monochaside D)。
化合物5和6均为无色胶状物, [α]$ {}_{\mathrm{D}}^{20} $分别为-26.9 (c 0.17, CH3OH) 和-24.2 (c 0.13, CH3OH)。通过IR、(+)-HR-ESI-MS及1D和2D NMR谱数据分析, 确定它们的平面结构分别与文献报道9-羟基芳樟醇3-O-β-D-葡萄糖苷(9-hydroxylinaloyl glucoside, 5)[22]和(6Z)-9-羟基芳樟醇3-O-β-D-葡萄糖苷[(6Z)-9-hydroxylinaloyl glucoside, 6][22, 23]的相同。但文献中未明确它们的绝对构型, 且相应化合物在氘代吡啶(C5D5N)[22]或氘代甲醇(CD3OD)[23]中的NMR数据, 与5或6在D2O中的(表 4) 差异较大。例如, 5和6的C-1和C-3与文献[23]报道化合物在CD3OD中的相差为Δδ +3.6和+2.5, 而C-6相差分别为+2.4和+1.9。进一步在CD3OD中测得5和6的NMR数据与文献[23]报道化合物的基本一致, 差别可归属于实验偏差或定标导致的整体位移。化合物5和6经酶水解后, 得到各自的苷元5a和6a及糖。经1H NMR谱和比旋光值[α]$ {}_{\mathrm{D}}^{20} $测定, 并与D-葡萄糖对照品的数据比较, 确证均为β-D-吡喃葡萄。另外, 5a在CD3OD和6a在CD3Cl中的1H NMR数据, 分别与文献报道9-羟基芳樟醇[22]和(6Z)-9-羟基芳樟醇[23]在相应溶剂中的数据一致。同时, 5a和6a的[α]$ {}_{\mathrm{D}}^{20} $分别为+15.8 (c 0.02, CH3OH) 和+14.3 (c 0.03, CH3OH), 均与(+)-(S)-tobacodiol[20]的一致。据此, 确证5a和6a均具有S构型。因此, 化合物5和6的结构得以确定。需要指出, 文献[22, 24]报道9-羟基芳樟醇3-O-β-D-葡萄糖苷(9-hydroxylinaloyl glucoside) 水解得到苷元的比旋光值[α]$ {}_{\mathrm{D}}^{24} $为+20.0 (c 0.05, CH3OH)[22]和+16.0 (c 0.40, CH3OH)[24], 且在文献[24]中明确指出苷元具有3S, 6E构型。然而, 报道(6Z)-9-羟基芳樟醇3-O-β-D-葡萄糖苷[(6Z)-9-hydroxylinaloyl glucoside] 的文献[23]中, 尽管通过酶水解得到了苷元, 但是在未能提供比旋光等能证明其构型的情况下, 给出了与化合物6相同的结构。鉴于植物中存在不同构型的芳樟醇衍生物[20, 21], 为了简化名称和便于区分, 此处将化合物5和6分别取俗名为鹿茸草苷E和F (monochasides E和F)。
化合物7为无色胶状物, [α]$ {}_{\mathrm{D}}^{20} $ -11.6 (c 0.09, CH3OH)。红外光谱显示其分子结构中存在羟基(3 374 cm-1) 和羰基(1 744 cm-1)。由(+)-HR-ESI-MS m/z 369.151 6 [M+Na]+ (C16H26O8Na计算值, 369.152 0) 和NMR谱数据(表 4), 确定其分子组成为C16H26O8, 不饱和度为4。在D2O中, 7的NMR谱数据显示其结构中除含有1个β-D-吡喃葡萄糖氧基单元外, 还存在两个甲基(分别与季碳和次甲基连接)、3个亚甲基(一个连氧δC 76.9)、3个次甲基、1个连氧的季碳(δC 88.8) 和1个酯羰基(δC 185.5)。由此, 初步推断7为一个单环单萜苷, 进一步通过2D NMR数据分析对其结构进行了确定。根据1H-1H COSY谱交叉峰H-5/H2-6/H2-7、H-8/H-9/H-5和H-8/H3-10 (图 2), 以及HMBC交叉峰C-1/H-5、H-8和H-9以及H3-10/C-7、C-8和C-9, 并结合它们的化学位移, 确定7的苷元结构中存在一个5-取代的8-甲基环戊烷9-甲酰基单元。同时, 通过HMBC交叉峰信号H3-11/C-3、C-4和C-5以及它们的化学位移, 推定连氧亚甲基CH2-3和甲基CH3-11均通过季碳C-4与环戊烷单元的CH-5连接。另外, 根据HMBC交叉峰H-1′/C-3确定β-葡萄糖氧基连接在C-3上。最后, 根据7的分子式需要, 结合C-4的化学位移, 推定甲酰基C-1与季碳C-4之间通过氧原子连接形成内酯环。因此, 化合物7的平面结构确定为如图 2所示。在7的NOESY谱中, 可观测到交叉峰H-3b/H-5、H-3b/H-9和H-9/H3-10, 由此确定7的相对构型如图 3所示。化合物7用蜗牛酶水解后, 从水解液中分离得到苷元7a和糖。其中, 糖经衍生化后, 通过与对照品D-和L-葡萄糖衍生物的GC比较, 确定7中的β-吡喃葡萄基单元具有D-构型。在7和7a的CD中, 显示苷元内酯π-π*跃迁的(-)-Cotton效应, 经与计算ECD谱比较(图 6), 确定了7的绝对构型。因此, 化合物7的结构得以确定, 命名为鹿茸草苷G (monochaside G)。
化合物8为无色胶状物, [α]$ {}_{\mathrm{D}}^{20} $ -12.6 (c 0.11, CH3OH)。红外光谱显示由羟基(3 364 cm-1) 的特征吸收峰。由(+)-HR-ESI-MS m/z 357.188 4 [M+Na]+ (C16H30O7Na计算值, 357.188 4) 和NMR谱数据(表 4), 确定其分子组成为C16H30O7, 不饱和度为2。比较8与7的13C NMR谱数据(表 4), 发现8的一个羟甲基[δC 65.5 (C-1)] 和次甲基[δC 38.1 (C-4)] 分别替代了7的内酯羰基和连氧季碳; 进一步比较二者的1H NMR谱数据发现, 8的仲甲基[δH 0.96, d, J = 7.8 Hz (C-11)] 取代了7的叔甲基。根据以上差异, 推定8是7内酯环被还原开裂且脱除一个氧原子的衍生物。该推断得到8的2D NMR数据分析的确证(图 2)。特别是根据8的HMBC谱中交叉峰H3-11/C-3、C-4和C-5以及H-1′/C-3, 结合它们的化学位移, 确证β-吡喃葡萄糖氧基连接在C-3上。另外, 根据8的NOESY交叉峰H2-1/H3-11和H-9/H3-10确定其相对构型如图 3所示。用前述同样的酶水解、衍生化和GC比较, 确证8中的β-吡喃葡萄糖基为D-构型。然而, 8的CD未显示明显(-)-Cotton效应, 且因酶水解后未能得到苷元, 故根据与7的潜在生源联系, 初步推测8和7的母核具有相同的绝对构型, 并得到计算NMR和DP4+概率分析(表 3) 的支持。因此, 化合物8的结构得以初步确定, 命名为鹿茸草苷H (monochaside H)。
化合物9为无色胶状物, [α]$ {}_{\mathrm{D}}^{20} $ -31.1 (c 0.46, CH3OH)。红外光谱显示有羟基(3 357 cm-1) 的特征吸收峰。由(+)-HRESIMS m/z 341.156 7 [M+Na]+ (C15H26O7Na计算值, 341.157 1) 和NMR谱数据(表 4), 确定其分子组成为C15H26O7, 不饱和度为3。经9在D2O中的1D和2D NMR数据分析, 确证其与文献[25]报道kankanoside D1具有相同的平面结构。尽管文献中描述通过酶水解得到了苷元并通过其波谱数据确定为R-rotundiol, 但是未提供与苷元构型相关的[α]$ {}_{\mathrm{D}}^{20} $值或CD数据。因此, 认为kankanoside D1的构型确定缺乏证据。另外, 9在D2O中的碳谱数据与文献[25]报道kankanoside D1在CD3OD中的差别显著, 例如C-8、C-9和C-1′的差异分别为Δδ +2.9、-2.5和-1.8。进一步测得9在CD3OD中的NMR数据与文献[25]报道kankanoside D1的完全一致。由于文献[25]报道kankanoside D1的[α]$ {}_{\mathrm{D}}^{20} $ -21.2 (c 0.60, CH3OH) 与9的存在相对较大的差异, 因此对9进行了酶水解, 从水解液中分离得到苷元9a和糖。其中, 苷元的[α]$ {}_{\mathrm{D}}^{20} $为-14.3 (c 0.02, CH3OH), 与文献[26]报道R-rotundiol的一致; 糖的1H NMR和[α]$ {}_{\mathrm{D}}^{20} $均与D-葡萄糖对照品的一致。化合物9的CD谱显示π-π*跃迁末端吸收的(-)-Cotton效应, 与计算ECD谱吻合良好(图 7)。因此, 化合物9即kankanoside D1的结构得以确证。
通过包括2D NMR等波谱数据解析, 并与文献报道相关化合物的数据比较, 另外两个已知化合物的结构分别鉴定为8-羟基香叶醇1-O-β-D-葡萄糖苷(8-hydroxygeraniol 1-O-β-D-glucoside, 10)[27]和8-羟基香叶醇8-O-β-D-葡萄糖苷(8-hydroxygeraniol 8-O-β-D-glucoside, 11)[28]。由于文献中报道它们在CD3OD和C5D5N中NMR数据与本实验在D2O中测得数据之间存在比较明显的溶剂效应差异, 故在表 5中列出了本实验的NMR数据。
以上研究结果证明, 鹿茸草中存在数目众多、且结构未曾发现的单萜苷类化学成分, 增添了鹿茸草及同属植物化学成分的结构多样性。尤其是, 新结构化合物1~4、7和8的发现, 增加了单萜苷类天然产物的结构多样性。尽管6[23]和9[25]的分子结构曾有报道, 然而文献中未能提供可证明它们构型的实验数据, 本研究首次阐明了它们的绝对构型。另外, 由于这些单萜苷类化合物在鹿茸草水提取物中以微量形式存在, 分离得到的样品量有限, 因此未能进行活性筛选评价, 相关工作有待通过分离富集或合成获得足够样品后进一步探究。
实验部分
收起
AUTOPOL V型旋光测定仪(美国Rudolph公司), Nicolet impact 5700型傅立叶变换红外光谱仪(美国Thermo Electron Corporation公司), JASCO V-650型紫外光谱仪(日本JASCO公司), JASCO J-815型CD测定仪(日本JASCO公司), SYS-600及Inova-500核磁共振仪(美国Varian公司, 以溶剂峰信号或甲醇定标为参照), Q Exactive Focus型质谱仪(美国Thermo Fisher Scientific公司), SSI-1500型高效液相色谱仪(美国科学系统公司), Sephadex LH-20 (瑞典Amersham Pharmacia公司), Toyopearl HW-40C凝胶树脂(日本TOSOH公司), AQ-C18反相色谱柱(日本Daisogel公司), PFP反相色谱柱(日本Daisogel公司), 柱色谱硅胶(200~300目) 及薄层色谱用硅胶GF254 (青岛海洋化工厂)。所有试剂若无特别说明, 均购自北京化工厂, 级别为分析纯或色谱纯。
鹿茸草(全草) 由哈尔滨市康隆药业有限责任公司提供, 标本现存于哈尔滨市康隆药业有限责任公司。
1 提取与分离
将干燥的Monochasma savatieri全草(47 kg) 粉碎并用水煎煮30 min (3×300 L)。将水提取物减压浓缩, 然后经HP-20大孔树脂柱色谱分离, 依次用水、50%乙醇和95%乙醇洗脱, 得到相应的馏分A~C。减压浓缩后, 50%乙醇洗脱部分(1 700 g) 经MCI分离, 依次用水、30%乙醇、50%乙醇和95%乙醇洗脱, 得到B1~B4。B2 (550 g) 经Sephadex LH-20凝胶柱色谱进行分离, 以乙醇和水为流动相, 梯度洗脱, 合并成分相同馏分并回收溶剂后得到B2-1~B2-19, 其中B2-6 (52.6 g) 经Sephadex LH-20凝胶柱色谱进行分离, 乙醇-水梯度洗脱, 薄层色谱检测, 合并相同组分后, 得到亚组分B2-6a~B2-6p。B2-6i (4.71 g) 用Toyopearl HW-40C凝胶柱色谱(水) 分离, 得到B2-6i-1~B2-6i-10。在Toyopearl HW-40C凝胶柱色谱上以水为洗脱溶剂分离B2-6i-4 (2.03 g) 得到B2-6i-4-1~B2-6i-4-5, 其中B2-6i-4-2 (330 mg) 及B2-6i-4-3 (320 mg) 分别经Flash柱色谱(乙酸乙酯-乙醇-水1∶0∶0~0∶0∶1) 分离, 得到组分B2-6i-4-2-1~B2-6i-4-2-13及B2-6i-4-3-1~B2-6i-4-3-10。将B2-6i-4-2-7~B2-6i-4-2-11及B2-6i-4-3-4~B2-6i-4-3-8合并为B2-6i-4-2-7 (232 mg), 采用制备薄层色谱(二氯甲烷-甲醇5∶1) 分离, 得到B2-6i-4-2-7A~B2-6i-4-2-7H, 其中, B2-6i-4-2-7F (23 mg) 经反相半制备型HPLC (PFP柱, 35%甲醇, 2.0 mL·min-1) 纯化, 得到化合物9 (tR = 27.2 min, 4.6 mg); B2-6i-4-2-7E (36 mg) 经反相半制备型HPLC (PFP柱, 35%甲醇, 2.0 mL·min-1) 纯化, 得到化合物5(tR = 33.2 min, 1.7 mg) 和6(tR = 41.7 min, 1.3 mg)。
通过Flash柱色谱进一步分离B2-6i-4-4(1.20 g) 和B2-6i-5(820 mg), 分别经Flash柱色谱(乙酸乙酯-乙醇-水1∶0∶0~0∶0∶1) 分离, 得到B2-6i-4-4-1~B2-6i-4-4-29和B2-6i-5-1~B2-6i-5-28。根据薄层色谱检测, 合并B2-6i-4-4-13和B2-6i-5-12为组分B2-6i-4-4-13(94 mg), 并经制备薄层色谱(乙酸乙酯-乙醇-水15∶2∶1) 制备得到亚组分B2-6i-4-4-13A~B2-6i-4-4-13F。其中, B2-6i-4-4-13F(22 mg) 经反相半制备型HPLC(AQ C18柱, 40%甲醇, 2.0 mL·min-1) 纯化, 得到化合物2(tR = 50.2 min, 1.5 mg)。B2-6i-6(1.12 g) 经Flash柱色谱(乙酸乙酯-乙醇-水1∶0∶0~0∶0∶1) 分离, 得到亚组分B2-6i-6-1~B2-6i-6-13。B2-6i-6-6(28 mg) 经反相半制备型HPLC(AQ C18柱, 48%甲醇, 2.0 mL·min-1) 分离, 得到化合物1(tR = 30.6 min, 1.1 mg)。B2-6i-6-9(139 mg) 经Flash柱色谱进行分离, 以甲醇和水为溶剂, 梯度洗脱, 得到B2-6i-6-9A~B2-6i-6-9C, 其中B2-6i-6-9A(42 mg) 通过反相半制备HPLC(PFP柱, 40%甲醇, 2.0 mL·min-1) 纯化, 得到化合物3(tR = 38.2 min, 1.5 mg)。将B2-6i-4-4-17、B2-6i-4-4-18、B2-6i-5-18~20、B2-6i-6-18、B2-6i-6-19合并为B2-6i-6-18(324 mg), 经Flash柱色谱分离, 二氯甲烷-甲醇(5∶1) 洗脱, 得到B2-6i-6-18A~B2-6i-6-18C。其中B2-6i-6-18B(227 mg) 通过制备薄层色谱(二氯甲烷-甲醇5∶1) 制备得到亚组分B2-6i-6-18B-1~B2-6i-6-18B-3。B2-6i-6-18B-1 (83 mg) 经反相半制备HPLC(PFP柱, 40%甲醇, 2.0 mL·min-1) 分离, 得到化合物7(tR = 26.3 min, 1.15 mg)。将B2-6i-4-4-16、B2-6i-5-17、B2-6i-6-15合并为B2-6i-6-15(332 mg), 经Flash柱色谱分离, 二氯甲烷-甲醇(5∶1) 洗脱, 得到B2-6i-6-15A~B2-6i-6-15D。其中B2-6i-6-15D(280 mg) 通过制备薄层色谱(乙酸乙酯-乙醇-水12∶2∶1) 制备得到亚组分B2-6i-6-15D-1~B2-6i-6-15D-6。B2-6i-6-15D-4(83 mg) 经反相半制备HPLC(AQ C18柱, 35%甲醇, 2.0 mL·min-1) 分离, 得到化合物4(tR = 41.9 min, 5.39 mg)、化合物8(tR = 54.9 min, 1.12 mg)、10(tR = 53.2 min, 1.12 mg) 和11(tR = 56.7 min, 1.09 mg)。
2 结构鉴定
化合物1: 无色胶状物; [α]$ {}_{\mathrm{D}}^{20} $ -19.8 (c 0.10, CH3OH); UV (CH3OH) λmax (log ε) 202 (3.73), 282 (2.50, sh) nm; CD (MeOH): 200 (Δε -1.10) nm; IR νmax 3 362, 2 957, 2 921, 2 851, 1 741, 1 677, 1 596, 1 463, 1 412, 1 377, 1 260, 1 078, 1 038, 925, 701 cm-1; 1H NMR (CD3OD, 600 MHz)、13C NMR (CD3OD, 150 MHz) 数据见表 1。(+)-HR-ESI-MS m/z 397.183 2 [M+Na]+ (C18H30O8Na计算值, 397.183 3)。
化合物2: 无色胶状物; [α]$ {}_{\mathrm{D}}^{20} $ -10.5 (c 0.15, CH3OH); UV (CH3OH) λmax (log ε) 202 (3.42), 221(3.59) nm; CD (MeOH): 222 (Δε -0.36) nm; IR νmax 3 365, 2 957, 2 924, 2 877, 2 854, 1 681, 1 637, 1 413, 1 377, 1 260, 1 204, 1 157, 1 076, 1 038, 929, 878, 801 cm-1; 1H NMR (D2O, 600 MHz)、13C NMR(D2O, 150 MHz) 数据见表 1。(+)-HR-ESI-MS m/z 353.156 8 [M+Na]+(C16H26O7Na计算值, 353.157 1)。
化合物3: 无色胶状物; [α]$ {}_{\mathrm{D}}^{20} $ -14.9 (c 0.09, CH3OH); UV (CH3OH) λmax (log ε) 202 (3.58), 229 (3.67) nm; IR νmax 3 380, 2 924, 1 678, 1 415, 1 379, 1 260, 1 157, 1 077, 1 041 cm-1; 1H NMR (CD3OD, 600 MHz)、13C NMR (CD3OD, 150 MHz) 数据见表 1; (+)-HR-ESI-MS m/z 331.175 1 [M+H]+ (C16H27O7计算值, 331.175 1)。
化合物4: 无色胶状物; [α]$ {}_{\mathrm{D}}^{20} $ -8.2 (c 0.21, CH3OH); UV (CH3OH) λmax (log ε) 203 (3.23) nm; IR νmax 3 378, 2 971, 2 921, 2 872, 1 674, 1 647, 1 454, 1 413, 1 369, 1 318, 1 262, 1 201, 1 159, 1 098, 1 077, 1 042, 914 cm-1; 1H NMR (D2O, 600 MHz)、13C NMR (D2O, 150 MHz) 数据见表 2; (+)-HR-ESI-MS m/z 355.171 4 [M+Na]+ (C16H28O7Na计算值, 355.172 7)。
化合物5: 无色胶状物; [α]$ {}_{\mathrm{D}}^{20} $ -26.9 (c 0.17, CH3OH); UV (CH3OH) λmax (log ε) 203 (3.37), 233 (2.56), 283 (2.37) nm; CD (MeOH): 223 (Δε +0.07), 285 (Δε -0.13) nm; IR νmax 3 367, 2 980, 2 919, 2 873, 1 643, 1 413, 1 377, 1 153, 1 076, 1 037, 1 015, 930 cm-1; 1H NMR (D2O, 600 MHz)、13C NMR (D2O, 150 MHz) 数据见表 2; (+)-HR-ESI-MS m/z 355.172 2 [M+Na]+ (C16H28O7Na计算值, 355.172 7)。
化合物6: 无色胶状物; [α]$ {}_{\mathrm{D}}^{20} $ -24.2 (c 0.13, CH3OH); UV (CH3OH) λmax (log ε) 203 (3.45) nm; CD (MeOH): 200 (Δε -1.52), 243 (Δε +0.29) nm; IR νmax 3 365, 2 969, 2 929, 2 875, 1 702, 1 641, 1 569, 1 454, 1 413, 1 376, 1 260, 1 154, 1 077, 1 037, 1 016, 926, 874 cm-1; 1H NMR (D2O, 600 MHz)、13C NMR (D2O, 150 MHz) 数据见表 2; (+)-HR-ESI-MS m/z 355.172 3 [M+Na]+ (C16H28O7Na计算值, 355.172 7)。
化合物7: 无色胶状物; [α]$ {}_{\mathrm{D}}^{20} $ -11.6 (c 0.09, CH3OH); UV (CH3OH) λmax (log ε) 203 (3.35), 229 (2.98), 278(2.45) nm; CD (MeOH): 214 (Δε -0.17) nm; IR νmax 3 374, 2 957, 2 925, 2 871, 1 743, 1 672, 1 592, 1 455, 1 416, 1 382, 1 305, 1 252, 1 163, 1 078, 887 cm-1; 1H NMR (D2O, 600 MHz)、13C NMR (D2O, 150 MHz) 数据见表 4; (+)-HR-ESI-MS m/z 369.151 6 [M+Na]+ (C16H26O8Na计算值, 369.152 0)。
化合物8: 无色胶状物; [α]$ {}_{\mathrm{D}}^{20} $ -12.6 (c 0.11, CH3OH); IR νmax 3 364, 2 954, 2 926, 2 870, 1 679, 1 591, 1 462, 1 417, 1 378, 1 260, 1 203, 1 167, 1 078, 1 029, 801 cm-1; 1H NMR (D2O, 500 MHz)、13C NMR (D2O, 125 MHz) 数据见表 4; (+)-HR-ESI-MS m/z 357.188 4 [M+Na]+ (C16H30O7Na计算值, 357.188 4)。
化合物9: 白色粉末; [α]$ {}_{\mathrm{D}}^{20} $ -31.1 (c 0.46, CH3OH); UV (CH3OH) λmax (log ε) 199 (4.02) nm; CD (MeOH): 202 (Δε -5.69) nm; IR νmax 3 357, 2 921, 2 883, 1 571, 1 438, 1 413, 1 381, 1 338, 1 161, 1 078, 1 044, 1 025 cm-1; 1H NMR (D2O, 500 MHz)、13C NMR (D2O, 125 MHz) 数据见表 4; (+)-HR-ESI-MS m/z 341.156 7 [M+Na]+ (C15H26O7Na计算值, 341.157 1)。
化合物10: 无色胶状物; [α]$ {}_{\mathrm{D}}^{20} $ -16.1 (c 0.11, CH3OH); UV (CH3OH) λmax (log ε) 204 (4.12) nm; IR νmax 3 374, 2 914, 2 875, 1 670, 1 444, 1 382, 1 157, 1 077, 1 041, 1 021, 897 cm-1; 1H NMR (D2O, 500 MHz)、13C NMR (D2O, 125 MHz) 数据见表 5; (+)-HR-ESI-MS m/z 355.171 9 [M+Na]+ (C16H28O7Na计算值, 355.172 7)。
化合物11: 无色胶状物; [α]$ {}_{\mathrm{D}}^{20} $ -21.1 (c 0.11, CH3OH); UV (CH3OH) λmax (log ε) 203 (4.08) nm; IR νmax 3 360, 2 921, 2 881, 1 676, 1 434, 1 389, 1 364, 1 203, 1 186, 1 134, 1 077, 1 020 cm-1; 1H NMR (D2O, 500 MHz)、13C NMR (D2O, 125 MHz) 数据见表 5; (+)-HR-ESI-MS m/z 355.171 9 [M+Na]+ (C16H28O7Na计算值, 355.172 7)。
3 化合物1~9的水解
化合物1 (约1.0 mg) 与2 mol·L-1三氟乙酸水溶液(1.0 mL) 在90 ℃下加热水解3 h。减压蒸干溶剂后将反应物溶解在1 mL水中, 用等体积乙酸乙酯萃取3次, 浓缩水层得到化合物1的糖部分。化合物2~9各取约1.0 mg, 溶于1 mL水中, 加入2.0 mg蜗牛酶, 于38 ℃下水浴加热24 h。加入1 mL甲醇终止反应, 并通过Sephadex LH-20 (甲醇-水1∶1) 分离, 得到各自的苷元和糖。将1~9各自水解得到的糖与对照品(D-甘露糖、D-半乳糖和D-葡萄糖) 共薄层对比, 展开剂为正丙醇-水-氨水(60∶30∶2.4), 结果显示均与D-葡萄糖对照品的Rf值一致。另外, 将1~4、7和8分别水解得到的糖以及D-型和L-型葡萄糖对照品(各1 mg), 分别溶解在无水吡啶(0.6 mL) 中, 加入2.0 mg L-半胱氨酸甲酯盐酸盐, 加热到60 ℃, 持续1 h。将反应混合物蒸干至无吡啶味, 加入0.5 mL N-三甲基硅咪唑, 并加热至60 ℃持续1 h。将反应混合物加入2 mL水中, 并用等体积正己烷萃取3次, 合并萃取液浓缩得到糖的噻唑三甲基硅醚化衍生物。用1 mL正己烷溶解后, 进行气相色谱分析。分析条件: FID检测器温度300 ℃, 起始温度200 ℃, 以10 ℃·min-1的速率程序升温至280 ℃, 并且维持35 min; 载气: N2。结果显示1~4、7和8水解得到糖的衍生物的保留时间均与D-葡萄糖一致。测得5、6和9水解得到糖的[α]$ {}_{\mathrm{D}}^{20} $分别为+39.2 (c 0.07, CH3OH)、+32.3 (c 0.03, CH3OH)、+36.5 (c 0.05, CH3OH), 并测得它们的1H NMR谱均与D-葡萄糖对照品的一致。
4 ECD、UV和NMR谱计算
应用Gaussian 16软件的GMMX模块, 在MMFF94分子力场中采用蒙特卡洛方式对化合物的构象进行搜索, 得到相对能量小于3.0 kcal·mol-1的优势构象。应用Gaussian 16程序、密度泛函算法和CPCM模型(conductor-like polarizable continuum model) 模拟溶剂效应, 在B3LYP/6-31+G(d, p) 水平上, 对搜索获得的构象进一步优化得到优化构象及其玻尔兹曼分布。在B3LYP/6-311+G(d, p) 水平上, 计算Gibbs自由能在3.0 kcal·mol-1以内的优化构象的各激发态能量、振子强度和转子强度。根据优化构象的玻尔兹曼分布概率, 通过加权平均化, 拟合得到理论计算的ECD和UV谱图(σ = 0.30 eV)。在MPW1PW91/6-311+G(d, p) 水平上, 用GIAO算法[29, 30]计算Gibbs自由能在3.0 kcal·mol-1以内的优化构象的NMR, 再通过加权平均化, 拟合得到理论计算的1H和13C NMR数据, 再经DP4+概率分析, 进行确证。
作者贡献: 石建功负责实验设计、数据分析, 以及文章的修改及定稿; 郭庆兰负责计算化学、数据分析及文章的修改; 刘琛负责化学实验实施及文章初稿的撰写; 朱承根和徐成博辅助开展化学实验; 穆滨负责药材的收集及鉴定。
利益冲突: 作者声明无利益冲突。
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2022年第57卷第8期
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doi: 10.16438/j.0513-4870.2022-0757
  • 接收时间：2022-06-12
  • 首发时间：2025-12-23
  • 出版时间：2022-08-12
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  • 收稿日期：2022-06-12
  • 修回日期：2022-06-18
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    1.中国医学科学院、北京协和医学院药物研究所, 天然药物活性物质与功能国家重点实验室, 北京 100050
    2.哈尔滨市康隆药业有限责任公司, 黑龙江 哈尔滨 150025

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石建功, Tel: 86-10-63025166, Fax: 86-10-63017757, E-mail:
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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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