基于UFLC-Triple TOF MS/MS技术分析竹节参中皂苷类成分
|
摘要
采用超快速液相色谱-三重四极杆飞行时间质谱技术对竹节参中皂苷类成分进行分析。采用色谱柱Synergi~(TM) Hydro-RP 100?(2.0 mm×100 mm,2.5μm),以0.1%甲酸-水(A)-0.1%甲酸-乙腈(B)为流动相进行梯度洗脱;在电喷雾负离子扫描模式下采集数据。根据高分辨质谱提供的准分子离子和碎片离子的精确分子质量信息,结合标准品对照与参考相关文献数据,初步鉴定出53种皂苷,包括18种原人参二醇型、21种原人参三醇型、10种齐墩果烷型和4种奥寇梯木醇型皂苷。本实验可为探索竹节参药材的药效物质基础和建立其药材品质的综合评价体系提供基础资料。
In this study, we analyzed the saponins of Panacis japonici Rhizoma by ultra-fast liquid chromatography coupled with triple quadrupole-time of flight tandem mass spectrometry(UFLC-Triple TOF MS/MS). The chromatographic separation was performed on a Synergi~(TM) Hydro-RP 100 ?(2.0 mm × 100 mm, 2.5 μm) with gradient elution using a mobile phase comprised of 0.1% formic acid solution(A)-0.1% formic acid acetonitrile(B). MS data were collected in the negative ion mode. Based on the accurate molecular mass information of quasi-molecular and fragment ions provided by highresolution mass spectrometry combined with standard reference data and relevant literature data, a total of 53 saponins werefinally identified, including 18 glycosides of protopanaxadiol(PPD), 21 glycosides of protopanaxatriol(PPT), 10 glycosides of oleanolic acid and 4 glycosides of ocotillone. This study paves the way for exploring the pharmacodynamic material basis of P. japonici Rhizoma and developing a comprehensive quality evaluation system.
In this study, we analyzed the saponins of Panacis japonici Rhizoma by ultra-fast liquid chromatography coupled with triple quadrupole-time of flight tandem mass spectrometry(UFLC-Triple TOF MS/MS). The chromatographic separation was performed on a Synergi~(TM) Hydro-RP 100 ?(2.0 mm × 100 mm, 2.5 μm) with gradient elution using a mobile phase comprised of 0.1% formic acid solution(A)-0.1% formic acid acetonitrile(B). MS data were collected in the negative ion mode. Based on the accurate molecular mass information of quasi-molecular and fragment ions provided by highresolution mass spectrometry combined with standard reference data and relevant literature data, a total of 53 saponins werefinally identified, including 18 glycosides of protopanaxadiol(PPD), 21 glycosides of protopanaxatriol(PPT), 10 glycosides of oleanolic acid and 4 glycosides of ocotillone. This study paves the way for exploring the pharmacodynamic material basis of P. japonici Rhizoma and developing a comprehensive quality evaluation system.
引文
[1]国家药典委员会.中华人民共和国药典:一部[S].北京:中国科技出版社,2015:138-139.
[2]涂星,徐新华,张燕,等.恩施地区濒危野生竹节参生态环境及伴生植物群落特征研究[J].中国中药杂志,2016,41(9):1596-1601.DOI:10.4268/cjcmm20160905.
[3]翟琨.竹节人参GAP基地土壤环境质量现状分析[J].湖北农业科学,2010,49(10):2477-2478.DOI:10.3969/j.issn.0439-8114.2010.10.044.
[4]武秋爽,陈平,张庆文.竹节参化学成分、药理活性及分析方法研究进展[J].亚太传统医药,2016,12(6):46-54.DOI:10.11954/ytctyy.201606020.
[5]李有贵.竹节人参皂苷对乙醇性肝损伤的保护机理研究[D].杭州:浙江大学,2011:108-110.
[6]DUN Y Y,LIU M,CHEN J,et al.Regulatory effects of saponins from Panax japonicus on colonic epithelial tight junctions in aging rats[J].Journal of Ginseng Research,2018,42:50-56.DOI:10.1016/j.jgr.2016.12.011.
[7]HE H B,XU J,XU Y Q,et al.Cardioprotective effects of saponins from Panax japonicus on acute myocardial ischemia against oxidative stress-triggered damage and cardiac cell death in rats[J].Journal of Ethnopharmacology,2012,140:73-82.DOI:10.1016/j.jep.2011.12.024.
[8]任冰.人参属药材竹节参和珠子参化学成分指纹图谱研究[D].武汉:武汉轻工大学,2015.
[9]MENG FC,WU Q S,WANG R,et al.A novel strategy for quantitative analysis of major ginsenosides in Panacis japonici Rhizoma with a standardized reference fraction[J].Molecules,2017,22(12):2067-2074.DOI:10.3390/molecules22122067.
[10]WU Q S,WANG C M,LU J J,et al.Simultaneous determination of six saponins in Panacis japonici Rhizoma using quantitative analysis of multi-components with single-marker method[J].Current Pharmaceutical Analysis,2017,13:289-295.DOI:10.2174/1573412912666160526165500.
[11]YOSHIZAK K,DEVKOTA H P,FUJINO H,et al.Saponins composition of rhizomes,taproots,and lateral roots of Satsuma-ninjin(Panax japonicus)[J].Chemical&Pharmaceutical Bulletin,2013,61(3):344-350.
[12]LIU Y,ZHAO J,CHEN Y,et al.Polyacetylenic oleanane-type triterpene saponins from the roots of Panax japonicas[J].Journal of Natural Products,2016,79(12):3079-3085.DOI:10.1021/acs.jnatprod.6b00748.
[13]XIE G X,NI Y,SU M M,et al.Application of ultra-performance LC-TOF MS metabolite profiling techniques to the analysis of medicinal Panax herbs[J].Metabolomics,2008,4(3):248-260.DOI:10.1007/s11306-008-0115-5.
[14]ZOU K,ZHU S,TOHDA C,et al.Dammarane-type triterpene saponins from Panax japonicas[J].Journal of Natural Products,2002,65(3):346-351.DOI:10.1021/np010354j.
[15]徐凤莲,张启云,姜丽,等.UHPLC-Q-TOF/MS法分析红参醇提液中化学成分[J].中药新药与临床药理,2015,26(4):529-534.DOI:10.3969/j.issn.1003-9783.2015.04.024.
[16]常相伟,李德坤,王彤,等.基于UHPLC-QTOF/MS的植物代谢组学技术鉴别林下山参的不同部位[J].药学学报,2016,51(10):1609-1615.DOI:10.16438/j.0513-4870.2016-0325.
[17]MAO Q,BAI M,XU J D,et al.Discrimination of leaves of Panax ginseng and P.quinquefolius by ultrahigh performance liquid chromatography quadrupole/time-of-flight mass spectrometry based metabolomics approach[J].Journal of Pharmaceutical&Biomedical Analysis,2014,97:129-140.DOI:10.1016/j.jpba.2014.04.032.
[18]WANG L L,HAN L F,YU H S,et al.Analysis of the constituents in“Zhu She Yong Xue Shuan Tong”by ultra high performance liquid chromatography with quadrupole time-of-flight mass spectrometry combined with preparative high performance liquid chromatography[J].Molecules,2015,20(11):20518-20537.DOI:10.3390/molecules201119712.
[19]WU R,LIN S,WANG J,et al.Rapid characterization of chemical constituents and metabolites of Qi-Jing-Sheng-Bai granule by using UHPLC-Q-TOF-MS[J].Journal of Separation Science,2018,41(9):1960-1972.DOI:10.1002/jssc.201701310.
[20]王邱,冯毅凡,芮雯,等.UPLC/Q-TOFMS对三七中皂苷类成分的快速化学表征[J].天然产物研究与开发,2014,26(8):1233-1239.DOI:10.16333/j.1001-6880.2014.08.018.
[21]LIU F,MA N,HE C,et al.Qualitative and quantitative analysis of the saponins in Panax notoginseng leaves using ultra-performance liquid chromatography coupled with time-of-flight tandem mass spectrometry and high performance liquid chromatography coupled with UV detector[J].Journal of Ginseng Research,2018,42:149-157.DOI:10.1016/j.jgr.2017.01.007.
[22]FAN X,RONG Y,WANG S.Analysis of NaoMaiTong metabolites using high-performance liquid chromatography/high-resolution mass spectrometry in rat urine[J].Chromatographia,2017,80:1-29.DOI:10.1007/s10337-017-3363-6.
[23]汪静静.不同产地和年限人参样品皂苷类成分的比较研究[D].合肥:安徽中医药大学,2015.
[24]ZHU G Y,LI Y W,HAU K P,et al.Protopanaxatriol-type ginsenosides from the root of Panax ginseng[J].Journal of Agricultural&Food Chemistry,2011,59(1):200-205.DOI:10.1021/jf1037932.
[25]TANG S Y,LIU S,LIU Z Q,et al.Analysis and identification of the chemical constituents of Ding-Zhi-Xiao-Wan prescription by HPLC-IT-MSn and HPLC-Q-TOF-MS[J].Chinese Journal of Chemistry,2015,33(4):451-462.DOI:10.1002/cjoc.201400789.
[26]戴雨霖,越皓,孙长江,等.高分离度快速液相色谱-四极杆-飞行时间质谱法分析酒制和醋制人参的皂苷类成分[J].分析化学,2015,43(8):1181-1186.DOI:10.11895/j.issn.0253-3820.150204.
[27]赵静,秦振娴,彭冰,等.基于UPLC-Q-TOF MS技术的三七中皂苷类成分质谱裂解规律研究[J].质谱学报,2017,38(1):97-108.DOI:10.7538/zpxb.2017.38.01.0097.
[28]MA X Q,XIAO H B,LIANG X M.Identification of ginsenosides in Panax quinquefolium by LC-MS[J].Chromatographia,2006,64(1/2):31-36.DOI:10.1365/s10337-006-0812-z.
[29]SUN T T,LIANG X L,ZHU H Y,et al.Rapid separation and identification of 31 major saponins in Shizhu ginseng by ultrahigh performance liquid chromatography-electron spray ionizationMS/MS[J].Journal of Ginseng Research,2016,40(3):220-228.DOI:10.1016/j.jgr.2015.07.008.
[30]WU W,SUN L,ZHANG Z,et al.Profiling and multivariate statistical analysis of Panax ginseng based on ultra-high-performance liquid chromatography coupled with quadrupole-time-of-flight mass spectrometry[J].Journal of Pharmaceutical&Biomedical Analysis,2015,107:141-150.DOI:10.1016/j.jpba.2014.12.030.
[31]ZHOU J,YI H,ZHAO Z X,et al.Simultaneous qualitative and quantitative evaluation of Ilex kudingcha C.J.tseng by using UPLC and UHPLC-qTOF-MS/MS[J].Journal of Pharmaceutical&B i o m e d i c a l A n a l y s i s,2 0 1 8,1 5 5:1 5-2 6.D O I:1 0.1 0 1 6/j.jpba.2018.02.037.
[32]王洪平,杨鑫宝,杨秀伟,等.吉林人参根和根茎的化学成分研究[J].中国中药杂志,2013,38(17):2807-2817.DOI:10.4268/cjcmm20131714.
[33]LI ZH,XIAO S,AI N,et al.Derivative multiple reaction monitoring and single herb calibration approach for multiple components quantification of traditional Chinese medicine analogous formulae[J].Journal of Chromatography A,2015,1376:126-142.DOI:10.1016/j.chroma.2014.12.024.
[34]ZOU K,ZHU S,MESELHY M R,et al.Dammarane-type saponins from Panax japonicus and their neurite outgrowth activity in SK-N-SH Cells[J].Journal of Natural Products,2002,65(9):1288-1292.DOI:10.1007/s00238-004-0600-7.
[35]ZHANG Y,HAN L F,SAKAH K J,et al.Bioactive protopanaxatriol type saponins isolated from the roots of Panax notoginseng(Burk.)F.H.Chen.[J].Molecules,2013,18(9):10352-10366.DOI:10.3390/molecules180910352.
[36]YANG H,LEE DY,KANG K B,et al.Identification of ginsenoside markers from dry purified extract of Panax ginseng by a dereplication approach and UPLC-QTOF/MS analysis[J].Journal of Pharmaceutical&Biomedical Analysis,2015,109:91-104.DOI:10.1016/j.jpba.2015.02.034.
[37]邹海艳,赵晖,邱葵,等.竹节参皂苷类化学成分的研究[J].世界中医药,2012,7(6):565-566.
[38]陈亚,邱明华,古昆,等.巨花雪胆中的两个新化合物[J].云南植物研究,2003,25(5):613-619.DOI:10.3969/j.issn.2095-0845.2003.05.013.
[39]LI S N,LIU C Y,LIU C M,et al.Extraction and in vitro screening of potential acetylcholinesterase inhibitors from the leaves of Panax japonicus[J].Journal of Chromatography B,2017,1061/1062:139-145.DOI:10.1016/j.jchromb.2017.07.019.
[40]JIANG Y,LIU F J,WANG Y M,et al.Dereplication-guided isolation of novel hepatoprotective triterpenoid saponins from Celosiae Semen by high-performance liquid chromatography coupled with electrospray ionization tandem quadrupole-time-of-flight mass spectrometry[J].Journal of Pharmaceutical&Biomedical Analysis,2017,132:148-155.DOI:10.1016/j.jpba.2016.10.001.
[41]HATTORI M,KAWATA Y,KAKIUCHI N,et al.Application of liquid chromatography/mass spectrometry to the qualitative analysis of saponins.II[J].Chemical&Pharmaceutical Bulletin,1988,36(11):4467-4473.DOI:10.1248/cpb.36.4467.
[42]TANAKA O,MORITA T,KASAI R,et al.Study on saponins of rhizomes of Panax pseudo-ginseng subs.himalaicus collected at Tzatogang and Pari-la,Bhutan-Himalaya[J].Chemical&Pharmaceutical Bulletin,2008,33(6):2323-2330.DOI:10.1248/cpb.33.2323.
[43]QIU S,YANG W Z,SHI X J,et al.A green protocol for efficient discovery of novel natural compounds:characterization of new ginsenosides from the stems and leaves of Panax ginseng as a case study[J].Analytica Chimica Acta,2015,893:65-76.DOI:10.1016/j.aca.2015.08.048.
[44]QI LW,WANG H Y,ZHANG H,et al.Diagnostic ion filtering to characterize ginseng saponins by rapid liquid chromatography with time-of-flight mass spectrometry[J].Journal of Chromatography A,2012,1230:93-99.DOI:10.1016/j.chroma.2012.01.079.
[2]涂星,徐新华,张燕,等.恩施地区濒危野生竹节参生态环境及伴生植物群落特征研究[J].中国中药杂志,2016,41(9):1596-1601.DOI:10.4268/cjcmm20160905.
[3]翟琨.竹节人参GAP基地土壤环境质量现状分析[J].湖北农业科学,2010,49(10):2477-2478.DOI:10.3969/j.issn.0439-8114.2010.10.044.
[4]武秋爽,陈平,张庆文.竹节参化学成分、药理活性及分析方法研究进展[J].亚太传统医药,2016,12(6):46-54.DOI:10.11954/ytctyy.201606020.
[5]李有贵.竹节人参皂苷对乙醇性肝损伤的保护机理研究[D].杭州:浙江大学,2011:108-110.
[6]DUN Y Y,LIU M,CHEN J,et al.Regulatory effects of saponins from Panax japonicus on colonic epithelial tight junctions in aging rats[J].Journal of Ginseng Research,2018,42:50-56.DOI:10.1016/j.jgr.2016.12.011.
[7]HE H B,XU J,XU Y Q,et al.Cardioprotective effects of saponins from Panax japonicus on acute myocardial ischemia against oxidative stress-triggered damage and cardiac cell death in rats[J].Journal of Ethnopharmacology,2012,140:73-82.DOI:10.1016/j.jep.2011.12.024.
[8]任冰.人参属药材竹节参和珠子参化学成分指纹图谱研究[D].武汉:武汉轻工大学,2015.
[9]MENG FC,WU Q S,WANG R,et al.A novel strategy for quantitative analysis of major ginsenosides in Panacis japonici Rhizoma with a standardized reference fraction[J].Molecules,2017,22(12):2067-2074.DOI:10.3390/molecules22122067.
[10]WU Q S,WANG C M,LU J J,et al.Simultaneous determination of six saponins in Panacis japonici Rhizoma using quantitative analysis of multi-components with single-marker method[J].Current Pharmaceutical Analysis,2017,13:289-295.DOI:10.2174/1573412912666160526165500.
[11]YOSHIZAK K,DEVKOTA H P,FUJINO H,et al.Saponins composition of rhizomes,taproots,and lateral roots of Satsuma-ninjin(Panax japonicus)[J].Chemical&Pharmaceutical Bulletin,2013,61(3):344-350.
[12]LIU Y,ZHAO J,CHEN Y,et al.Polyacetylenic oleanane-type triterpene saponins from the roots of Panax japonicas[J].Journal of Natural Products,2016,79(12):3079-3085.DOI:10.1021/acs.jnatprod.6b00748.
[13]XIE G X,NI Y,SU M M,et al.Application of ultra-performance LC-TOF MS metabolite profiling techniques to the analysis of medicinal Panax herbs[J].Metabolomics,2008,4(3):248-260.DOI:10.1007/s11306-008-0115-5.
[14]ZOU K,ZHU S,TOHDA C,et al.Dammarane-type triterpene saponins from Panax japonicas[J].Journal of Natural Products,2002,65(3):346-351.DOI:10.1021/np010354j.
[15]徐凤莲,张启云,姜丽,等.UHPLC-Q-TOF/MS法分析红参醇提液中化学成分[J].中药新药与临床药理,2015,26(4):529-534.DOI:10.3969/j.issn.1003-9783.2015.04.024.
[16]常相伟,李德坤,王彤,等.基于UHPLC-QTOF/MS的植物代谢组学技术鉴别林下山参的不同部位[J].药学学报,2016,51(10):1609-1615.DOI:10.16438/j.0513-4870.2016-0325.
[17]MAO Q,BAI M,XU J D,et al.Discrimination of leaves of Panax ginseng and P.quinquefolius by ultrahigh performance liquid chromatography quadrupole/time-of-flight mass spectrometry based metabolomics approach[J].Journal of Pharmaceutical&Biomedical Analysis,2014,97:129-140.DOI:10.1016/j.jpba.2014.04.032.
[18]WANG L L,HAN L F,YU H S,et al.Analysis of the constituents in“Zhu She Yong Xue Shuan Tong”by ultra high performance liquid chromatography with quadrupole time-of-flight mass spectrometry combined with preparative high performance liquid chromatography[J].Molecules,2015,20(11):20518-20537.DOI:10.3390/molecules201119712.
[19]WU R,LIN S,WANG J,et al.Rapid characterization of chemical constituents and metabolites of Qi-Jing-Sheng-Bai granule by using UHPLC-Q-TOF-MS[J].Journal of Separation Science,2018,41(9):1960-1972.DOI:10.1002/jssc.201701310.
[20]王邱,冯毅凡,芮雯,等.UPLC/Q-TOFMS对三七中皂苷类成分的快速化学表征[J].天然产物研究与开发,2014,26(8):1233-1239.DOI:10.16333/j.1001-6880.2014.08.018.
[21]LIU F,MA N,HE C,et al.Qualitative and quantitative analysis of the saponins in Panax notoginseng leaves using ultra-performance liquid chromatography coupled with time-of-flight tandem mass spectrometry and high performance liquid chromatography coupled with UV detector[J].Journal of Ginseng Research,2018,42:149-157.DOI:10.1016/j.jgr.2017.01.007.
[22]FAN X,RONG Y,WANG S.Analysis of NaoMaiTong metabolites using high-performance liquid chromatography/high-resolution mass spectrometry in rat urine[J].Chromatographia,2017,80:1-29.DOI:10.1007/s10337-017-3363-6.
[23]汪静静.不同产地和年限人参样品皂苷类成分的比较研究[D].合肥:安徽中医药大学,2015.
[24]ZHU G Y,LI Y W,HAU K P,et al.Protopanaxatriol-type ginsenosides from the root of Panax ginseng[J].Journal of Agricultural&Food Chemistry,2011,59(1):200-205.DOI:10.1021/jf1037932.
[25]TANG S Y,LIU S,LIU Z Q,et al.Analysis and identification of the chemical constituents of Ding-Zhi-Xiao-Wan prescription by HPLC-IT-MSn and HPLC-Q-TOF-MS[J].Chinese Journal of Chemistry,2015,33(4):451-462.DOI:10.1002/cjoc.201400789.
[26]戴雨霖,越皓,孙长江,等.高分离度快速液相色谱-四极杆-飞行时间质谱法分析酒制和醋制人参的皂苷类成分[J].分析化学,2015,43(8):1181-1186.DOI:10.11895/j.issn.0253-3820.150204.
[27]赵静,秦振娴,彭冰,等.基于UPLC-Q-TOF MS技术的三七中皂苷类成分质谱裂解规律研究[J].质谱学报,2017,38(1):97-108.DOI:10.7538/zpxb.2017.38.01.0097.
[28]MA X Q,XIAO H B,LIANG X M.Identification of ginsenosides in Panax quinquefolium by LC-MS[J].Chromatographia,2006,64(1/2):31-36.DOI:10.1365/s10337-006-0812-z.
[29]SUN T T,LIANG X L,ZHU H Y,et al.Rapid separation and identification of 31 major saponins in Shizhu ginseng by ultrahigh performance liquid chromatography-electron spray ionizationMS/MS[J].Journal of Ginseng Research,2016,40(3):220-228.DOI:10.1016/j.jgr.2015.07.008.
[30]WU W,SUN L,ZHANG Z,et al.Profiling and multivariate statistical analysis of Panax ginseng based on ultra-high-performance liquid chromatography coupled with quadrupole-time-of-flight mass spectrometry[J].Journal of Pharmaceutical&Biomedical Analysis,2015,107:141-150.DOI:10.1016/j.jpba.2014.12.030.
[31]ZHOU J,YI H,ZHAO Z X,et al.Simultaneous qualitative and quantitative evaluation of Ilex kudingcha C.J.tseng by using UPLC and UHPLC-qTOF-MS/MS[J].Journal of Pharmaceutical&B i o m e d i c a l A n a l y s i s,2 0 1 8,1 5 5:1 5-2 6.D O I:1 0.1 0 1 6/j.jpba.2018.02.037.
[32]王洪平,杨鑫宝,杨秀伟,等.吉林人参根和根茎的化学成分研究[J].中国中药杂志,2013,38(17):2807-2817.DOI:10.4268/cjcmm20131714.
[33]LI ZH,XIAO S,AI N,et al.Derivative multiple reaction monitoring and single herb calibration approach for multiple components quantification of traditional Chinese medicine analogous formulae[J].Journal of Chromatography A,2015,1376:126-142.DOI:10.1016/j.chroma.2014.12.024.
[34]ZOU K,ZHU S,MESELHY M R,et al.Dammarane-type saponins from Panax japonicus and their neurite outgrowth activity in SK-N-SH Cells[J].Journal of Natural Products,2002,65(9):1288-1292.DOI:10.1007/s00238-004-0600-7.
[35]ZHANG Y,HAN L F,SAKAH K J,et al.Bioactive protopanaxatriol type saponins isolated from the roots of Panax notoginseng(Burk.)F.H.Chen.[J].Molecules,2013,18(9):10352-10366.DOI:10.3390/molecules180910352.
[36]YANG H,LEE DY,KANG K B,et al.Identification of ginsenoside markers from dry purified extract of Panax ginseng by a dereplication approach and UPLC-QTOF/MS analysis[J].Journal of Pharmaceutical&Biomedical Analysis,2015,109:91-104.DOI:10.1016/j.jpba.2015.02.034.
[37]邹海艳,赵晖,邱葵,等.竹节参皂苷类化学成分的研究[J].世界中医药,2012,7(6):565-566.
[38]陈亚,邱明华,古昆,等.巨花雪胆中的两个新化合物[J].云南植物研究,2003,25(5):613-619.DOI:10.3969/j.issn.2095-0845.2003.05.013.
[39]LI S N,LIU C Y,LIU C M,et al.Extraction and in vitro screening of potential acetylcholinesterase inhibitors from the leaves of Panax japonicus[J].Journal of Chromatography B,2017,1061/1062:139-145.DOI:10.1016/j.jchromb.2017.07.019.
[40]JIANG Y,LIU F J,WANG Y M,et al.Dereplication-guided isolation of novel hepatoprotective triterpenoid saponins from Celosiae Semen by high-performance liquid chromatography coupled with electrospray ionization tandem quadrupole-time-of-flight mass spectrometry[J].Journal of Pharmaceutical&Biomedical Analysis,2017,132:148-155.DOI:10.1016/j.jpba.2016.10.001.
[41]HATTORI M,KAWATA Y,KAKIUCHI N,et al.Application of liquid chromatography/mass spectrometry to the qualitative analysis of saponins.II[J].Chemical&Pharmaceutical Bulletin,1988,36(11):4467-4473.DOI:10.1248/cpb.36.4467.
[42]TANAKA O,MORITA T,KASAI R,et al.Study on saponins of rhizomes of Panax pseudo-ginseng subs.himalaicus collected at Tzatogang and Pari-la,Bhutan-Himalaya[J].Chemical&Pharmaceutical Bulletin,2008,33(6):2323-2330.DOI:10.1248/cpb.33.2323.
[43]QIU S,YANG W Z,SHI X J,et al.A green protocol for efficient discovery of novel natural compounds:characterization of new ginsenosides from the stems and leaves of Panax ginseng as a case study[J].Analytica Chimica Acta,2015,893:65-76.DOI:10.1016/j.aca.2015.08.048.
[44]QI LW,WANG H Y,ZHANG H,et al.Diagnostic ion filtering to characterize ginseng saponins by rapid liquid chromatography with time-of-flight mass spectrometry[J].Journal of Chromatography A,2012,1230:93-99.DOI:10.1016/j.chroma.2012.01.079.
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |