超高效液相色谱-四极杆静电场轨道阱高分辨质谱联用法分析不同西洋参加工品的皂苷类成分
|
摘要
采用超高效液相色谱-四极杆静电场轨道阱高分辨质谱联用法(UPLC Orbitrap HRMS)对西洋参不同加工品中的皂苷类成分差异进行分析。高分辨质谱条件为电喷雾电离源,轨道阱质量分析器,负离子模式采集。结果显示,根据一级质谱精确质荷比信息,获得化合物的精确分子量;根据二级串联质谱信息,获得化合物的碎片信息。总结了不同类型皂苷的特征质谱碎裂规律,并对碎裂规律进行比对,初步归属和鉴定西洋参中55种皂苷类成分,其中原人参二醇型皂苷成分28种、原人参三醇型皂苷成分17种、奥克梯隆型皂苷成分5种和齐墩果烷型皂苷成分5种。通过比较不同西洋参加工品中皂苷类组成的差异,为揭示不同加工方法对西洋参皂苷成分的影响规律提供了依据,并为西洋参的开发利用以及阐明药效物质基础提供了参考。
An ultra-performance liquid chromatography-Q exactive orbitrap high resolution mass spectrometric( UPLC Orbitrap HRMS) method was utilized for the analysis of ginsenosides compositions in different processd Panax quinquefoliums L. roots. The electrospray ionization( ESI) ion source and orbitrap mass analyzer were equipped,and negative ion mode was used for data collection. On the basis of accurate mass to charge in MS,the accurate molecular weights of ginsenosides were acquired. Based on the second stage of tandem MS data,the fragmentations of ginsenosides were obtained. The characteristic MS fragmentation pathways of different types of ginsenosides were summarized. According to these fragmentation rules,55 ginsenosides in Panax quinquefoliums L. roots were identified,among which protopanaxdiol( PPD) type ginsenosides were 28, protopanaxtriol( PPT)type ginsenosides were 17,oleanane( OLE) type ginsenosides and ocotillol( OCO) type ginsenosides were both 5. The ginsenosides compositions of PPD,PPT,OCO and OLE types in different processd Panax quinquefoliums L. roots were compared. The results obtained provided the information for influences of different processing on ginsenosides composition of Panax quinquefoliums L. roots. The research also provided a reference for the exploitation and utilization of Panax quinquefoliums L. roots,and a clarification for its bio-effectiveness material basis.
An ultra-performance liquid chromatography-Q exactive orbitrap high resolution mass spectrometric( UPLC Orbitrap HRMS) method was utilized for the analysis of ginsenosides compositions in different processd Panax quinquefoliums L. roots. The electrospray ionization( ESI) ion source and orbitrap mass analyzer were equipped,and negative ion mode was used for data collection. On the basis of accurate mass to charge in MS,the accurate molecular weights of ginsenosides were acquired. Based on the second stage of tandem MS data,the fragmentations of ginsenosides were obtained. The characteristic MS fragmentation pathways of different types of ginsenosides were summarized. According to these fragmentation rules,55 ginsenosides in Panax quinquefoliums L. roots were identified,among which protopanaxdiol( PPD) type ginsenosides were 28, protopanaxtriol( PPT)type ginsenosides were 17,oleanane( OLE) type ginsenosides and ocotillol( OCO) type ginsenosides were both 5. The ginsenosides compositions of PPD,PPT,OCO and OLE types in different processd Panax quinquefoliums L. roots were compared. The results obtained provided the information for influences of different processing on ginsenosides composition of Panax quinquefoliums L. roots. The research also provided a reference for the exploitation and utilization of Panax quinquefoliums L. roots,and a clarification for its bio-effectiveness material basis.
引文
[1]Ko S K.J.Korean Soc.Appl.Biol.Chem.,2009,52(2):198-201.
[2]Xu Y Z,Ren Y,Wang J X,Sun M,Zhao X Y,Liu Y.J.Chin.Med.Mater.(许云章,任烨,王静霞,孙美,赵小燕,刘圆.中药材),2014,37(10):1743-1748.
[3]Qi L W,Wang C Z,Yuan C S.Phytochemistry,2011,72(8):689-699.
[4]Lee M R,Yun B S,Sung C K.J.Ginseng Res.,2012,36:93-101.
[5]Wang L,Wang Y P,Xu S Q,Sun C H,Yan S,Liu J Y,Wang Y Y,Hou W,Jin Y P.Special Wild Econ.Anim.Plant Res.(王蕾,王英平,许世泉,孙成贺,焉石,刘继永,王艳艳,侯威,金银萍.特产研究),2007,3:73-77.
[6]Zhao J Y,Zhou D X,Zhai P G.J.Zhejiang Chin.Med.Univ.(赵珺彦,周大兴,翟鹏贵.浙江中医药大学学报),2011,35(5):755-757.
[7]Ma B L,Qin X H,Shi Z X.J.Jiangxi College Tradit.Chin.Med.(马宝兰,秦绪花,史载祥.江西中医学院学报),2011,23(5):88-92.
[8]Liang H,Li B,Liu Y F,Feng L J,Song Y G.Pharm.Today(梁洪,李波,刘艳芳,冯丽洁,宋艳刚.今日药学),2017,27(8):528-531.
[9]Li L,Chen H.Chin.Med.Herald(李岚,陈华.中药医药导报),2011,8(20):103-105.
[10]Zeng F,Wang X M,Yang M,Lu Z Q,Guo D A.J.Chin.Pharm.Sci.,2007,16:277-281.
[11]Zhang X,Ma X,Si B,Zhao Y.Biomed.Chromatogr.,2011,25(6):646-651.
[12]Wang J,Bai H L,Liu C M,Li L.Chromatographia,2010,71(3/4):267-271.
[13]Sun X B,Chen P,Cook S L,Jackson G P,Harnly J M,Harrington P B.Anal.Chem.,2012,84(8):3628-3634.
[14]Luo Y Y,Liu J X,Liu X H,Wang S N,Hua Y J,Lan C W,Xing Q Q.J.Instrum.Anal.(罗益远,刘娟秀,刘训红,王胜男,华愉教,兰才武,邢清清.分析测试学报),2017,36(1):73-79.
[15]Steinmann D,Ganzera M.J.Pharm.Biomed.Anal.,2011,55(4):744-757.
[16]Qin Y,Yin J B,Du D S,Cao J,Yin C L,Cheng Z H.J.Instrum.Anal.(秦艳,尹建兵,杜冬生,曹捷,尹成乐,程志红.分析测试学报),2017,36(1):9-17.
[17]Yang M,Sun J H,Lu Z Q,Chen G T,Guan S H,Liu X,Jiang B H,Ye M,Guo D A.J.Chromatogr.A,2009,1216(11):2045-2062.
[18]Shi Y,Sun C J,Zheng B,Gao B,Sun A M.Food Anal.Method,2013,6(1):112-122.
[19]Guo Y Y,Wu W,Qin Q J,Sun J H,Liu S Y.J.Chin.Spectrom.Soc.(郭迎迎,吴巍,秦秋杰,孙靖辉,刘淑莹.质谱学报),2014,35(1):79-84.
[20]Zhong W,Dai Y L,Li X Y,Wang Y B,Yue H,Liu S Y.J.Chin.Spectrom.Soc.(钟薇,戴雨霖,李晓宇,王一博,越皓,刘淑莹.质谱学报),2015,36(6):529-534.
[21]Bai X,Huang X,Liu S Y.Drug Eval.Res.(白雪,黄鑫,刘淑莹.药物评价研究),2015,38(6):652-655.
[22]Wu W,Sun L,Zhang Z,Guo Y Y,Liu S Y.J.Pharm.Biomed.Anal.,2015,(107):141-150.
[2]Xu Y Z,Ren Y,Wang J X,Sun M,Zhao X Y,Liu Y.J.Chin.Med.Mater.(许云章,任烨,王静霞,孙美,赵小燕,刘圆.中药材),2014,37(10):1743-1748.
[3]Qi L W,Wang C Z,Yuan C S.Phytochemistry,2011,72(8):689-699.
[4]Lee M R,Yun B S,Sung C K.J.Ginseng Res.,2012,36:93-101.
[5]Wang L,Wang Y P,Xu S Q,Sun C H,Yan S,Liu J Y,Wang Y Y,Hou W,Jin Y P.Special Wild Econ.Anim.Plant Res.(王蕾,王英平,许世泉,孙成贺,焉石,刘继永,王艳艳,侯威,金银萍.特产研究),2007,3:73-77.
[6]Zhao J Y,Zhou D X,Zhai P G.J.Zhejiang Chin.Med.Univ.(赵珺彦,周大兴,翟鹏贵.浙江中医药大学学报),2011,35(5):755-757.
[7]Ma B L,Qin X H,Shi Z X.J.Jiangxi College Tradit.Chin.Med.(马宝兰,秦绪花,史载祥.江西中医学院学报),2011,23(5):88-92.
[8]Liang H,Li B,Liu Y F,Feng L J,Song Y G.Pharm.Today(梁洪,李波,刘艳芳,冯丽洁,宋艳刚.今日药学),2017,27(8):528-531.
[9]Li L,Chen H.Chin.Med.Herald(李岚,陈华.中药医药导报),2011,8(20):103-105.
[10]Zeng F,Wang X M,Yang M,Lu Z Q,Guo D A.J.Chin.Pharm.Sci.,2007,16:277-281.
[11]Zhang X,Ma X,Si B,Zhao Y.Biomed.Chromatogr.,2011,25(6):646-651.
[12]Wang J,Bai H L,Liu C M,Li L.Chromatographia,2010,71(3/4):267-271.
[13]Sun X B,Chen P,Cook S L,Jackson G P,Harnly J M,Harrington P B.Anal.Chem.,2012,84(8):3628-3634.
[14]Luo Y Y,Liu J X,Liu X H,Wang S N,Hua Y J,Lan C W,Xing Q Q.J.Instrum.Anal.(罗益远,刘娟秀,刘训红,王胜男,华愉教,兰才武,邢清清.分析测试学报),2017,36(1):73-79.
[15]Steinmann D,Ganzera M.J.Pharm.Biomed.Anal.,2011,55(4):744-757.
[16]Qin Y,Yin J B,Du D S,Cao J,Yin C L,Cheng Z H.J.Instrum.Anal.(秦艳,尹建兵,杜冬生,曹捷,尹成乐,程志红.分析测试学报),2017,36(1):9-17.
[17]Yang M,Sun J H,Lu Z Q,Chen G T,Guan S H,Liu X,Jiang B H,Ye M,Guo D A.J.Chromatogr.A,2009,1216(11):2045-2062.
[18]Shi Y,Sun C J,Zheng B,Gao B,Sun A M.Food Anal.Method,2013,6(1):112-122.
[19]Guo Y Y,Wu W,Qin Q J,Sun J H,Liu S Y.J.Chin.Spectrom.Soc.(郭迎迎,吴巍,秦秋杰,孙靖辉,刘淑莹.质谱学报),2014,35(1):79-84.
[20]Zhong W,Dai Y L,Li X Y,Wang Y B,Yue H,Liu S Y.J.Chin.Spectrom.Soc.(钟薇,戴雨霖,李晓宇,王一博,越皓,刘淑莹.质谱学报),2015,36(6):529-534.
[21]Bai X,Huang X,Liu S Y.Drug Eval.Res.(白雪,黄鑫,刘淑莹.药物评价研究),2015,38(6):652-655.
[22]Wu W,Sun L,Zhang Z,Guo Y Y,Liu S Y.J.Pharm.Biomed.Anal.,2015,(107):141-150.