LC-ESI-MS-MS鉴定菥蓂中芥子油苷及有机酸类成分-于金英

2014-06-252014-11-19“”2010ZX09401-306-3-15*[e-mail]20152767-72491001-688020151-0067-07LC-ESI-MS/MS12233412*161113724000653ThermoFisherScientific2012004400065-LC-ESI-MS/MS。ThermoScientificSyncronisC18150×2．1mm3μm0．1%A-B0．35mL/min254nm。101169。、、。LC-ESI-MS/MSＲ284.1ADOI10．16333/j．1001-6880．2015．01．014IdentificationofGlucosinolatesandOrganicAcidsinThlaspiarvenseL．byLC-ESI-MS/MSYUJin-ying12WANGYun-hong2LIUGuo-qiang3WANGBin-hao3PANZheng4YANGＲong-ping12*1ChengduUniversityofTraditionalChineseMedicineTCMChengdu611137China2ChongqingAcademyofChineseMateriaMedicaChongqing400065China3ThermoFisherScientificShanghaiDemonstrationCenterShanghai201200China4CollegeofBio-InformationChongqingUniversityofPostsandTelecommunicationsChongqing400065ChinaAbstractTheobjectiveofthisstudywastoidentifythemaincomponentsofThlaspiarvenseL．byLC-ESI-MS/MS．TheseparationwasperformedonThermoScientificSyncronisC18column150mm×2．1mm3μmwithamobilephaseconsistingof0．1%formicacidinwaterAandacetonitrileBforgradientelution．TheanalysiswasperformedinpositiveandnegativeionmodeusingfullscanmodewithESIsource．TenglucosinolatesandelevenorganicacidswerewellseparatedandidentifiedfromtheextractsofT．arvense．9glucosinolateswereidentifiedforthefirsttimefromT．ar-venseincludingsixpairsofstructuralisomers．Thenewmethodwasaccuraterapidandeffective．ItlaidthefoundationforfurtherresearchofT．arvense．KeywordsThlaspiarvenseL．LC-ESI-MS/MSglucosinolatesorganicacidsThlaspiarvenseL．Thla-spiL．12。《》。、、、、、、。、6。、、34%23。45。。-LC-ESI-MS/MS1011。11．1ThermoQ-Exactive-ThermoFisherScientificDionexULtiMate3000Mil-liporeMilli-QMilliporeAB204-NMettlerToledo。1．2SIGMA101016464。。22．1ThermoScientificSyncronisC18150×2．1mm3μm0．1%A/B0～28min95%～40%A28～40min40%～10%A40～45min10%A45～45．1min10%～95%A45．1～50min95%A。0．35mL/min5μL254nm30℃。2．2ESI+3．0KV/-2．8KV40arb10arb300℃350℃FullMS70000dd-MS217500NCE35SteppedNCE50%m/z100～1000。n-Bu-tylamine、Caffeine、MＲFAUltramark1621Sodiumdodecylsulfate、So-diumtaurocholateUltramark16211ppm。2．324h10．32mg25mL1mL0．4128mg。2．4100g1531h1g/mL50%100mL。2．5LC-MS。3LC-MSC、H、O、NS1ppmXcaliburMS2ChemspiderMassFrontier7．021。3．1β-D-、Ｒ1Fig.1NegativeionMSspectraofsinigrin86Vol.27Ｒ。。。1。M-H-m/z358．02734MS/MS6m/z259．01239、195．03311、96．96005、95．95228、79．9573574．99092MassFron-tier7．06M-H-C4H6NS-、M-H-C4H5O4NS-、M-H-C4H5O4NS-C6H10O-、M-H-C4H5O4NS-C6H10O-H-。MS22。2Fig.2MS2fragmentationcharacteristicsofsinigrinundernegativeionmode3．2LC-MS254nmTIC3。ESI。1MS2。3HPLCFig.3HPLCandtotalioncurrentchromatogramsofT．arvense1Table1IdentificationofchemicalconstituentsfromT．arvenseNo．ＲTM-H-m/zM+NH4+m/zM+H+m/zMS2m/zFormulaCompound11．15358．0273425919596957974C10H17O9NS21-Propenylglucosinolate96Vol.27LC-ESI-MS/MS21．75358．0273425919596957974C10H17O9NS2Sinigrin33．15372．0197225919596957974C11H19O9NS24-Butenylglucosinolate44．22374．0186625919596957974C11H21O9NS2n-Butylglucosinolate54．98374．0186625919596957974C11H21O9NS2Isobutylglucosinolate68．12400．0496425919596957974C12H19O10NS22-keto-4-Pentenylglucosinolate78．45408．0432425919596957974C14H19O9NS2Benzyl-glucosinolate89．37388．0862425919596957974C12H23O9NS2n-Pentylglucosinolate99．77388．0862425919596957974C12H23O9NS22-Methylbutylglucosinolate1010．17388．0862425919596957974C12H23O9NS2Isopentylglucosinolate111．15133．014281157271C4H6O5D-+-Malicacid121．61133．014281157271C4H6O5L---Malicacid131．23191．019781291118785C6H8O7Citricacid141．68191．019781291118785C6H8O7Isocitricacid1521．25348．2739629527717310967C18H34O5Pinellicacid1624．12309．2052629127318911981C18H28O4Ostopanicacid1725．97307．1897628927118915912579C18H26O4916-Dioxo-101214-octadecatrienoicacid1826．28313．2369129527725913510781C18H32O49-Octadecenedioicacid1928．37315．252592972792611099581C18H34O4OctadecanedioicAcid2033．73295．22635277295241151C18H30O39-oxo-1012-Octadecadienoicacid2134．38295．22635277295241151C18H30O313-oxo-911-Octadecadienoicacid3．3121．15min1．75minM-H-m/z358．02734。C10H17O9NS2。M-H-m/z358．02734MS/MS6m/z259．01239、195．03311、96．96005、95．95228、79．9573574.99092MassFrontier7．01、26M-H-C4H6NS-、M-H-C4H5O4NS-、M-H-C4H5O4NS-C6H10O-、M-H-C4H5O4NS-C6H10O-H-。78Chemspider121-pro-penylglucosinolateSinigrin。3～103．15、4．22、4．98、8．12、9．37、9．77、10．17minC11H19O9NS2、C11H21O9NS2、C11H21O9NS2、C12H19O10NS2、C12H23O9NS2、C12H23O9NS2、C12H23O9NS2。458、910。3～10MS212m/z259．01239、195．03311、96．96005、95．95228、79．9573574．99092MassFrontier7．03～10M-H-C4H6NS-、M-H-C4H5O4NS-、M-H-C4H5O4NS-C6H10O-、M-H-C4H5O4NS-C6H10O-H-。78Chemspi-der74-butenylglucosinolaten-butylglucosinolateisobutylglucosinolate2-keto-4-pentenylglucosinolatebenzyl-glucosinolaten-pentylglucosinolate2-methylbutylglucosinolateisopentylglucosinolate。2。07Vol.272Table2ChemicalstructureofglucosinolateCompoundGeneralchemicalstructureofglucosinolateＲＲside-chainstructure1-PropenylglucosinolateSinigrin4-Butenylglucosinolaten-ButylglucosinolateIsobutylglucosinolate2-keto-4-PentenylglucosinolateBenzyl-glucosinolaten-Pentylglucosinolate2-MethylbutylglucosinolateIsopentylglucosinolate2-2--4-2-3．411121．15min1.61minM-H-m/z133.01428。C4H6O5。M-H-m/z133.01408MS/MS3m/z115.00362、72.99