全 文 :2016
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Vol41,No.7 April,2016
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IdentificationofchemicalconstituentsinScrophulariae
RadixbyHPLCITTOFMS
WANGJingzhe,XUFeng,LIUZhen,MALiman,SHANGMingying,LIUGuangxue,CAIShaoqing
(SchoolofPharmaceuticalSciences,PekingUniversity,Beijing100191,China)
[Abstract] ThisexperimentwasperformedtoestablishaqualitativeanalysisonchemicalconstituentsofScrophulariaeRadixby
HPLCESIITTOFMS.TheanalysiswasconductedonaC18column(Kromasil1005,46mm×250mm,5μm)with01% formic
acidacetonitrileasthemobilephaseforgradientelution;ESIionsourcewasusedformassspectra,anddatawerecolectedinnegative
andpositivemodesTheresultsshowedthat64compoundsfromScrophulariaeRadixhadbeenidentifiedbyanalyzingnegativeionmass
dataincludingelementcompositionandbycomparingwithdatafromliteratureTwonewcompounds(4hydroxy6Omethylcatalpol
andacetylangorosideC)andseventeenknowncompoundsweredetectedfromScrophulariaeRadixforthefirsttimeSeventeenknown
compoundsincludedtwelveiridoidglycosides,threephenylpropanoidglycosidesandtwootherkindcompoundsThisstudywilprovide
chemicalbasisforelucidationoftheefectivesubstanceintheScrophulariaeRadix.
[Keywords] ScrophulariaeRadix;HPLCESIITTOFMS;iridoidglycosides;phenylpropanoidglycosides
doi:10.4268/cjcmm20160717
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Table1 MSdataofidentifiedconstituentsfromScrophulariaeRadix
No tR/min ïó [M+HCOO]-/m/zÄÔ/ppm +æ-ï/m/z _V®¼
P1 14990C15H22O10 4071177 -442 4071177[M+HCOO]-,3611138[M-H]-,1990617
[M-H-glucosyl]-,1810504[M-H-glucosyl-H2O]-,
1690520[M-H-glucosyl-HCHO]-,1630426[M-H-glu
cosyl-2H2O]-,1510504[M-H-glucosyl-H2OHCHO]-
catalpol[14]
P2 20498C16H26O11 4391438 -433 4171382[M+Na]+,4391438[M+HCOO]-,3931369
[M-H]-,2310888[M-H-glucosyl]-,2130782[M-H-
glucosyl-H2O]-,1950626[M-H-glucosyl-2H2O]-,
1830616[M-H-glucosyl-HCHO]-,1630452[M-H-glu
cosyl-2H2OCH3OH]-
4hydroxy6Omethylcatalpol
P3 20757C15H22O9 3911230 -409 3691146[M+Na]+,3911230[M+HCOO]-,3451208
[M-H]-,1830671[M-H-glucosyl]-,1650671[M-H-
glucosyl-H2O]-,1350581[M-H-glucosyl-H2OHCHO]-
aucubin[15]
P4 21298C21H32O14 5531747 -488 5531747[M+HCOO]-,5071705[M-H]-,3451203
[M-H-glucosyl]-[aucubin-H]-,3271006[M-H-glu
cosyl-H2O]-
6Oβglucosylaucubin[16]
P5 21782C21H32O14 5531761 -235 5311640[M+Na]+,5531761[M+HCOO]-,5071681
[M-H]-,3230981[2glucosyl-H]-,1830330[M-H-
2glucosyl]-[aucubinHglucosyl]-,1790563[glucose-H]-,
1610463[glucosyl-H]-
6′Oβglucosylaucubin[17]
P6 22240C15H26O10 4111490 -438 3891418[M+Na]+,4111490[M+HCOO]-,3651440
[M-H]-[hargagideH+2H]-,3471288[M-H-H2O]-,
2030935[M-H-glucosyl]-,1790567[glucose-H]-,
1610481[glucosyl-H]-
dihydroharpagide[18]
P7 24748C21H32O14 5531761 -235 5531761[M+HCOO]-,5071677[M-H]-,3451133[M-
H-glucosyl]-,3271006[M-H-glucosyl-H2O]-,1790575
[glucose-H]-
6Oβglucosylaucubinisomer
P8 25407C21H32O14 5531750 -434 5531750[M+HCOO]-,5071746[M-H]-,3230940
[2glucosyl-H]-,1830747[M-H-2glucosyl]-,1790448
[glucose-H]-
6′Oβglucosylaucubin
isomer
P9 25523C15H24O8 3771427 -689 3551284[M+Na]+,3771427[M+HCOO]-,3311348
[M-H]-,1790543[glucose-H]-
ningpogosideA[19]
P10 25815C21H32O14 5531756 -325 5531756[M+HCOO]-,5071686[M-H]-,3451176
[M-H-glucosyl]-,1830788[M-H-2glucosyl]-,1790702
[glucose-H]-
6Oβglucosylaucubinisomer
P11 26140C21H32O14 5531760 -253 5531760[M+HCOO]-,5071710[M-H]-,3230966
[2glucosyl-H]-
6′Oβglucosylaucubin
isomer
P12 26315C21H34O15 5711881 018 5492845[M+Na]+,5711881[M+HCOO]-,5251828
[M-H]-,3631358[M-H-glucosyl]-[hargagide-H]-,
3451142[M-H-glucosyl-H2O]-,1830663[M-H-
2glucosyl-H2O]-,1650560[M-H-2glucosyl2H2O]-
6Oβglucosylharpagide[20]
P13 26698C21H32O14 5531749 -452 5531749[M+HCOO]-,5071689[M-H]-,3230959
[2glucosyl-H]-,1610563[glucosyl-H]-
6′Oβglucosylaucubin
isomer
P14 26982C15H24O10 4091348 -098 4091348[M+HCOO]-,3631304[M-H]-,2010781
[M-H-glucosyl]-,1830669[M-H-glucosyl-H2O]-,
1650604[M-H-glucosyl-2H2O]-,1570574[M-H-glucosyl
-CH3CHO]-,1390425[M-H-glucosyl-H2OCH3CHO]-
harpagide[15]
P15 27215C21H34O15 5711885 088 5491856[M+Na]+,5711885[M+HCOO]-,5251825
[M-H]-,3230938[2glucosyl-H]-,2010740[M-H-
2glucosyl]-,1830714[M-H-2glucosyl-H2O]-,1790593
[glucose-H]-
6′Oβglucosylharpagide[21]
·9521·
2016
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Vol41,No.7 April,2016
,*
1
No tR/min ïó [M+HCOO]-/m/zÄÔ/ppm +æ-ï/m/z _V®¼
P16 27598C21H34O15 5711869 -193 5491792[M+Na]+,5711869[M+HCOO]-,5251792
[M-H]-,3631648[M-H-glucosyl]-,3230946[2gluco
syl-H]-,2010760[M-H-2glucosyl]-,1830714[M-H-
2glucosyl-H2O]-
6′Oβglucosylharpagide
isomer
P17 28290C21H34O15 5711862 -315 5491669[M+Na]+,5711862[M+HCOO]-,5251796
[M-H]-,3631246[M-H-glucosyl]-,3230954[2gluco
syl-H]-,2010800[M-H-2glucosyl]-,1830686[M-H-
2glucosyl-H2O]-
6′Oβglucosylharpagide
isomer
P18 28790C16H24O10 4211335 -404 3991205[M+Na]+,4211335[M+HCOO]-,3751286
[M-H]-,2130757[M-H-glucosyl]-,1950673[M-H-
glucosyl-H2O]-,1830677[M-H-glucosyl-HCHO]-,
1630433[M-H-glucosyl-H2OCH3OH]-,1510461[M-
H-glucosyl-HCHOCH3OH]-
6Omethylcatalpol[15]
P19 29207C16H26O10 4231490 -425 4011377[M+Na]+,4231490[M+HCOO]-,3771424
[M-H]-,2150921[M-H-glucosyl]-,1970828[M-H-
glucosyl-H2O]-,1790696[glucose-H]-,1610484
[glucosyl-H]-
3,4dihydromethylcatalpol[22]
P20 30373C21H28O13 48714351) -452 4871435[M-H]-,1790376[cafeicacid-H]-,1350577
[cafeicacidHCO2]-
cistanosideF[15]
P21 30848C16H24O9 4051381 -518 3831260[M+Na]+,4051381[M+HCOO]-,3591317
[M-H]-,1970837[M-H-glucosyl]-,1650488[M-H-
glucosyl-CH3OH]-,1350489[M-H-glucosyl-CH3OH
HCHO]-
6Omethylaucubin[23,24]
P22 32373C21H28O14 50313771) -576 5031377[M-H]-,3411034[sucrosylH+H2O]-,
3230779[sucrosylH+H2O]-,1790374[cafeicacid-H]-,
1610343[cafeoyl-H]-
6OcafeoylβDfructo
furanosyl2αDglucopyrano
side[25]
P23 35132C26H40O16 60722621) 296 6072262[M-H]-,4611635[M-H-rhamnosyl]-,
4431561[M-H-rhamnosyl-H2O]-,3111071[M-H-rh
amnosylarabinosyl-H2O]-,1613469[glucosyl-H]-
deferuloylangorosideC[26]
P24 35415C21H28O13 48714761) 390 5111261[M+Na]+,4871476[M-H]-,1630375[M-H-
sucrosyl]-,[cumaricacid-H]-,1451054[cumaroyl-H]-
6Opcoumaroylsucrose[25]
P25 35840C18H26O10 40114471) -150 4471525[M+HCOO]-,4011447[M-H]-,2691014[M-
H-arabinosyl]-,1610523[glucosyl-H]-
phenylmethyl6OαLara
binopyranosylβDglucopyr
anoside[27]
P26 36823C22H30O14 5631604 -249 5411503[M+Na]+,5171560[M-H]-,5631604
[M+HCOO]-,1930560[ferulicacid-H]-、[M-H-sucros
yl]-,1750414[feruloyl-H]-
6′Oferuloylsucrose[28]
P27 40065C30H38O16 65320921) 077 6532092[M-H]-,4911566[M-H-glucosyl]-,2910847
[M-H-catalpol]-
premnacorymbosideB[29]
P28 40273C19H28O10 4611660 -108 4611660[M+HCOO]-,4151591[M-H]-,1490397[ara
binosylH+H2O]-[M-H-phenethylglucosyl]-
phenethyl βprimevero
side[30]
P29 40648C24H30O13 52516251) 209 5491499[M+Na]+,5251625[M-H]-,5071513
[M-H-H2O]-,3230771[cafeoyl+glucosyl-H]-,1610219
[cafeoyl-H]-
6″Ocafeoylharpagide[31]
P30 41265C27H38O17 6792089 -029 6572172[M+Na]+,6792089[M+HCOO]-,6331985
[M-H]-,4851475[M-H-cinnamoyl-H2O]-,3230864
[sucrosyl-H]-[M-H-cinnamicacidglucosyl]-
6OcinnamoylDfructo
furanosylOglucopyrano
side[31]
P31 41523C21H28O12 5171537 -503 5171537[M+HCOO]-,4711471[M-H]-,3230935[su
crosyl-H]-,[M-H-cinnamicacidglucosyl]-,1610557[glu
cosyl-H]-
sibiriosideAisomer
P32 44123C24H30O12 50916521) -255 5331607[M+Na]+,5091652[M-H]-,3070789[cour
maroyl+glucosyl-H]-,1630425[courmaricacid-H]-,
1610612[glucosyl-H]-
8Ocourmaroylharpagide
isomer
·0621·
I:è
:
GÝ_±
HPLCESIITTOFMS
à
,*
1
NotR/min ïó [M+HCOO]-/m/zÄÔ/ppm +æ-ï/m/z _V®¼
P3344782C29H36O15 62319591) -353 6471903[M+Na]+,6231959[M-H]-,4611606[M-
H-cafeoyl]-,3151036[M -H -cafeoylrhamnosyl]-,
2970946[M-H-cafeoylrhamnosyl-H2O]-
acteoside[15]
P3445848C21H28O12 5171543 -387 5171543[M+HCOO]-,4711503[M-H]-,3230953[su
crosyl-H]-、[M-H-cinnamoylglucosyl-H2O]-,1610557
[glucosyl-H]-
sibiriosideA[15]
P3546198C35H46O19 76925501) -143 7692550[M-H]-,5932011[M-H-ferulicacid+H2
O]-,4471468[M-H-ferulicacid+H2Oarabinosyl]-,
4611559[M-H-feruloylrhamnosyl]-,4291368[M-H-fer
uloylrhamnosyl-H2O]-
scrophulosideB1[32]
P3648323C29H36O15 62319451) -578 6231945[M-H]-,4611588[M-H-cafeoyl]-,3150980
[M-H-cafeoylrhamnosyl]-
isoacteoside[33]
P3748473C22H30O13 5471645 -420 5251321[M+Na]+,5471645[M+HCOO]-,5011619
[M-H]-,3230915[sucrosyl-H]-[M-H-methylcinnamic
acid]-
sibiriosideB[34]
P3848915C35H46O19 76925331) -364 7692533[M-H]-,5932015[M-H-feruloyl]-,4471398
[M-H-feruloylarabinosyl]-
scrophulosideB1isomer
P3949615C24H30O13 5711679 193 5491589[M+Na]+,5251624[M-H]-,3812213,
4431637,3230795[cafeoyl+glucosyl-H]-,2010800[M-
H-cafeoylglucosyl]-,5711679[M+HCOO]-,1829433
[M-H-cafeoylglucosyl]-,1790356[cafeicacid-H]-,
1610223[cafeoyl-H]-
6″Ocafeoylharpagideiso
mer
P4051857C30H40O16 7012266 -456 7012266[M+HCOO]-,6552184[M-H]-,5071673[M-
H-cinnamoyl-H2O]-,3271006[harpagideH-H2O]-[M-
H-cinnamoylglucosyl2H2O]-
6OαDgalactopyranosyl
harpagosideisomer
P4152548C36H48O19 78326971) -255 8072765[M+Na]+,7832697[M-H]-,6072179[M-
H-feruloyl]-,5892677[M-H-feruloyl-H2O]-,4611592
[M-H-feruloylrhamnosyl]-,3291231[M-H-feruloylrham
nosylarabinosyl]-
angorosideC[15]
P4252890C30H38O15 63721211) -267 6372121[M-H]-,4751766[M-H-cinnamoyl]-,
4611537[M-H-cinnamoylCH2]-,3291247[M-H-cin
namoylrhamnosyl]-
cistanosideC[35]
P4353115C36H48O19 78327011) -204 7832701[M-H]-,6072177[M-H-feruloylrhamnosyl]-,
5892087[M-H-feruloyl-H2O]-,4611591[M-H-feruloyl
rhamnosyl]-,4431566[M-H-feruloylrhamnosyl-H2O]-,
3291149[M-H-feruloylrhamnosylarabinosyl]-
angorosideCisomer
P4453290C24H30O12 50916591) -118 5331662[M+Na]+,5091659[M-H]-,3470936[M-
H-glucosyl]-,3290949[M-H-glucosyl-H2O]-,1830714
[harpagideHglucosyl-H2O]-,1630420[courmaricacid-
H]-
8Ocourmaroylharpagide[15]
P4553440C32H40O17 69521901) -043 6952190[M-H]-,5331622[M-H-glucosyl]-,3330949
[M-H-glucosyl-catalpol]-,1630414[courmaricacid-
H]-,1449913[courmaroyl-H]-
scrophulosideA2[32]
P4653765C32H40O17 69521951) 029 6952195[M-H]-,5331667[M-H-glucosyl]-,3331035
[M-H-glucosyl-catalpol]-,1450289[courmaroyl-H]-
scrophulosideA2isomer
P4753823C25H32O13 53917611) -167 5631732[M+Na]+,5391761[M-H]-,3451247[M-
H-feruloyl-H2O]-[harpagideH-H2O]-,1930518[ferulic
acid-H]-,1830714[harpagideHglucosyl-H2O]-,1750458
[feruloyl-H]-
6″Oferuloylharpagide[31]
P4853998C30H38O15 63721271) -173 6372127[M-H]-,4611601[M-H-cinnamoylCH2]-,
3151036[M-H-cinnamoylrhamnosylCH2]-
cistanosideCisomer
P4954057C30H40O16 7012271 -385 6792184[M+Na]+,7012271[M+HCOO]-,6552213
[M-H]-,5071651[M-H-cinnamoyl-H2O]-,3451165
[M-H-cinnamoyl-H2Oglucosyl]-,[harpagideH-H2O]-
6OαDgalactopyranosyl
harpagoside[15]
·1621·
2016
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}
Vol41,No.7 April,2016
,*
1
NotR/min ïó [M+HCOO]-/m/zÄÔ/ppm +æ-ï/m/z _V®¼
P5054557C30H40O16 7012317 271 7012317[M+HCOO]-,6552191[M-H]-,5071663[M-
H-cinnamoyl-H2O]-
6OαDgalactopyranosyl
harpagosideisomer
P5155223C38H50O20 8712848 -333 8492618[M+Na]+,8712848[M+HCOO]-,8252728
[M-H]-,7832651[M-H-acetyl]-,7652528[M-H-ace
tyl-H2O]-,6492128[M-H-feruloyl]-,6072319[M-H-
feruloylacetyl]-,5892035[M-H-feruloylacetyl-H2O]-,
4611553[M-H-feruloylacetylrhamnosyl]-,4431438[M-
H-feruloylacetylrhamnosyl-H2O]-,3291247[M-H-feru
loylacetylrhamnosylarabinosyl]-
acetylangorosideC
P5256282C31H40O15 6972365 229 6752321[M+Na]+,6972365[M+HCOO]-,6512288
[M-H]-,5051616[M-H-rhamnosyl]-,4751781[M-H-
feruloyl]-,4571662[M-H-feruloyl-H2O]-,3291171[M-
H-feruloylrhamnosyl]-
cistanosideD[15]
P5357828C24H30O11 5391745 -464 5171632[M+Na]+,5391745[M+HCOO]-,4931693
[M-H]-,3451138[M-H-cinnamoyl-H2O]-,2010733[M-
H-cinnamoyl-H2Oglucosyl]-,1830726[M-H-cinnamoylglu
cosyl2H2O]-,1790765[glucose-H]-,1650540[M-H-cin
namoylglucosyl3H2O]-,1610583[glucosyl-H]-
harpagosideisomer[36]
P5458403C25H32O12 5691865 -193 5471826[M+Na]+,5691865[M+HCOO]-,5231836
[M-H]-,3451132[M-H-methoxycinnamoyl-H2O]-
8Omethoxycinnamoyl
harpagideisomer
P5558878C30H40O16 7012284 -200 7012284[M+HCOO]-,6792350[M+Na]+,6552165
[M-H]-,5071682[M-H-cinnamoyl-H2O]-,3451175
[M-H-cinnamoyl-H2Oglucosyl]-,[harpagideH-H2O]-
6OαDgalactopyranosyl
harpagosideisomer
P5659387C31H40O15 6972377 402 6972377[M+HCOO]-,6512279[M-H]-,4731681[M-
H-methoxylcinnamoyl-H2O]-,3271063[M-H-methoxylcin
namoyl-H2Orhamnosyl]-[aucubinH-H2O]-
undulosideⅢ[37]
P5760853C30H40O16 7012277 -299 6792027[M+Na]+,7012277[M+HCOO]-,6552208
[M-H]-,5071671[M-H-cinnamoyl-H2O]-,3411092
[2glucosylH+H2O]-,3231031[2glucosyl-H]-,1790702
[glucose-H]-
6″OαDgalactopyrano
sylharpagoside[38]
P5861845C24H30O11 5391769 -019 5171644[M+Na]+,5391769[M+HCOO]-,4931712
[M-H]-,3451148[M-H-cinnamoyl-H2O]-,1830971
[M-H-cinnamoyl-H2Oglucosyl]-,1650599[M-H-cin
namoyl2H2Oglucosyl]-,1610571[glucosyl-H]-
harpagoside[15]
P5964693C25H32O12 5691844 -562 5471735[M+Na]+,5691844[M+HCOO]-,5231772
[M-H]-,3451138[M-H-methoxylcinnamoyl-H2O]-
1790503[glucose-H]-,1650586[M-H-methoxylcinnamoyl
2H2Oglucosyl]-
8Omethoxycinnamoyl
harpagide[15]
P6070110C33H42O17 7552370 -450 7552370[M+HCOO]-,7092307[M-H]-,6491994[M-
H-acetyl-H2O]-,5471845[M-H-glucosyl]-,5171683
[M-H-glucosyl-CH2O]-
scrophulosideA5[32]
P6172058C35H44O17 73525501) 598 7592325[M+Na]+,7352550[M-H]-,6932347[M-
H-acetyl]-,6512325[M-H-2acetyl]-,5051685[M-H-
2acetyl-rhamnosyl]-,3291179[M-H-2acetyl-rhamnosyl
feruloyl]-
diacetylmartynoside[39]
P6278758C43H50O19 9152879 -535 9152879[M+HCOO]-,8692947[M-H]-,7072281[M-
H-glucosyl]-,6472078[M-H-glucosyl-acetyl-H2O]-,
5931957[M-H-acetyl-H2Omethoxylcinnamoyl-H2O-
C3H4O]-
scrophulosideA4[40]
P6379458C42H48O18 8852795 -316 8852795[M+HCOO]-,8392803[M-H]-,6772158[M-
H-glucosyl]-,6171974[M-H-glucosyl-acetyl-H2O]-,
5631883[M-H-acetyl-H2Omethoxylcinnamoyl-H2O-
C3H4O]-
scrophulosideB4[41]
·2621·
I:è
:
GÝ_±
HPLCESIITTOFMS
à
,*
1
NotR/min ïó [M+HCOO]-/m/zÄÔ/ppm +æ-ï/m/z _V®¼
P6490817C20H28O2 29920011) -535 3012119[M+H]+,2992001[M-H]-,2271082[M-H-
C4H8O]-
sugiol[40]
å
:1)
|_V±Èïï
m/z[M-H]-。
©Hï
,
ì
20
MÏQMBCèêÄ
P6,P12,P1417,P29,P32,P39,P40,P44,P47,P49,
P50,P5355,P5758,P59
ÖnD÷7à
;
Ó$
P6
(dihydroharpagide),P15(6Oβglucosylharpagide)
¬
P12(6′Oβglucosylharpagide)ÊÓ¦Õ÷°
(P16
¬
P17)
GÝ$HºkÚ
。
P6
±÷îâ
:
¿ZïPó@[^Þç$~
dÈïï
m/z4111490[M+HCOO]-
¬
m/z3651440[M -H]-,
k á Ó ï ó
C15H26O10,káÄÔ-438。^Þç$M]m/
z3471288[M-H2O-H]
-,2030935[M-glucosyl
-H]-,1790567,1610481
èæ-ï
。
Ø>a
÷=>¬Ý¦^=>[á|_V¯nê±Á
rã
dihydroharpagide[18]。
P12[20],P15[21],P16,P17
±÷îâ
:
¿Z
ïPó@[^Þç$M]
P12
¬
P15
±Èïï
`
m/z5711881[M+HCOO]-
¬
m/z
5711885[M +HCOO]-,
k á Ó ï ó
C21H34O15,káÄÔ`018,088,àïü
¦Õ÷°
。
Ó$
P15
ZïPó@^ÞçL/
æ-
m/z5251825,3230938,2010740,
1830714,1790593。
Ó$
m/z2010781
[M-
2glucosyl-H]-,m/z1830714
[M -H -
2glucosyl-H2O]
-,
a÷
2
æ-ïu¯nê
ê ~ ± + æ - ï
,m/z323093 0
[2glucosyl-H]-,m/z1790593[glucose-H]-,
à
ï[á
P15
÷
harpagide
ê~÷Áz
2
Á
±·¸£
,
^[á|_V
6′Oβglu
cosylharpagide[21]。
§
P12
±^ÞçL/æ-Ñ
P15
,
}ÉB
m/z3230930
æ-ï
,
àï
[á|_V÷$±
2
ï·¸£¥6zÁ
,
^[á|_V
6Oβglucosylharp
agide[20]。P16
¬
P17
¿ZïPó@[^Þç$
MaáäÓÈïï`
m/z5711869
[M+HCOO]-
¬
m/z5711862[M+HCOO]-,
Ý×=>káÓïóu
C21H34O15,^æ-
ïM]
m/z32309,
àïQ¸[áÓu
6′Oβ
glucosylharpagide(P12)
±¦Õ÷°
,
]q
2。
q
2
MÏQMBCèêÄÝ7
(
a
harpagide
¨
)
Fig2 MSfragmentationruleofcyclopentanetypeiridoidglycosides(egharpagide)
MBQMBCèêÄ
,
m¬£ê
ÝY±»ï
m/z18307[M-H]-,
Ó
+æ-ï
:m/z16506[M-H2O-H]
-
¬
m/z
13506[M-H2O-CH2O-H]
-,
]q
3。
©Hï
,
ì
10
MBQMBCèêÄ
P3P5,P7,
P8,P10,P11,P13,P21,P56
ÖnD÷7à
。
Ó$
·3621·
2016
y
4
z ³
41
ų
7
}
Vol41,No.7 April,2016
P4(6Oβglucosylaucubin)ÊÓ¦Õ÷°(P7¬
P10),P5(6′Oβglucosylaucubin)ÊÓ¦Õ÷°
(P8,P11,P13)、P21(6Omethylaucubin)
¬
P56(un
dulosideⅢ)GÝ$HºkÚ。
q
3
MBQMBCèêÄÝ7
(
a
aucubin
¨
)
Fig3 MSfragmentationruleofcyclopentenetypeiridoidglycosides(egaucubin)
P5,P8,P11,P13
÷±îâ
:
¿ZïPó@
[^Þç$M]
P5
±Èïï
m/z
5531761[M +HCOO]-,
k á Ó ï ó
C21H32O14,káÄÔ -235。ZïPó@^
ÞçL/æ-
m/z3230981,1830330,179056
3,1610463。
Ó$
m/z3230981
[2glucosyl-
H]-,m/z1830330
[M-H-2glucosyl]-,
Ñ
[aucubin-H-glucosyl]-
æ-[c
,m/z1790563
[glucose-H]-,m/z1610463
[glucosyl-
H]-。
Ø>a÷æ-ïvâ[á|_V$¿
aucubin
ê~Ê
2
Á·¸£÷-¨
,
V^
=>[á|_V
6′Oβglucosylaucubin[17]。
P8,P11,P13
¿ZïPó@[^Þç$M]ÓÈ
ïï`
m/z5531750[M+HCOO]-,
5531760[M +HCOO]-,5531749[M +
HCOO]-,
Ý×=>káÓïóu
C21H32O14,å^æ-ïÑ P5æ-ï[c,à
ï[áÓu
6′Oβglucosylaucubin(P5)±¦Õ
÷°
,
]q
3。
P21
÷±îâ
:
¿Zï[^Þç$M]È
ïï
m/z4051381[M+HCOO]-,
Ý
×Þç=>káÓïó
C16H24O9,káÄÔ
-518。
^ÞçL/æ-
m/z1970837,
1650488,1350489。
Ó$
m/z1970837[aucu
binglucosyl+CH2]
-
[M-H-glucosyl]-,m/z
1650488
[M-H-glucosyl-CH3OH]
-,m/z
1350489
[M -H -glucosyl-CH3OH -
HCHO]-。
Ø>÷gÞçæ-vâ[á|_V
$¿·¸£
、
t1¬(1÷-¨
,
V
^kÚ
,
[á|_V
6Omethylaucu
bin[2324]。
MtMÏQMBCèêÄ
,
m¬£ê
ÝY±»ï
m/z21307[M-H]-,
Ó
+æ-ï
m/z1950673[M-H2O-H]
-
¬
m/z1830677[M-CH2O-H]
-,
]q
4。
©Hï
,
ì
10
MtMÏQMBCèêÄ
P1,
P2,P1819,P27,P4546,P60,P62,P63
ÖnD÷
7à
。
Ó$
P19(3,4dihydromethylcatalpol)(
GÝ
Ç
),P27(premnacorymbosideB),P60(scrophulo
sideA5),P45(scrophulosideA2)ÊÓ¦Õ÷°
(P46)
uGÝ$HºkÚ
,P2(4hydroxy6O
methylcatalpol)
¥_V
。
P2
÷7à
:
¿ZïPó[^Þç$M]
ÓÈïï
m/z4391438[M+HCOO]-,
Ý×Þç=>káÓïó
C16H26O11,k
áÄÔ
-433。
ZïPó@^ÞçL/æ
-
m/z2310888,2130782,1950260,
1830616,1630452。
Ó $
m/z2130782,
1950260,1830616,1630452
u
6Ometh
ylcatalpol
±+æ-ï
。
|_VÑ
6Ometh
ylcatalpol(P18)
ïó
(C16H24O10)ñ H2O,
àï[á|_VÊ
6Omethylcatalpol
$üm
¢VÖ§Ï
,
¹
4hydroxy6Omethylcatalpol,
]q
4,5。
ïýð¿GÝ$m±[ ÕMBCèê
Ä
,P9(ningpogosideA)。
252
ÛêÄ
GÝ$ÛêÄL/
ëÉÊα,β¥m¬¼8¼(M=148)、K
¼
(M=194)、
©ª¼
(M=180)
¬?¼
(M=
164)
è
,
Ñ·¸£
(M=180)、
RD£
(M=164)
Ê
·4621·
I:è
:
GÝ_±
HPLCESIITTOFMS
à
q
4
MtMÏQMBCèêÄÝ7
(
a
6Omethylcatalpol
¨
)
Fig4 MSfragmentationruleofepoxycyclopentanetypeiridoidglycosides(eg6Omethylcatalpol)
q
5 4hydroxy6Omethylcatalpol
÷
Fig5 Structureof4hydroxy6Omethylcatalpol
K£
(M=150)
è÷Ûê
,
¦O£÷÷
OBm¨÷Á
。
ÛêÄ¿{±0
@
,
wmÂÛÄ÷U~$µV
,
.§VR
D£1
(146),
QYVK£1
(132),
]q
6。
Ø>a÷ÛêÄ^ÞçÝ7
,
¿GÝ$
ô
19
ÛêÄ
,
`
P20,P22,
P24,P26,P30,P31,P3338,P4143,P48,P51,
P52,P61。
Ó$
P26(6′Oferuloylsucrose),P37
(sibiriosideB),P61(diacetylmartynoside),P35(scro
phulosideB2)ÊÓ¦Õ÷°(P38)GÝ$Hº
kÚ
,P51(acetylangorosideC)
¥_V
。
P51
÷7à
:
¿ZïPó[^Þç$M]
ÓÈïï
m/z8712848[M+HCOO]-,
k
áÓïó
C38H50O20,káÄÔ -333。^
ÞçL/æ-
m/z7832651,7652528,
6492128,5892035,6072319,4611553,
3291247。
Ó $
m/z7832651,6492128,
5892035,6072319,4611553,3291247
u
angorosideC(P41)
±+æ-ï
;m/z7832651
[M-H-acetyl]-
¬
m/z7652528
[M-H-
acetyl-H2O]
-,
àï[á|_V-BÑ
angoro
sideC
±÷¬åBm 1
,
[á|_V
angorosideC
±m _ã
acetylangorosideC。
¦O
M]æ-ï
m/z6492128[M-H-feruloyl]-,
m/z4611553[M-H-feruloyl-acetylrhamnosyl]-
m/z6492128
$µV
188(
m RD£1
)
<
ä±æ-ï
,
àï[ám _m¿RD£1÷
,
¦Ùäþí8
,
[ám 1ÁzíLRD£
÷$
2
p
3
í±1
,
[á÷]q
7。
q
6
ÛêÄÝ7
(
a
angorosideC
¨
)
Fig6 MSfragmentationruleofphenylpropanoidglycosides(egangorosideC)
·5621·
2016
y
4
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41
ų
7
}
Vol41,No.7 April,2016
q
7 acetylangorosideC
M{±÷
Fig7 ProbablestructureofacetylangorosideC
253
<`
MBCèê¬Û
êÄð
,
ÁôD
2
m¨êÄ
P23(deferuloy
langorosideC)
¬
P28(phenethylβprimeveroside)、1
¨êÄ
P25(phenylmethyl6OαLarabinopy
ranosylβDglucopyranoside)¬ 1èÄ_V
P64(sugiol)。
Ó$
P25
¬
P28
GÝ$HºkÚ
。
P25
¬
P28
±÷7à
:
¿ZïPó[^Þ
ç$M]
P28
Èïï
m/z4611660[M+
HCOO]-,
Ý×Þç=>káÓïó
C19H28O10,káÄÔ -108。ZïPó^Þ
ç$L/æ-
m/z1490397[arabinose-H]-,
m/z4151557[M-H]-
$µV
266(
m¨¬
·¸£1Á±æ-ï
),
Scifinder
=>
¬^kÚ[á
P28
phenethylβpri
meveroside[30]。
¿ZïPó[^Þç$M]
P25
Èïï
m/z4011447[M-H]-,
Ý×
Þç=>káÓïó
C18H26O10,káÄÔ
-150ppm。
ZïPó^ÞçL/æ-
m/z
2691014,161052 3,145105 4;
Ó $
m/z
2691014
[M-H-arabinosyl]-,m/z1610523
[glucosyl-H]-,
[á
P25
$çëBK£¬
·¸£÷-¨
;
Œ
P25
Ñ
P28
ïó
(C19H28
O10)ÔCH2;àï[áP25ÑP28¦Å,
Scifinder
=>¬^kÚ[á|_V
phenylmethyl 6OαLarabinopyranosylβDglucopyr
anoside[27]。
26
GÝ$HºkÚ±_V¿$±
¿GÝ$ô±
64
_V
,
2
¥_V
ð
,17
GÝ$HºkÚ
。
@¸^
,
ì
17
_V¿$±ÖnDu
,
]*
2,
Ó$
13
_V¿GÝ&Óâ$XkÚ¸
,
Óá
4
_V$
P12(6Oβglucosylharpagide)¬ P15
(6′Oβglucosylharpagide)¿_&,P25(phe
nylmethyl6OαLarabinopyranosylβDglucopyrano
side)
¿©&
,P26(6′Oferuloylsucrose)
¿
Xí&$
,
|L&uGÝ&±Î²
[43],
]*
2。
*
2
GÝ$Hºô±_V¿$±
Table2 Distributionofthefirstidentifiedconstituentsfrom
ScropharariaeRadixinplants
No
_V
P4 6Oβglucosylaucubin
GÝ&[tÐÇ
[16]
P5 6′Oβglucosylaucubin
GÝ&¡Ç
[17]
P6 dihydroharpagide
GÝ&GÝÇ
[18]
P12 6Oβglucosylharpagide
_&
[20]
P15 6′Oβglucosylharpagide
_&
[21]
P19 3,4dihydromethylcatalpol
GÝ&GÝÇ
[22]
P21 6Omethylaucubin
GÝ&FÍÇ
[2324]
P25 phenylmethyl6OαLarabinopyranosyl
βDglucopyranoside
©&
[27]
P26 6′Oferuloylsucrose
Xí&
[28]
P27 premnacorymbosideB
GÝ&GÝÇ
[29]
P28 phenethylβprimeveroside
GÝ&FÀÇ
[30]
P35 scrophulosideB1 GÝ&GÝÇ[32]
P70 sibiriosideB
GÝ&ý¢Ç
[34]
P37 scrophulosideA2 GÝ&GÝÇ[32]
P56 undulosideⅢ
GÝ&[tÐÇ
[37]
P60 scrophulosideA5 GÝ&GÝÇ[32]
P61 diacetylmartynoside
GÝ&GÝÇ
[39]
3
sÑÚs
9«¬p
HPLCESIITTOFMS
()ìGÝ
_Önà
,
@¸[^Þç$Èïï
¬^Þç$±æ-ïvâ
,
¬V^=>
ôGÝ_
64
,
RSÛêÄ
19
、
M
·6621·
I:è
:
GÝ_±
HPLCESIITTOFMS
à
BCèêÄ
41
、

4
。
GÝ$HºkÚ±
_V
19
;
GÝ&$HºkÚ_V
6
,
`
P2(4hydroxy6Omethylcatalpol),P12(6O
βglucosylharpagide), P15 (6′Oβglucosylharp
agide),P25(phenylmethyl6OαLarabinopyranosyl
βDglucopyranoside),P26(6′Oferuloylsucrose),
P51(acetylangorosideC),
Ó$
P2
¬
P51
¥_
V
。
GÝL/ÛêĬMBCèêÄ
,
9^<â±
19
ÛêÄ_V÷
,
¦Å
,
|ı÷ë¼
(
8¼
、
K¼¬©ª¼è
)
Ñ·¸£
、
RD£p£èb
Vê
(
£
),
Ó$
8
_VYʦÕ÷°
。
¿<â±
41
MBCèêÄ_V$
,
MÏQM
BCèêÄ
20
,
u
harpagide
Ѽp·¸
£bV§
,
Ó$
15
_VYʦÕ÷°
;
M
BQMBCèêÄ
10
,
u
aucubin
Ѽ
¬·¸£bV§
,
Ó$
7
_VYʦÕ÷
°
;
MtMÏQMBCèêÄ
10
,
u
6O
methylcatalpol
Ѽ
、
·¸£pm¨èbV§
,
Ó$
2
_VߦÕ÷°
。
«¬æ*
úGÝ$ëB]±÷±_
,
p¦
Õ÷°
,
p¦Å
,
p»÷Áz·¸£=À
¬íL¥¦
;
àïGÝ¿m,ÉO
,
÷
±_VBM{+ãÂhÅ0
[44]。
@¸
HPLCESIITTOFMS
()DöÈîFì
GÝ$æ-_ÖnÅÆà
,
jwDGݱ
_vâ
,
Gݱ,ÉÞ1i«¬#GD
·>
。
[
q=
]
[1]
$%,
.
[1
[S].2010:108.
[2]
B4Ø
.
¥/$,.
[M].
23
:
_g)dP«
,2002:
336.
[3]
Ô?
,
¦þ
,
~?
.
Gݱ_«¬
[J].
«
¬
,2008,28(2):254.
[4]
DúA
,
¦Ò÷
,
Ý^£
,
è
.
GÝ$±Û
[J].
$
,
,1999,30(7):487.
[5]
XÆ÷
,
DAú
,
(
,
è
.
GÝ#Ö±ô0¬ôtðµ
[J].
³,1999(9):614.
[6]
5ú
,
DÀ
,
Dð|
,
è
.
GÝᤱ,É«¬
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