全 文 :2016
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Vol41,No.9 May,2016
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、HPLC
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NMR
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1~7
¡^Ó
tricin4′O[threoβguaiacyl(7″Omethyl)glyceryl]ether(1),
tricin4′O[erythroβguaiacyl(7″Omethyl)glyceryl]ether(2),5′methoxyhydnocarpinD(3),palstatin(4),(8R,7′S,8′R)5,
5′dimethoxy7oxolariciresinol9′ODxylopyranoside(5),9ODglucopyranoside(6),(-)haplomyrtoside(7)。
_ª¨
1,3~5
¼Ba,IÎqï
(H5N1)
·!
,IC50¡^Ó065,021,032#056μmol·L
-1,SI(SI=TC50/IC50)¡^Ó125,35,
106,78。
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BioactivelignansfromSilybummarianum
ZHANGYan,PENGYubo,CHENXiaozhong,SONGLiyan
(JiamusicolegeofHeilongjiangUniversityofChineseMedicine,Jiamusi154007,China)
[Abstract] TheseedsofSilybummarianumwereextractedbyhotwater,andtheextractwasisolatedbyD101macroporousresin,
MCIresin,MPLC,HPLC,etalAsaresult,7compoundsincludingtricin4′O[threoβguaiacyl(7″Omethyl)glyceryl]ether
(1),tricin4′O[erythroβguaiacyl(7″Omethyl)glyceryl]ether(2),5′methoxyhydnocarpinD(3),palstatin(4),(8R,7′S,8′
R)5,5′dimethoxy7oxolariciresinol9′ODxylopyranoside(5),9ODglucopyranoside(6),and(-)haplomyrtoside(7)wereiso
latedandidentifiedforthefirsttimeCompounds1,3,4,and5exhibitedactivityagainstinfluenzaA(H5N1)withIC50valueof065,
021,032,and056μmol·L-1,respectivelyCompounds1,2,6,and7exhibitedcytotoxityagainstHepG2withIC50valueof
035,025,053,066μmol·L-1,respectively
[Keywords] Silybummarianum;lignan;antiinfluenzavirusactivity;cytotoxity
doi:10.4268/cjcmm20160915
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SPD
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mm,10μm)í7ç;Xm MPLC:BiotageDE
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5mL·min-1),
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W_ª¨
7(10mg,tR=37min)。
3
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1
öíÜ
,
Ï
-ÜæÚ!õö
。
1HNMR(CDCl3,500MHz)δ:660(1H,s,H3),
615(1H,s,H6),640(1H,s,H8),708(1H,s,H
2′),708(1H,s,H6′),385(2H,s,H3′,5′),692
(1H,brs,H2″),677(1H,brs,H5″),681(1H,
m,H6″),447(1H,d,J=60,H7″),445(1H,m,
H8″),392(1H,dd,J=120,44Hz,H9″a),375
(1H,dd,J=120,33Hz,H9″b),385(3H,s,3″
OCH3),386(3H,s,7″OCH3);
13CNMR(CDCl3,
125MHz)δ:1660(C2),1055(C3),1835(C4),
1535(C5),1005(C6),1671(C7),953(C8),
1595(C9),1057(C10),1278(C1′),1048(C
2′),1547(C3′),1405(C4′),1545(C5′),
1048(C6′),555(C3″
#
H5″OCH3),1313(C
1″),1123(C2″),1489(C3″),1481(C4″),
1157(C5″),1223(C6″),839(C7″),869(C
8″),618(C9″),559(3″OCH3),558(7″OCH3)。
ÂfÃ7=òÖ^»
[3]
k{_ª¨[þ
,
£]
`Ú_ª¨Ó
tricin4′O[threoβguaiacyl(7″O
methyl)glyceryl]ether。
_ª¨
2
öíÜ
,
Ï
-ÜæÚ!õö
。
1HNMR(CDCl3,500MHz)δ:661(1H,s,H3),
616(1H,s,H6),642(1H,s,H8),709(1H,s,H
2′),709(1H,s,H6′),385(2H,s,H3′,5′),695
(1H,brs,H2″),678(1H,brs,H5″),682(1H,
m,H6″),490(1H,d,J=45Hz,H7″),446(1H,
m,H8″),395(1H,dd,J=120,44Hz,H9″a),
376(1H,dd,J=120,33Hz,H9″b),387(3H,
s,3″OCH3),388(3H,s,7″OCH3);
13CNMR
(CDCl3,125MHz)δ:1663(C2),1056(C3),
1837(C4),1539(C5),1006(C6),1671(C
7),955(C8),1597(C9),1059(C10),1272
(C1′),1049(C2′),1549(C3′),1407(C4′),
1546(C5′),1049(C6′),556(C3″
#
H5″
OCH3),1315(C1″),1125(C2″),1491(C3″),
1482(C4″),1158(C5″),1206(C6″),748(C
7″),869(C8″),619(C9″),556(3″OCH3),557
(7″OCH3)。ÂfÂfÃ7=òÖ^»[3]k{
_ª¨[þ
,
£]`Ú_ª¨Ó
tricin4′O[erythro
βguaiacyl(7″Omethyl)glyceryl]ether。
_ª¨
3
öíÜ
,
Ï
-ÜæÚ!õö
。
1HNMR(CDCl3,500MHz)δ:705(1H,d,J=20
Hz,H2″),685(1H,d,J=81Hz,H5″),689(1H,
dd,J=91,20Hz,H6″),379(3H,s,C3″OMe),
395(3H,s,C5″OMe),678(1H,s,H3),620
(1H,d,J=21Hz,H6),655(1H,d,J=23Hz,H
8),363(1H,m,H11a),339(1H,m,H11b),426
·5561·
2016
y
5
z À
41
ÁÀ
9
}
Vol41,No.9 May,2016
(1H,m,H12),499(1H,d,J=91Hz,H13),729
(1H,d,J=21Hz,H2′),735(1H,d,J=21Hz,
H6′);13CNMR(CDCl3,125MHz)δ:1643(C2),
1039(C3),1818(C4),1234(C5),1258(C
6),1629(C7),942(C8),1573(C9),1036(C
10),618(C11),786(C12),759(C13),568
(COMe),1227(C1′),1082(C2′),442(C3′),
1366(C4′),1482(C5′),1029(C6′),1278(C
1″),1175(C2″),479(C3″),1476(C4″),1154
(C5″),1206(C6″)。
ÂfÂfÃ7=òÖ^»
[4]
k{_ª¨[þ
,
£]`Ú_ª¨Ó
5′me
thoxyhydnocarpinD。
_ª¨
4
öíÜ
,
Ï
-ÜæÚ!õö
。
1HNMR(CDCl3,500MHz)δ:698(1H,s,H3),
617(1H,d,J=25Hz,H6),650(1H,d,J=25
Hz,H8),336(1H,dd,J=110,40Hz,H11a),
360(1H,J=d,110Hz,H11b),425(1H,ddd,J=
110,80,10Hz,H12),493(1H,d,J=80Hz,
H13),730(1H,d,J=35Hz,H2′),390(3H,s,
5′OCH3),675(2H,s,H2″,6″),375(2H,s,H3″,
5″);13CNMR(CDCl3,125MHz)δ:1630(C2),
1045(C3),1819(C4),1616(C5),995(C6),
1648(C7),945(C8),1578(C9),1039(C
10),600(C11),785(C12),766(C13),1222
(C1′),1083(C2′),1445(C3′),1368(C4′),
1490(C5′),1029(C6′),556(5′OCH3),1263
(C1″),1053(C2″,6″),1478(C3″,5″),1361(C
4″),560(C3″,5″)。
ÂfÂfÃ7=òÖ^»
[4]
k{_ª¨[þ
,
£]`Ú_ª¨Ó
palstatin。
_ª¨
5
öíÜ
。1HNMR(CDCl3,500
MHz)δ:773(1H,brs,H2),775(1H,brs,H6),
485(1H,m,H8),468(1H,dd,J=110,80Hz,
H9a),440(1H,t,J=80Hz,H9b),385(3H,s,
OCH3),728(1H,brs,H2′),728(1H,brs,H
6′),539(1H,d,J=85Hz,H7′),316(1H,m,H
8′),448(1H,dd,J=115,30Hz,H9′a),395
(1H,dd,J=115,45Hz,H9′b),382(3H,s,
OCH3),478(1H,d,J=82Hz,H1″),406(1H,t,
J=85Hz,H2″),413(1H,t,J=85Hz,H3″),
406(1H,m,H4″),430(1H,dd,J=110,50Hz,
H5″a),368(1H,t,J=110Hz,H5″b);13CNMR
(CDCl3,125MHz)δ:1279(C1),1079(C2),
1486(C3),1437(C4),1489(C5),1084(C
6),1985(C7),492(C8),706(C9),565
(OCH3),1312(C1′),1052(C2′),1495(C3′),
1378(C4′),1495(C5′),1053(C6′),845(C
7′),535(C8′),765(C9′),566(OCH3),1057
(C1″),747(C2″),788(C3″),711(C4″),673
(C5″)。
ÂfÃ7=òÖ^»
[5]
k{_ª¨[
þ
,
£]`Ú_ª¨Ó
(8R,7′S,8′R)5,5′dime
thoxy7oxolariciresinol9′ODxylopyranoside。
_ª¨
6
öíÜ
。1HNMR(CDCl3,500
MHz)δ:695(1H,d,J=20Hz,H2),670(1H,d,
J=80Hz,H5),780(1H,dd,J=80,20Hz,H
6),555(1H,d,J=65Hz,H7),356(1H,m,H
8),401(1H,m,H9a),382(1H,m,H9b),377
(3H,s,OCH3),675(1H,brs,H2′),668(1H,
brs,H6′),257(1H,brt,J=80Hz,H7′),177
(1H,m,H8′),352(2H,t,J=65Hz,H9′),380
(3H,s,OCH3),430(1H,d,J=76Hz,H1″),328
(1H,m,H2″),327(1H,m,H3″),323(1H,m,H
4″),332(1H,m,H5″),368(1H,t,J=110Hz,H
6″a),358(1H,m,H6″b);13CNMR(CDCl3,125
MHz)δ:1346(C1),1109(C2),1495(C3),
1477(C4),1169(C5),1195(C6),892(C7),
533(C8),727(C9),567(OCH3),1368(C
1′),1182(C2′),1457(C3′),1478(C4′),
1295(C5′),1143(C6′),330(C7′),358(C
8′),623(C9′),566(OCH3),1046(C1″),756
(C2″),786(C3″),717(C4″),689(C5″),629
(C5″)。
ÂfÃ7=òÖ^»
[5]
k{_ª¨[
þ
,
£]`Ú_ª¨Ó
9ODglucopyranoside。
_ª¨
7
öíÜ
。1HNMR(CDCl3,500
MHz)δ:552(1H,d,J=35Hz,Hl″),455(1H,d,
J=35Hz,H2″),395(1H,d,J=100Hz,H4″α),
445(1H,d,J=100Hz,H4″β),372(1H,d,
J=115Hz,H5″α),375(1H,d,J=115Hz,
H5″β),405(3H,s,OCH3),770(1H,s,H5),705
(1H,s,H8),556(1H,d,J=140Hz,H10),677
(1H,d,J=18 Hz,H2′),603(2H,s,3′,
4′OCH2O),694(1H,d,J=78Hz,H5′),674
(1H,dd,J=78,18Hz,H6′);13CNMR(CDCl3,
125MHz)δ:1365(C1),1300(C2),1195(C3),
·6561·
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JPQ$ARSmÝ©¨·!
1464(C4),1276(C4a),1016(C5),1527(C
6),1497(C7),1105(C8),1323(C8a),1726
(C9),687(C10),1025(OCH2O),1302(C1′),
1115(C2′),1488(C3′,C4′),1089(C5′),
1246(C6′),563(OCH3),1126(Cl″),788(C
2″),803(C3″),759(C4″),643(C5″)。
ÂfÂ
fÃ7=òÖ^»
[6]
k{_ª¨õ[þ
,
£
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(-)haplomyrtoside。
4
·!ºò
,IÎqï
(A/Hanfang/1/47,H5N1)
òoú
û
:
¤
5% CO2,37℃÷øS,,MDCKlã±ê
96
YÓ®8
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ÿï
MDCK
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ï
1×10-5,
©
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5% CO2,37℃÷øSKÓ,¼qïÏÒq
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m
35
h),
stx
a,IÎqï%=M^
(IC50)。
á ¡_ª¨
1,3,4,5
¼Ba,IÎqï
(H5N1)
·!
,IC50¡^Ó 065,021,032,056
μmol·L-1,SI¡^Ó125,35,106,78;Ú!Ï
,
(
.E
)IC50Ó 28μmol·L
-1,SI
Ó
11501。
lï·!òoúû
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10%
:
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/mL
lX>
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37℃,5% CO2Z8Ó24h。Yò
aï3C
^
(01,1,10μmol·L-1),|C^ïÞ3Cþ
nY
,
¤
37℃,5% CO2Z8Ó4d。Í:Ó
>ÿ
,
|Y2ù
MTT
Î>
(04g·L-1,RPMI1640
Ö
)100μL,37℃ [4h。Íf>,|Y2ù
DMSO150μL,¯ 550mëߤ¶ºÃÕ540nm,
ÂüÃÕ
405nm
Sº`
A。
á ¡_ª¨
1,2,
6,7
¼B,B¥l
(HepG2)
·!
,IC50
¡^Ó
035,025,053,066μmol·L-1,Ú!Ï
,ëc
IC50Ó0012μmol·L
-1。
[
uv=w
]
[1]
d/
.
$L,B8«¡}_Ö,}È!
[M].
Õv
:
á9&
()Öm÷
,1982:266.
[2]
ß8%
,
6
,
!ü
,
É
.
JPQåB$¼B,-_·!(ã
§_«¡
[J].
I*A,&
,2015,38(4):35.
[3] BaiN,HeK,RolerM,etal.Flavonolignansandotherconstitu
entsfromLepidiummeyeniwithactivitiesinantiinflammatoryand
humancancercellines[J].JAgricFoodChem,2015,63(9):
2458.
[4] StermitzFR,TawaraMatsudaJ,LorenzP,etal.5′Methoxyhyd
nocarpainDandpheophorbideA:berberisspeciescomponentsthat
potentiateberberinegrowthinhibitionofresistantstaphylococcus
aureus[J].JNatProd,2000,63(8):1146.
[5] SuDM,TangW Z,HuYC,etal.Lignanglycosidesfrom
Neoalsomitraintegrifoliola[J].JNatProd,2008,71(5):784.
[6] GzlerB,GzlerT,HesseM,etal.MinorlignansfromHaplo
phylumcappadocicum[J].Phytochemistry,1996,42(3):689.
[
xy-0
]
·7561·