全 文 ：t , J = 713H z, H 24) , 3169 (1H , d, J = 1115H z, H 21′
a) , 3174 (1H , d, J = 1115 H z, H 21′b) , 3190 (1H , d,
J = 918 H z, H 23′) , 3178 (1H , dd, J = 918, 315 H z,
H 24′) , 3182- 3184 (1H , m , H 25′) , 3165 (1H , dd, J =
1213, 210 H z, H 26′a) , 3175 (1H , dd, J = 1213, 115
H z, H 26′b)。13C2NM R谱数据见表 1。将化合物ÒÊ
的13C2NM R 谱数据与文献[8 ]报道的正丁基O 2Β2D 2
吡喃果糖苷的数据相比较, 两者基本一致。因此鉴定
化合物ÒÊ 为正丁基O 2Β2D 2吡喃果糖苷。此外根据
HM Q C谱和DQ F 2CO SY 谱准确地归属了Β2D 2吡
表 1　化合物Ò～ ÒÊ 的碳谱数据
Table 1　13C-NM R data of compounds Ò - ÒÊ
碳位 Ò Ó ÒÊ
苷元
1 　　　6210 　　　6212 　　　6117
2 3314 3314 3313
3 2014 2012 2015
4 1412 1413 1413
果糖
1′ 6117 6211 6316
2′ 10818 10512 10116
3′ 8313 7816 7018
4′ 7816 7714 7116
5′ 8410 8314 7111
6′ 6217 6510 6512
喃果糖的碳、氢信号, 纠正了文献报道的 Β2D 2吡喃
果糖部分 1′, 3′, 4′, 5′, 6′位碳信号归属的错误。
References:
[ 1 ]　Sash ida Y, O gaw a K, Kitada M , et a l1 N ew aurone
gluco sides and phenylp ropano id gluco sides from B id ens p ilosa
[J ]1 Chem P harm B u ll, 1991, 39 (3) : 70927111
[ 2 ]　M arkham K R , T ernaiB, Stan ley R , et a l1 Carbon213 NM R
studies of flavono ids2Ë natu rally occurring flavono id
glyco sides and their acylated derivatives [J ]1 T etrahed ron ,
1978, 34 (5) : 1389213971
[ 3 ]　W ang J P, H ui Q S, Q in D Y, et a l1 Chem ical constituen t
studies on B id ens bip inna ta É [J ]1 Ch in T rad it H erb D rug s
(中草药) , 1992, 23 (5) : 22922311
[ 4 ]　Gong Y H 1 13C2N M R Chem ica l S h if t of N a tu ra l O rg an ic
Comp ound s (天然有机化合物13C2NM R核磁共振化学位移)
[M ]1 Kunm ing: Yunnan Science and T echno logy Pub lish ing
House, 19861
[ 5 ]　M izu tan i K, Yuda M , T anaka O , et a l1 Chem ical studies on
Ch inese tradit ional m edicine, D angshen É 1 Iso lation of (Z ) 2
32and (E ) 222hexenyl Β2D 2gluco sides [J ]1 Chem P harm B u ll,
1988, 36 (7) : 2689226901
[ 6 ]　Kitajim a J , Ish ikaw a T , T anaka Y1 W ater2so lub le
constituen ts of fennel alkyl glyco sides [J ]1 Chem P harm
B u ll, 1998, 46 (10) : 1643216461
[ 7 ]　Chen Y G, Zhu Y, W ei J X, et a l1 Chem ical constituen t
studies on Cod onop sis p ilosu la [J ]1 Ch ina J Ch in M ater M ed
(中国中药杂志) , 1995, 20 (10) : 61126121
[ 8 ]　Hou X Y, Chen F Q 1 Studies on chem ical constituen ts of
L ilium brow n ii [J ]1 A cta P harm S in (药学学报) , 1998, 33
(12) : 92329261
Chem ica l com position of essen tia l o il in cultured Cordycep s s inens is
HU Zheng1, 2, YE M ao2qing1, YU H uai2dong1, FAN Y ing1, L I H ua2p ing1, ZOU Guo2lin1Ξ
(11 Co llege of L ife Sciences, W uhan U niversity, W uhan 430072, Ch ina; 21 D epartm ent of B io logical
Engineering, H ubei Po lytechn ic U niversity, W uhan 430068, Ch ina)
冬虫夏草挥发油成分分析
胡　征1, 2, 叶茂青1, 于怀东1, 范　莹1, 李华屏1, 邹国林1
(11 武汉大学生命科学学院, 武汉　430072; 　21 湖北工学院 生物工程系, 武汉　430068)
1　 In troduction
Cordy cep s sinensis (Berk1) Sacc1 is a parasit ic
fungu s on the larvae of L eid op tera1 T he fru it ing
bodies of C 1 sinensis have been u sed as food and
ton ic herbal m edicine fo r a variety of d ieases fo r
cen tu ries, nam ed Dong2Chong2X ia2Cao in
m andarin1 C 1 sinensis ex tract has been u sed fo r the
trea tm en t of hyperg lycem ia, hyperlip idem ia,
resp ira to ry and liver d iseases, renal dysfunct ion,
renal fa ilu re [1 ] , and its an t iox idan t p ropert ies have
also been w idely u sed1 T he ex tract of C 1 sinensis
has been show n to increase the level of h igh2energy
pho sphates in mou se liver [2 ] and stero idogenesis[3 ] ,
superox ide dism u tase act ivity in red b lood cell
(RBC) , and to decrease p lasm a m alonedia ldehyde
and oxygen free radica ls in o lder pat ien ts1 R ecen t
·579·中草药　Ch inese T radit ional and H erbal D rugs　第 35 卷第 9 期 2004 年 9 月
Ξ 收稿日期: 2003212220
repo rts have show n C 1 sinensis ex tract can be
beneficia l to au to imm une diseases and has
an t itumo r p ropert ies[4～ 6 ] 1 How ever, lit t le is
know n abou t act ive ingredien ts of C 1 sinensis
ex tract o r its m echan ism of act ion on anyth ing of
the u ses described above1 Som e b ioact ive
con st ituen ts from Cordy cep s species have been
rep ro ted including co rdyce2p in [7, 8 ] , oph ico rd in and
one k ind of adeno sine derivat ives [9 ] w as found, bu t
there is no m uch at ten t ion devo ted to essen t ia l o il
of C 1 sinensis1
H erein the compo sit ion of the essen t ia l o il
from the m ycelia of cu ltu red C 1 sinensis has been
described, the analyt ic resu lts by m ean s of GC2M S
are repo rted in the fo llow ings1
2　M a ter ia ls and m ethods
211 　M ateria ls: C 1 sinensis (CCTCC A F99009 )
st ra in w as ob ta ined from Ch ina Cen ter fo r T ype
Cu ltu re Co llect ion (CCTCC) , W uhan U n iversity,
W uhan, Ch ina1 Carrier gases fo r GC2M S and all
chem icals w ere rou t inely u sed of the h ighest pu rity
grade1
212 　Cu ltu red of C 1 sinensis: CCTCC A F99009
w as first cu ltu red on po ta to dex tro se agar p la tes
fo r fou r days at 28 ℃1 T hen the starter cu ltu res
w ere tran sferred to nu trien t b ro th con ta in ing (gö
L ) : pep tone 10, g luco se 30, VB 1 0105, KH 2PO 4
1, M gSO 4 012, a t pH 610, on a ro tary shaker a t
120 röm in fo r fou r days at 28 ℃1 T he m ycelium of
C 1 sinensis w as harvested and then sto red at -
80 ℃1
213 　 Ex tract ion m ethods: T he m ycelium of C 1
sinensis w as co llected and fragm en ta ted by Son ic
D ism em b rato r in ice w ater1 Pu rif ied w ater, 250
mL w as added and sub jected to hydrodist illa t ion
fo r fou r hou rs to ex tract the essen t ia l o ils th rough
dist illa t ion appara tu s1 A nd ether w as the
ex tract ive so lven t1 T he essen t ia l o il decan ted from
dist illa t ion w ater w as trea ted w ith anhydrou s
sodium su lphate to m ake it mo istu re2free, ref ined,
and m easu red1 O il yield w as est im ated and the the
compo sit ion of o il w as analyzed by GC2M S1
Emp loying th is m ethod, 0135% of to ta l o il yield
w as recovered from the hydro so l1
T he hydro2dist illa t ion of the aeria l parts gave
tran sparen t yellow ish o il w ith an especia lly th ick
odo r1
214 　 A nalyt ic condit ion s of GC2M S: GC2M S
( T hermo F inn igon T race GC + T race M Sp lus,
cap illa ry DB 21M S system fit ted w ith a 30 m ×0125
mm ) 1 T emperatu re p rogramm e w as 20 ℃öm in
from 60 ℃ to 150 ℃, then 3 ℃öm in from 160 ℃
to 170 ℃ and 15 ℃öm in from 170 ℃ to 220 ℃,
last 8 ℃öm in from 220 ℃ to 260 ℃, and kep t 6
m in at 260 ℃1 H elium w as u sed as carrier gas a t a
f low of 1 mL öm in1 M ass spectra w ere reco rded
over 50- 450 am u w ith ion iza t ion energy 70 eV and
ion sou rce temperatu re 220 ℃1 T he N IST ’98
L ib raries database w as u sed1
3　Results and d iscussion
311 　 R esu lts: Straw yellow essen t ia l o il w ith
specia l odo r w as ex traced from C 1 sinensis by
steam dist illing in st rum en t, 0135% of to ta l o il
yield ( dry w eigh t ) w as recovered from the
hydro so l by th is m ethod1
T he chem ical compo sit ion s of the essen t ia l o il
of C 1 sinensis w ere analyzed by GC2M S1 T he resu lt
show ed that 72 peak s w ere separa ted and 41 of
them w ere iden t if ied1 T he m ain con ten ts of the
essen t ia l o il w ere 9, 122octadeceno ic acid, n2
hexadecano ic acid, o leic acid, 17à2
m ethyltesto sterone, and to luene1 It w as repo rted
fo r the first t im e that the essen t ia l o il yields w ere
est im ated and the essen t ia l o il compo sit ion of C 1
sinensis analyzed by GC2M S1 F rom the resu lts, the
au tho r can get the conclu sion that the con ten t of
essen t ia l o il of C 1 sinensis included p len ty of arom a
compounds, octadeceno ic acid, hexadecano ic acid,
and their grease ram ifica t ion w h ich had specia l
arom a1 T he essen t ia l o il of C 1 sinensis also
con ta ined lo ts of un satu ra ted fa t ty acid, stero l,
and dip lterpene compound, w h ich w o rked as the
h igh m edicine value of C 1 sinensis1
In herbalism , C 1 sinensis has been u sed fo r
renal dysfunct ion and renal fa ilu re, tha t
researchers con sidered rela ted to the stero l sex
ho rmone in C 1 sinensis1 In th is research, the
au tho r found the essen t ia l o il of C 1 sinensis
·679· 中草药　Ch inese T radit ional and H erbal D rugs　第 35 卷第 9 期 2004 年 9 月
con ta ined arom atic compound, d ip lterpene, and
stero l compound, w h ich m aybe the in term edia te
m etabo lite o r u lt im a m etabo lite of the stero l
m etabo lizing of C 1 sinensis1 R ecen t researches also
show ed the stero l m at ter of C 1 sinensis had
an t icancer act ivity [6 ]1
In the test, the vert icio l and som e structu re
analog in C 1 sinensis w ere first found1 V ert icio l w as a sub stance strongly resem b ling w ith calad iumalkali in st ructu re w h ich w as a m edicat ion fo rasp ira to ry disease1 T he au tho r a lso found thecon ten t and compo se of the essen t ia l o il of C 1sinensis rela ted w ith cu ltu red t im e and condit ion1Fu rther w o rk is under go ing in the L abo rato ry fo rth is1
Table 1　Chem ica l componen ts of essen tia l o il in C1 s inens is
N o1 Componen ts Relative
con ten tö%
　1 oxetane, 32(12m ethylethyl) 　　1100
2 1142dioxane22, 52dione 0108
3 to luene 5184
4 n2p ropyl acetate 2146
5 furfu ral 0121
6 fthylbenzene 0157
7 benzene, 1, 32dim ethyl 0148
8 n2benzyloxycarbonyl2L 2tyro sine 0126
9 benzene, p ropyl 0119
10 phenyletnyl alocho l 1194
11 benzene, 1, 2, 42triethyl 0126
12 benzene, 1, 32b is (12m ethylethyl) 0175
13 tetradecane 0113
14 cho lestero l 0152
15 eudesm a24 (14) , 112diene 0169
16 bu tylated hydroxyto luene 2145
17 92octadeceno ic acid (Z ) 2m ethylester 1181
18 2H 2benzocyclohep ten222one, 3, 4, 4a, 5,
　6, 7, 8, 92octahydro24a2m ethyl, (S ) 0148
19 eugeno l 3108
20 testo sterone p rop ionate 3119
21 testo sterone 0152
22 17a2m ethyltesto sterone 5116 N o1 Componen ts Relativecon ten tö%23 1H 2cyclop ropa (a) naph thalene, 1a2, 3, 3a,　4, 5, 6, 7b2octahydro21, 1, 3a272tetram ethyl 　　119424 52azu lenem ethano l, 1, 2, 3, 4, 5, 6, 7, 82octa2 2189　hydro2a, a, 3, 82tetram ethyl (- ) 2aristo lene 116325 22naph thalenem ethano l, decahydro2à, à, 4a2　trim ethyl282m ethylene2[ 2r2(2à, 4aà, 8aá) ] 119026 selina262en242o l 015027 22naph thalenem ethanel, 1, 2, 3, 4, 4a, 5, 6,　8a2octahydro2a, a, 4a, 82tetram ethyl 013228 42nonylpheno l 010829 hep tadecane 014630 nonadecane 013731 22pen tadecanone, 6, 10, 142trim ethyl 011232 verticio l 011233 heneico sane 015134 22112pen tadecenal 014335 n2hexadecano ic acid 1612736 hexadecane 015937 andro st272ene, (5a) 212138 9, 122octadeceno ic acid 1814739 o leic acid 910540 9, 122octadecadieno ic acid, ethyl ester 019341 undecane 2121
References:
[ 1 ]　Zhu J S, H alpern G M , Jones K, et a l1 T he scien tific
rediscovery of an ancien t Ch inese herbal m edicine: Cordy cep s
sinensis: Part É [J ]1 J A ltern Comp lem en t M ed , 1998, 4
(3) : 28923031
[ 2 ]　M anabe N , Sugimo to M , A zum a Y, et a l1 Effects of the
m ycelia ex tract of cu ltu red Cordy cep s sinensis on in v ivo
hepatic energy m etabo lism in the mouse [J ]1 J p n J
P harm acol, 1996, 70 (1) : 852881
[ 3 ]　W ang S M , L ee L J , L in W W , et a l1 Effect of a w ater2
so lub le ex tract of Cordy cep s sinensis on stero idogenesis and
cap su lar mo rpho logy of lip id drop let in cu ltu red rat
adrenoco rtical cell [J ]1 Cell B iochem , 1998, 69 ( 4 ) : 4832
4891
[ 4 ]　L in C Y, Ku F M , Kuo Y C, et a l1 Inh ib it ion of activated
hum an m esangial cell p ro liferation by the natu ral p roduct of
Cordy cep s sinensis (H 12A ) : an imp lication fo r treatm en t of
IgA m esangial neph ropathy [J ]1 J L ab C lin M ed , 1999, 133
(1) : 552631 [ 5 ]　N akam ura K, Yam aguch i Y, Kago ta S, et a l1 A ctivation ofin v ivo Kupffer cell function by o ral adm in istration ofCordy cep s sinensis in rats [J ]1 J p n J P harm acol, 1999, 79(4) : 50525081[ 6 ]　Bok J W , L erm er L , Ch ilton J , et a l1 A ntitumo r stero ls fromthe m ycelia of Cordy cep s sinensis [J ]1 P hy tochem istry , 1995,51 (7) : 89128981[ 7 ]　Cunningham K G, M anson W , Sp ring F S, et a l1Co rdycep in, a m etabo lic p roduct iso lated from cultu res ofCordy cep s sinensis L ink [J ]1 N atu re, 1950, 166: 94929521[ 8 ]　Kredich N M , Guarino A J1 Homocitru llyam i2noadeno sine, anucleo side, a nucleo side iso lated from Cody cep s m ilita ris [J ]1J B iolog Chem , 1961, 236: 3300233021[ 9 ]　Furuya T , H iro tan i M , M atsuzaw a M N 162( 22H ydro2xyethyl ) adeno sine, a b io logically active compound fromcultu red m ycelia of Cordy cep s and Isa ria species [J ]1P hy tochem istry , 1983, 22 (11) : 2509225121
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·779·中草药　Ch inese T radit ional and H erbal D rugs　第 35 卷第 9 期 2004 年 9 月