全 文 ：cm
- 1峰。在酰胺Ë 区域有明显的表征Α螺旋的1 293
cm
- 1 峰。在表征 C2C 骨架伸缩振动的 870～ 960
cm
- 1区域有 924 cm - 1的强峰, 表明 Α螺旋的存在。
综上所述, 火菇素蛋白的二级结构主要为 Α螺旋和Β折叠, 而无规则卷曲含量较少。
21212　火菇素蛋白的侧链环境: 酪氨酸在约 830 和
850 cm - 1出现由环吸收振动和面弯曲振动产生的费
米共振双峰。由这对谱带的强度比可以反映出蛋白
质中酪氨酸所处的环境。当其强度比为 013～ 015
时, 表示酪氨酸残基“埋藏”在疏水环境并在其OH
基和负电荷受体之间形成强氢键, 当强度比为
1125～ 1140 时, 则表明酪氨酸残基全部暴露于溶剂
中。对火菇素蛋白, 测得 I848∶ I826= 1101。据这对谱
带强度比值及 C raig 等确定的方程[8 ] , 定量计算出
“埋藏”和“暴露”的酪氨酸残基占酪氨酸残基总数的
34% 和 66%。
21213　S2S 键的空间结构: 在拉曼光谱中, S2S 和
C2C 伸缩振动的谱带出现在 500～ 700 cm - 1; 两个
半胱氨酸侧链形成的二硫桥, 其C2C2S2S2C2C 键可
能有 3 种构型, 可由 S2S 键的振动频率进行判断:
510 cm - 1 谱带属于扭曲2扭曲2扭曲式构型, 525
cm
- 1谱带属于扭曲2扭曲2反式构型, 540 cm - 1谱带
属于反式2扭曲2反式构型。在火菇素蛋白的拉曼图 谱中, S2S 振动频率出现在 537 cm
- 1处, 表明火菇素
蛋白的C2C2S2S2C2C 侧链为反式2扭曲2反式构型。
References:
[ 1 ]　Kom atsu N , T erakaw a H , N akan ish i K1 F lamm ulin, a basic
p ro tein of F lamm u lina velu tip es w ith an titumo r activit ies
[J ]1 J A n tibiot S er A , 1963, 16 (3) : 13921431
[ 2 ]　W atanabe Y, N akan ish i K, Kom aisu N 1 F lamm ulin, an an ti2
tumo r substance [J ]1 B u ll Chem S oc, 1964, 37 ( 5) : 7472
7501
[ 3 ]　Zhou K S, Peng J F, Zhang C K1 A new m ethod of separa2
t ion and b ioactivity assay of flamm ulin [J ]1 Ch in J B iochem
M ol B iol (中国生物化学与分子生物学学报) , 2003, 19 (2) :
23422391
[ 4 ]　P restrelsk i S J , A rakaw a T , Carpen ter J F, et a l1 Separation
of freezing2and drying2induced denatu ration of lyoph ilized
p ro teins using stress2specific stab ilization Ê 1 Structu ral
studies using infrared spectro scopy [J ]1 A rch B iochem B io2
p hy s, 1993, 303 (2) : 46524731
[ 5 ]　Byler D M , Susi H 1 Exam ination of the secondary structu re
of p ro teins by deconvo lved FT IR spectra [J ]1 B iop olym ers,
1986, 25 (3) 46924871
[ 6 ]　Griebenow K, Klibanov A M 1 L yoph ilization2induced re2
versib le changes in the secondary structu re of p ro teins [J ]1
P roc N a tl A cad S ci U SA , 1995, 92 (24) : 109692109761
[ 7 ]　Sh ie M , Dobrov E N , T ikchonenko T I1 A comparative
study of the structu re of tobacco mo saic virus and cucum ber
virus 4 by laser Ram an spectro scopy [J ]1 B iochem B iop hy s
R es Comm un, 1978, 81 (3) : 90729141
[ 8 ]　C raig W S, Gaber B P1 L aser Ram an scattering from an en2
zym e of w ell2docum ented structu re, hum an carbon ic anhy2
drase B [J ]1 J A m Chem S oc, 1977, 99 (12) : 4130241341
Chem ica l con stituen ts of Rheum g labr icau le (É )
W E I Yu2hu i, ZHAN G Cheng2zhong, L I Chong, TAO Bao2quanΞ
(D epartm ent of N atural D rugs, L anzhou M edical Co llege, L anzhou 730000, Ch ina)
Abstract: Object　To study the chem ical con st ituen ts in the roo t of R heum g labricau le1 M ethods　
Compounds w ere iso la ted by variou s co lum n ch rom atograph ies w ith silica gel1 T heir st ructu res w ere eluci2
dated by spectra l analysis (M S, 1H 2NM R , 13C2NM R ) and chem ical evidence1 Results　F ive compounds
w ere iso la ted from the ch lo rofo rm part, w h ich w ere iden t if ied as ch rysophano l (É ) , physcion (Ê ) , a loe2
emodin (Ë ) , emodin (Ì ) , and Β2sito stero l (Í ) 1 Conclusion　A ll above compounds are ob ta ined from
th is p lan t fo r the first t im e1
Key words: Po lygonaceae; R heum g labricau le G1 Sam ; an th raqu inones
光茎大黄化学成分研究 (É )
魏玉辉, 张承忠3 , 李　冲, 陶保全
(兰州医学院药学院 天然药物教研室, 甘肃 兰州　730000)
摘　要: 目的　对光茎大黄根部的化学成分进行研究。方法　采用硅胶柱色谱分离、重结晶、M S、1H 2NM R、
13C2NM R等技术进行分离、鉴定结构。结果　从该植物中分离并鉴定了 5 个化合物, 分别是大黄酚 (ch rysophano l,
·237· 中草药　Ch inese T radit ional and H erbal D rugs　第 35 卷第 7 期 2004 年 7 月
Ξ 收稿日期: 2003210205
作者简介: 魏玉辉, 男, 兰州医学院 2002 级研究生, 主要从事天然药物化学研究。　E2m ail: stonew yh@ 29111net3 通讯作者　T el: (0931) 8289512
É )、大黄素甲醚 (physcion, Ê )、芦荟大黄素 (a loe2emodin, Ë )、大黄素 (emodin, Ì )、Β2谷甾醇 (Β2sito stero l, Í )。结
论　该 5 个化合物均为首次从该植物中分离得到。
关键词: 蓼科; 光茎大黄; 蒽醌类
中图分类号: R 28411　　　文献标识码: A 　　　文章编号: 0253 2670 (2004) 07 0732 03
　　R heum g labricau le G1 Sam is dist ribu ted in
W udu, W en and M ing Coun ty of Gan su P rovince
in Ch ina1 A s a Ch inese fo lk herb m edicine, it w as
repo rted [1 ] tha t it can clear aw ay heat and tox ic m a2
teria ls, starch and coo l the b lood1 It is app lied fo r
pu rg ing and all k inds of haemo rrhage1 T he re2
search show s its pu rgat ive act ion is sim ilar to that
of R 1 of f icina le Baill1 It w as no t repo rted abou t
study on chem ical con st ituen ts of R 1 g labricau le1
T he au tho r studied chem ical con st ituen ts of R 1
g labricau le in o rder to m ake su re the reliab ility in
u sing drugs, comparing w ith that of R 1 of f icina le1
Exper im en ta l section spactrum
Genera l experim en ta l p rocedu res1 M elt ing
po in ts w ere determ ined on a X- 4 dig ita l mo to rm i2
cro2m elt ing po in t appara tu s and are unco rrected1
V G ZAB - H S m ass spectrom eter w as u sed to
reco rd the E I2M S1 NM R spectra w as m easu red on
a Bu rker AM - 400 spectrom eter, u sing TM S as
in ternal standard1 Coup ling con stan ts (J values)
are g iven in H z·Si gel (100- 200 m u) and Si gel
G ( bo th from Q ingdao M arine Chem ical Group
Co1, Q ingdao , Shandong P rovince, Ch ina ) w ere
u sed fo r co lum n ch rom atography and TL C,
respect ively1
P lan t m ateria l1 A ll roo ts of R 1 g labricau le
w ere co llected in W udu Coun ty, Gan su P rovince in
Ch ina, in A ugu st, 2001, and iden t if ied by P rof.
Zhao R u2neng, from L anzhou M edical Co llege1 A
voucher specim en is depo sited in the M u seum of
M edicinal P lan t, L anzhou M edical Co llege1
Extraction and isola tion
T he air2dried and pu lverized roo ts of R 1
g labricau le (410 kg) w ere soaked and ex tracted ten
t im es w ith 95% E tOH in no rm al tempera tu re, 24
hou rs each t im e1 A fter removal of so lven t, ob2
ta ined 488 g pow der samp le1 T he samp le w as sub2
jected to co lum n ch rom atography on silica gel and
elu ted w ith CHC l3, E tOA c, and E tOH , respect ive2
ly1 T he elu tes w ere co llected in 300 mL po rt ion s,
mon ito red by TL C1 F ive compounds in th is d isser2
ta t ion w ere ob ta ined from the part w h ich had been
elu ted w ith CHC l31 Compound É w as ob ta ined by
pu rif ing w ith CHC l3 and E tOA c from fr2; fr18 -
fr22 elu ted w ith petro leum ether2E tOA c (15∶1,
10∶1) and petro leum ether2acetone (5∶1, 3∶1)
w ere sub jected to repeated co lum n ch rom atography
to yield compound Ê , Ì , and Í ; Compound Ë
w as ob ta ined by pu rif ing w ith E tOA c and acetone
from fr24- fr371
Structura l iden tif ica tion
Compound É ( ch rysophano l) : yellow p iece
(E tOA c) , mp 204- 206 ℃, Bo rn tr a¨ger react ion
show ed red, (A cO ) 2M g react ion show ed salmon
p ink, E I2M S m öz : 254[M + ], 239, 237, 226, 1981
1H 2NM R (CDC l3 ) ∆: 12108 ( 1H , s, C12OH ) ,
11196 (1H , s, C 82OH ) , 7178 (1H , dd, J = 810,
112 H z, C 52H ) , 7164 (1H , t, J = 810 H z, C 62H ) ,
7160 (1H , d, J = 112 H z, C 42H ) , 7126 (1H , dd,
J = 810, 112 H z, C 72H ) , 7105 ( 1H , d, J = 112
H z, C 22H ) , 2144 (3H , s, A r2CH 3) 1 13C2NM R are
seen in T ab le 11 A ll above data are con sisten t w ith
tho se of ch rysophano l in reference [2 ]1
Table 1　Spectra l data of compounds É - Ì
C É Ê Ë Ì
1 　 16213 　 16615 　 16115 　 16414
2 12415 10617 11913 10719
3 14913 16215 15317 16512
4 12113 11012 11711 10817
5 11919 12113 12016 12411
6 13619 14814 13713 14812
7 12413 12415 12414 12014
8 16216 16512 16113 16114
9 19214 19018 19116 18916
10 18118 18210 18113 18112
4Α 13312 13512 13310 13510
10Α 13315 13312 13312 13217
8Α 11518 11316 11413 11313
9Α 11316 10812 11518 10819
CH 3 2212 2212 2115
OCH 3 5611
CH 2OH 6210
　　Compound Ê (physcion ) : sa lmon p ink nee2
dles (E tOA c) , mp 215- 217 ℃, Bo rn tra¨ger reac2
·337·中草药　Ch inese T radit ional and H erbal D rugs　第 35 卷第 7 期 2004 年 7 月
t ion show ed red, (A cO ) 2M g react ion show ed
salmon p ink, E I2M S m öz : 284 [M + ], 269, 2561
1H 2NM R (CDC l3 ) ∆: 12131 ( 1H , s, C12OH ) ,
12111 (1H , s, C82OH ) , 7161 (1H , b rs, C 42H ) ,
7135 (1H , d, J = 214 H z, C52H ) , 7107 (1H , b rs,
C 22H ) , 6168 ( 1H , d, J = 214 H z, C 72H ) , 3194
( 3H , s, OCH 3 ) , 2145 ( 3H , s, A r2CH 3 ).
13C2NM R are seen in T ab le 11 A ll above data are
con sisten t w ith tho se of physcion in reference [2 ]1
Compound Ë ( a loe2emodin ) : Salmon p ink
needles (acetone) , mp 235 - 236 ℃, Bo rn tr a¨ger
react ion show ed red, (A cO ) 2M g react ion show ed
salmon p ink, E I2M S m öz : 270 [ M + ], 2541
1H 2NM R (DM SO 2d6) ∆: 11192 (1H , s, C 12OH ) ,
11185 (1H , s, C 82OH ) , 7176 (1H , dd, J = 210,
810 H z, C52H ) , 7164 (1H , dd, J = 810, 810 H z,
C 62H ) , 7163 ( 1H , d, J = 112 H z, C 42H ) , 7134
(1H , dd, J = 210, 810 H z, C72H ) , 7123 (1H , d,
J = 112 H z, C 22H ) , 5159 (1H , 2OH ) , 4160 (2H ,
s, 2CH 2OH ) 1 13C2NM R are seen in T ab le 11 A ll
above data are con sisten t w ith tho se of a loe2emodin
in reference [3 ]1
Compound Ì (emodin) : R ed gra in (E tOA c) ,
mp 263- 264 ℃, Bo rn tra¨ger react ion show ed red,
(A cO ) 2M g react ion show ed salmon p ink, E I2M S
m öz : 270 [M + ], 2551 1H 2NM R (DM SO 2d6 ) ∆:
12103 (1H , s, C 12OH ) , 11195 (1H , s, C 82OH ) ,
11135 (1H , s, C 62OH ) , 7139 (1H , d, J = 112 H z,
C 42H ) , 7108 ( 1H , d, J = 112 H z, C 22H ) , 7105
(1H , d, J = 214 H z, C52H ) , 6153 (1H , d, J = 214
H z, C 72H ) , 2136 (3H , s, M e) 1 13C2NM R are seen
in T ab le 11 A ll above data are con sisten t w ith
tho se of emodin in reference [4 ]1
Compound Í ( Β2sito stero l) : W h ite needles
(E tOA c) , mp 143- 144 ℃1 H 2SO 42E tOH , L ieber2
m ann react ion show ed po sit ive1 T he data of
1H 2NM R , 13C2NM R are con sisten t w ith tho se of Β2
sito stero l1
Thank Prof. Zhao Ru-neng for iden tify ing the plan t
and thank the staff of In stitute of Lanzhou Physica l Chem -
istry, Ch inese Academy of Sc iences for NM R spectra1
References:
[ 1 ]　Shen S L. Researches and investigates on u tilization of fo lk
drug conditions of R heum L 1 of Gansu [J ]1 Ch in T rad it H erb
D rug s (中草药) , 1998, 29 (10) : 7001
[ 2 ]　Song L , Zhang C Z, L i C, et a l1 Studies on chem ical cons2
t ituen ts of R heum un inerve [J ]1 J Ch in M ed M ater (中药
材) , 2003, 26 (4) : 2601
[ 3 ]　Yang X W , L i J X, Zhao J , et a l1 Studies on R hubarb [J ]1
Ch in T rad it H erb D rug s (中草药) , 1998, 29 (5) : 2891
[ 4 ]　Yang X W , Gu ZM , M a C M , et a l1 A new indo le derivative
iso lated from the roo t of T uber F leecef low er [J ]1 Ch in T rad it
H erb D rug s (中草药) , 1998, 29 (1) : 51
赶山鞭挥发油化学成分的 GC-M S 分析
董建勇Ξ
(甘肃中医学院, 甘肃 兰州　730000)
　　赶山鞭 H yp ericum a ttenua tum Cho isy 系藤黄
科金丝桃属植物。该属植物约 400 种, 除了南北两极
地或荒漠地及大部分热带地外世界广布。我国约有
55 种 8 亚种, 几乎产于全国各地, 主要集中在西南,
其中滇西北分布有近五分之二的种类, 甘肃产约 7
种[1 ]。本属植物约三分之二的种类在民间被用于治
疗多种疾病[2 ]。国内外对金丝桃属植物展开了深入
的有效成分研究, 已完成了本属多数植物的成分检
测。并对约 70 种植物进行了详细的研究, 共发现 90
多种成分, 主要有双蒽酮、黄烷酮醇、黄酮及黄酮醇、
香豆素、酚酸、间苯三酚衍生物、胡萝卜素、挥发油类
等[3 ]。挥发油类有 Α2蒎烯、月桂酸、柠檬烯等, 认为这
些成分是抗真菌的有效成分[4 ]。传统中医药学认为
赶山鞭性平, 味辛苦涩, 能清热解毒, 利湿, 收敛止
血。主要用于治疗心脏病、类风湿性关节炎、内脏出
血、细菌感染、炎症等。对赶山鞭挥发油化学成分的
·437· 中草药　Ch inese T radit ional and H erbal D rugs　第 35 卷第 7 期 2004 年 7 月
Ξ 收稿日期: 2003211212
基金项目: 国家博士后流动站基金资助项目
作者简介: 董建勇 (1963- ) , 山东成武县人, 博士、副教授, 兰州大学化学博士后科研工作站从事科研工作, 主要从事中药有效成分分离
和中药新药临床研究。