全 文 ：收稿日期:2002-08-25.
作者简介:禚如朋(1976-),男 ,博士 ,研究方向:海洋天然药物化学.
A new bioactiveα-branched , α-unsaturated aldehyde from
sea anemone anthoplelura xanthogrammica(Berkly)
ZHUO Ru-peng1;FU Hong-zheng1;JI Yu-bin2;LIN Wen-han1
(1.National Laboratory of Natural and Bionmimetic Drugs , Peking University , Beijing 100083 , China;
2.Institute of Materia Medica ,Harbin of University Commerce ,Harbin 150076 , China)
Abstract:A new α-branched ,α-unsaturated aldehyde , namely (Z)-2-pentadecy1-2-
heneicosanal(1),was isolated from the sea anemone anthoplelura xanthogrammica(Berkly).The
structure of 1 was determined by extensively spectoscopic analysis.Compound 1 showed moderate
growth inhibitory activity aganinse HL-60 cells.
Key words:(Z)-2-pentadecy1-2-heneicosanic aldehyde;sea anemone;anthoplelura xan-
thogrammica(Berkly)
中图分类号:R284　　　　　文献标识码:A　　　　　文章编号:1004-1842(2002)05-0496-03
黄海葵中新不饱和脂肪醛的化学结构
禚如朋1 ,付宏征1 ,季宇彬2 ,林文翰1
(1.北京大学 天然药物及仿生药物国家重点实验室 , 北京　100083;
2.哈尔滨商业大学 药物研究所 , 黑龙江 哈尔滨 150076)
摘　要:从黄海葵 anthoplelura xanthograminica(Brerkly)中 , 分离得到一种新颖结构的α-不饱和醛类化
学物 ,其化学结构经各种波谱解析得以确定;化合物 1对肿瘤细胞HL-60 具有抑制活性。
关键词:黄海葵;不饱和醛;结构确定
lntroduction
Bioactive factors such as neuro-and cardion-tox-
ic principles ,haemolytic toxins , and proteinase inhibitors
have been found in sea anemones , both in nematocyst
tentacles and in whole animals
[ 1-3] .Evidence has been
reported for the existence of antitumor substance in sea
anemone.No studies have been conducted to date on the
chemical nature of antitumor substance in sea anemone.
Results and discussion
During our investigation on constituents from the
sea anemone anthoplelura xanthogrammica(Berkly).
collected along the coast of Qingdao China , a new bioac-
tive α-branched ,α-unsaturated aldehyde ,namely (Z)
-2-pentadecy1-2-heneicosanal(1)was isolated
using Si gel column chromatography ,1 possessed moder-
ate growth-inhibitory activity against HL-60 cell.
Compound 1 ,white crystals ,mp.60 ～ 70℃,had the
molecular formula C36H70O , on the basis of HREIMS
(m/z 518.5525 (M+), C36 H70 O requires m/ z
518.5427).The IR absorption at 1687 cm-1 suggested
the presence of an α, β-unsaturated carbonyl group.
The 13　C NMR spectrum of 1(Table 1)showed an alde-
hyde δ195.38(d), two olefinic carbons(δ155.41(d),
δ143.82(s), a number of methylenes (δ22.69 ～
第 18 卷 第 5 期
2002 年 10月 　　　　
哈 尔 滨 商 业 大 学 学 报(自然科学版)
Journal of Harbin University of Commerce Natural Sciences Edition
　　　 Vol.18 No.5
Oct.2002
31.92), and two methylδ14.12(q).The proton signals
δ9.3(s)and δ6.44(dd ,1H , J=7.8Hz , 6.9Hz)were
assigned for an aldehydic proton and olefinic proton , re-
spectively;and the proton signals at δ0.88(t , 6H ,
6.6Hz), 1.26(m), 1.49(m , 2H), 2.22(t , 2H , J =
7.2Hz), and 2.36(dt ,2H , J=6.9 ,7.8Hz)were resem-
ble to those of Botryals , indicatible to characteristic of
saturated lipid chain.
　　The length of the two alky1 chains annexed to α
and β position of of the α,β unsaturated aldehyde was
determined by the typical fragments of electron impact
(EI)mass spectrum , in which the fragment at m/ z 279
was more aboundant than the ion peak at m/ z 321.The
evidence was explained that a form cleavage fragment
was more stable than that of b form cleavage , suggest that
a pentadecyl group annexed to β position and octadecyl
group annexed to αposition of the α, β -unsaturated
aldehyde.The configuration of the double bond was as-
signed as Z form on the basis of the allyic carbon chemi-
cal shifts , in which (Z)-configuration is 195.01 ,
154.76 , 144.12 and (E)-configuration is 190.97 ,
149.20 ,140.55.
Table 1　1HNMR and 13CNMR data of compound 1 in CDCl3
No. δc(ppm) δH(ppm) J(Hz)
17′ 195.38(d) 9.36(s)
16′ 143.82(s)
15′ 24.02(t) 2.22(t , 2H) 7.2
C4 to C18, C4′to C14′ 29.69～ 29.36(t) 1.26(m)
3 , 3′ 31.92(t) 1.26(m)
2 , 2′ 22.69(t) 1.26(m)
1 , 1′ 14.12(q) 0.88(t , 6H) 6.6
19 155.41(d) 6.44(dd ,2H) 7.7, 6.9
18 28.93(t) 2.36(dt , 2H) 7.8, 6.9
17 29.69(t) 1.49(m2H)
　　Compound 1 showed moderate growth -inhibitory
activity against HL-60 cells , and the experimental data
is:when the concentration of drug is 25 μg/ml , the in-
bibitory rate is 43.47%,50μg/ml is 51.65%, and 100
μg/ml is 58.18.
Experimental Section
General Expeimental Procedures.IR spectra were
recorded on a Perkin -Elmer 983 spectrophotometer ,
NMR spectra were measured with VXR-300S and Joel
AL300 apectrometer.C -multiplicities were assigned
based on DEPT experiment.EIMS and HREIMS were
botained with a micromass auto spec spectrometer.Melt-
ing point was recorded on a XT-4melting point appara-
tus and uncorrected;optical ration was done on Perkin
Elmer 243B polarimeter.Thin layer chromatography
(TLC)was performed on Silica HF254(10 -40 μm ,
Qingdao Marine Chemical Factory , China).Separation
and purification were performed on Silica gel 200 ～ 300
mesh(Qingdao Marine Chemical Factory ,China).
Animal Material.The sea anemone anthoplelura
·497·第 5期　ZHUO Ru-peng:A new bioactiveα-branched ,α-unsaturated aldehyde from sea anemone anthoplelura xanthogrammica(Berkly)
xanthogrammica(Berkly)was collected from the coast of
Qingdao in November 1997.A voucher specimen is de-
posited at National Laboratory of Natural and Biomimetic
Drugs ,Peking University.
Extraction and lsolation.Wet specimens(10 kg)
were homogenized in batches in a blender for 5 min with
10 L 95%ethanol;The mixture was allowed to stand for
1 week at 20 ℃ with occasional stirring and was fil-
tered.The filtrate was evaporated under reduced pressure
to give EtOH extract ,which was partitioned between H2O
and EtOAc , and the aqueous layer was extracted with
BuOH to afford fractions EtOAc-(7.8 g),BuOH-(10
g), and H2O-soluble portions.
The EtOAc fraction(4 g)was chromatographed on
a Si gel column(40 g), and eluted with petroleum ether-
Me2CO(20:1 ,10:1 , 5:1 , 2:1 and 1:1 , each 500 ml),
CHCl3-MeOH(20:1 , 10:1 , 5:1 and 2:1 , each 500
ml), and MeOH (200 ml)gradiently to tweleve frac-
tions.Fraction 2(1 g),was subjected to normal phase Si
gel column chromatography repeatedly to give compound
1(4.0 mg).
Compound 1:white crystals(4.0 mg), mp.67 ～
70℃;IR(KBr)2918 , 2848 , 1687 cm-1;1H NMR , see
Table 1;13C NMR , see Table 1;HREIMS m/z 518.5525
(calcd for C36)H70O 518.5427);EIMS[M] +518 ,m/x:
307 ,293 ,279 ,149 ,111 ,97 ,83 , 71.
Cytotoxic Activity.In a 25-well plate ,HL-60 cells
(1×105 cells)were inoculated in 2 ml of Dulbecco s
modified Eagle s medium supplemented with 10% fetal
bovine serum.The tested compounds were maintained at
37 ℃in 5%CO2.Seventy-two hours after inoculation ,
the cells were stained with crysstal violet , and the cell
growth was determined by microscopic observation.
Acknowledgment
The specie is identified by Mr.LIAN Shao-Xing ,
in Institute for Marin Research , CAS , for kindly making
identification of the sea anemone.The authors thank
Teacher WANG Rui-Qing ,Peking University of Nation-
al Laboratory of Natural and Biomimetic Drugs , for mea-
suring the biological activity.
References
[ 1] KEM W.R.Sea anemone toxins:Structure and action.In:The Biology of
Nematocysts[ M] .(Hessinger , D.and Lenhoff , H., Eds.).New York:
Academic Press , 1988:375～ 405.
[ 2] TABRAH F., KASHIWAGI M.NORTTON T.R., Int.J.Chin , Pharma-
col[ J] .Ther.Toxicol., 1972 , 4 , 420.
[ 3] METAGER P.CASADEVALL.E.Tetrahedron Lett[ J] .1988 , 29(23),
pp.2831～ 2834.
哈尔滨商业大学 2002年鉴定项目
1.黑龙江省旅游教育发展战略的研究(黑龙江省教育厅项
目)
项目负责人:杨铭铎　教授
2.黑龙江省主要自然灾害预防及综合治理对策研究(黑龙
江省科技厅项目)
项目负责人:刘　功　教授
3.东北解放区人民货币研究(黑龙江省教育厅项目)
项目负责人:张新知　副教授
4.粉末蜂蜜及蜂胶系列食品的开发(黑龙江省科技厅项目)
项目负责人:叶怀义　教授
5.关于中国与美国商品学科学体系的比较研究(黑龙江省
科技厅项目)
项目负责人:白世贞　副教授
6.国际商务风险的预防与依法解决(黑龙江省科技厅项目)
项目负责人:庞春祥　讲师
7.加入WTO 对我国会计影响的研究(黑龙江省科技厅项
目)
项目负责人:张劲松　教授
8.21世纪会计与会计教育改革研究(黑龙江省教育厅项
目)
项目负责人:齐兴利　教授
9.对国有商业银行不良资产处置方法的研究(黑龙江省教
育厅项目)
项目负责人:孔薇巍　副教授
10.对公共财政下农村财源建设的研究(黑龙江省财政厅项
目)
项目负责人:李秉坤　副教授
11.中国边疆地区经济的超常发展研究(黑龙江省教育厅项
目)
项目负责人:张翠玉　教授
12.英语语用文化教学与交际能力的相关研究(黑龙江省教
育厅项目)
项目负责人:王　颖　副教授
13.抗肾衰胶囊的研制与开发(黑龙江省科技厅项目)
项目负责人:张　翠　副教授
14.消红散对慢性肾小球肾炎 C3b、IC、RFIR作用的实验研
究(黑龙江省教育厅项目)
项目负责人:张　翠　副教授
15.CD-A型智能称量控制器(黑龙江省信息产业厅项目)
项目负责人:赵　清　副教授
·498· 哈尔 滨商业大 学学报(自然 科学版)　　　　　　　　　　　　　　第 18 卷