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十雄角果木树皮的化学成分研究



全 文 :第47卷第6期 华中师范大学学报(自然科学版) Vol.47 No.6
2013年12月 JOURNAL OF HUAZHONG NORMAL UNIVERSITY(Nat.Sci.) Dec.2013
收稿日期:2013-07-09.
基金项目:国家自然科学基金项目(21272136,31070313);广东省重大科技专项(2011A080403020).
*通讯联系人.E-mail:wwujun68@163.com.
文章编号:1000-1190(2013)06-0794-03
十雄角果木树皮的化学成分研究
王 慧1,邹 坤1,吴 军2*
(1.三峡大学 天然产物研究与利用湖北省重点实验室,湖北 宜昌443002;
2.暨南大学 药学院 海洋药物研究中心,广州510632)
摘 要:通过溶剂提取法、正反相硅胶柱色谱和高效液相色谱等方法,从十雄角果木(Ceriops de-
candra)树皮的95%乙醇提取物中分离得到了6个单体化合物,并通过理化性质和波谱数据鉴定
其结构,分别为:(-)-丁香树脂酚 (1),(-)-松脂酚 (2),β-谷甾醇 (3),豆甾醇 (4),棕榈酸 (5)和
3,4-二羟基苯甲酸乙酯 (6).所有化合物均为首次从该植物中分离得到.
关键词:十雄角果木;(-)-丁香树脂酚;(-)-松脂酚;棕榈酸;3,4-二羟基苯甲酸乙酯
中图分类号:O629 文献标识码:A
  角果木属(Ceriops)植物为生长在热带、亚热
带海岸潮间带的红树科(Rhizophoraceae)真红树
植物.该属植物全球有5个种,即角果木(Ceriops
tagal)、十雄角果木(C.decandra)、澳洲角果木
(C.australis)、C.zippeliana 和C.pseudode-
candra.角果木和十雄角果木广泛分布于非洲、马
达加斯加、南亚的沿海及南太平洋岛屿上;澳洲角
果木仅分布于澳洲的中部地区;C.zippeliana分
布于东南亚;而C.pseudodecandra主要分布于澳
大利亚、新几内亚和斯兰岛[1-4].该属植物在我国有
一个物种,即角果木,仅分布于海南岛[5-6].在我国,
角果木的叶子煎熬后用于治疗疟疾[3-4];在印度,十
雄角果木作为一种民间草药用于治疗腹泻、阿米巴
病、出血和恶性溃疡[5].研究表明,二萜和三萜为角
果木属植物C.decandra的主要次级代谢产物类
型[7-11].为了深入地研究十雄角果木的化学成分,
本实验首次对该植物树皮的95%乙醇提取物进行
了研究,从其氯仿萃取部位共分离鉴定了6个化合
物,分别为:(-)-丁香树脂酚 (1),(-)-松脂酚
(2),β-谷甾醇 (3),豆甾醇 (4),棕榈酸 (5)和3,4-
二羟基苯甲酸乙酯 (6).
1 仪器与材料
Bruker AV-400核磁共振仪,Bruker AV-500
核磁共振仪(TMS为内标,瑞士 Bruker公司);
SHMADZU LC-6AD控制器;SPD-20A 检测器,
日本岛津公司;色谱柱为 YMC-Pack ODS-5-A
(250mm×10mm i.d.,5μm,半制备型;250mm
×4.5mm i.d.,5μm,分析型);AB API 2000液
质联用仪;Perkin-Elmer Model 341旋光测定仪;
薄层硅胶GF254和柱色谱硅胶(100~200目)为青
岛海洋化工厂产品;ODS反相硅胶为日本YMC公
司产品;高效液相色谱所用试剂为色谱纯,其余均
为分析纯.
实验材料于2009年采集于印度 Godavari河
口红树林湿地,并经由印度红树植物分类学家
Mr.Tirumani Satyanandamurty鉴定为十雄角果
木Ceriops decandra (Griff.)Ding Hou的树皮.
该植物标本编号为 NO.CD001,存放于暨南大学
药学院海洋药物研究中心.
2 提取与分离
干燥十雄角果木树皮7.4kg粉碎后,用95%
乙醇浸提5次,每次48h.提取液合并后减压蒸干.
提取物经水混悬后,分别用醋酸乙酯、正丁醇萃取
3次.取醋酸乙酯部位浸膏加水混悬,氯仿萃取得
到氯仿萃取部位浸膏65.2g.该部位浸膏经正相硅
胶柱色谱分离,石油醚-丙酮系统[100∶0(10.0
L),100∶1(10.0L),50∶1(10.0L),30∶1
(10.0L),20∶1(10.0L),10∶1(10.0L),5∶
1(10.0L),3∶1(10.0L),2∶1(10.0L),1∶1
(10.0L),1∶2(10.0L),V/V]梯度洗脱得到
 第6期 王 慧等:十雄角果木树皮的化学成分研究 795 
285个流分.流分78~113合并后,经反相硅胶柱
色谱[丙酮-水系统,30∶70(3.5L),45∶55(3.5
L),60∶40(3.5L),75∶25(3.5L),90∶10
(3.5L),100∶0(4.0L),V/V]和重结晶(氯仿),
得到化合物3(5.4mg)和4(5.3mg).流分173~
204合并后,经反相硅胶柱色谱[丙酮-水系统,45
∶55(1.0L),60∶40(1.0L),75∶25(1.0L),
90∶10(1.0L),100∶0(1.5L),V/V]和重结晶
(丙酮),得到化合物5(4.6mg).流分214~238
合并后,经反复 HPLC制备(YMC-Pack 250×10
mm i.d.,YMC-Pack 250×4.6mm i.d.,32∶68
的乙腈-水;40∶60的甲醇-水,V/V)得到化合物1
(5.2mg,22min),2(4.9mg,26min)和6(3.5
mg,45min).化合物1~化合物6的结构如图1
所示.
图1 化合物1~6的结构式
Fig.1 Structures of compounds 1~6
3 结构鉴定
化合物1:无色固体,[α]25D -28.4(c 0.38,丙
酮),分子式:C22H26O8.ESIMS(m/z):441.0
[M+Na]+,417.3[M-H]-.1 H NMR (400
MHz,CDCl3):δH 6.59 (4H,s,H-2,2’,6,
6’),5.50(2H,s,-OH),4.74(2H,d,J=4.4
Hz,H-7,7’),4.29(2H,dd,J=8.8,6.8Hz,
H-9e,9’e),3.91(2H,dd,J=6.8,4.0Hz,H-
9a,9’a),3.91 (12H,s,3,3’,5,5’-OMe),
3.10(2H,m,H-8,8’).13C NMR (100MHz,
CDCl3):δC147.2(C-3,3’,5,5’),134.3(C-4,
4’),132.1(C-1,1’),102.8(C-2,2’,6,6’),
86.1(C-7,7’),71.8(C-9,9’),56.4(3,3’,5,
5’-OMe),54.4(C-8,8’).以上数据与文献[12]报
道一致,故鉴定化合物1为(-)-丁香树脂酚.
化合物2:无色固体,[α]25D -14.0(c 0.35,丙
酮),分子式:C20H22O6.ESIMS(m/z):381.0[M
+Na]+,357.2[M-H]-.1 H NMR(400MHz,
CDCl3):δH6.90(2H,d,J=2.0Hz,H-2,2’),
6.88(2H,s,H-5,5’),6.82(2H,dd,J=8.0,
2.0Hz,H-6,6’),5.60(2H,s,-OH),4.74
(2H,d,J=4.4Hz,H-7,7’),4.25(2H,dd,J
=9.0,6.8Hz,H-9e,9’e),3.88(2H,dd,J=
9.2,3.6Hz,H-9a,9’a),3.91(12H,s,3,3’,
5,5’-OMe),3.10(2H,m,H-8,8’).13 C NMR
(100MHz,CDCl3):δC146.7(C-3,3’),145.3
(C-4,4’),133.0(C-1,1’),119.0(C-6,6’),
114.3(C-5,5’),108.6(C-2,2’),85.9(C-7,
7’),71.7(C-9,9’),56.0(3,3’-OMe),54.2
(C-8,8’).以上数据与文献[13]报道一致,故鉴定
化合物2为(-)-松脂酚.
化合物3:无色针状晶体(氯仿),分子式:
C30H52O.薄层色谱检识,其Rf 值在多个溶剂系统
中与 β-谷甾醇标准品一致,且
1 H NMR (500
MHz,CDCl3):δH5.35(1H,br s,H-6),3.52
(1H,m,H-3),1.01(6H,s,H3-19,26),0.98
(3H,s,H3-21),0.88 (3H,J=6.7Hz,H3-
28),0.85(3H,s,H3-22),0.82(3H,J=6.7
Hz,H3-29).以上数据与文献[14]报道一致,故鉴定
化合物3为β-谷甾醇.
化合物4:无色针状晶体(氯仿),分子式:
C30H50O.薄层色谱检识,其Rf 值在多个溶剂系统
中与豆甾醇标准品一致,且1 H NMR (500MHz,
CDCl3):δH5.35(1H,br s,H-6),5.15(1H,
dd,J=15.0,8.5Hz,H-22),5.12(1H,dd,J
=15.0,8.5Hz,H-23),3.55(1H,m,H-3),
1.01(6H,s,H3-19,26),0.98(3H,s,H3-21),
0.83(3H,s,H3-22),0.80 (3H,s,H3-28),
0.70(3H,s,H3-29).以上数据与文献[14]报道一
致,故鉴定化合物4为豆甾醇.
化合物5:无色片状晶体(丙酮),分子式:C16
H32O2.ESIMS(m/z):255.3 [M - H]-.1 H
NMR(400MHz,CDCl3):δH0.88(3H,m,H3-
16),1.63(2H,m,H-15),2.35(2H,m,H-
2).13C NMR (100MHz,CDCl3):δC179.9(C-
1),34.0(C-2),24.7(C-3),31.9(C-14),22.7
(C-15),14.1(C-16).以上数据与文献[15]报道一
796  华中师范大学学报(自然科学版)   第47卷
致,故鉴定化合物5为棕榈酸.
化合物6:无色固体,分子式:C9H10O4.ES-
IMS(m/z):181.1 [M - H]-,217.0 [M +
Cl]-.1 H NMR(400MHz,DMSO-d6):δH7.35
(d,J=2.1Hz,H-3),7.30(dd,J=8.2,2.1
Hz,H-5),6.79 (d,J=8.2 Hz,H-6),4.22
(2H,dd,J=14.2,7.1Hz,OCH2CH3),1.28
(3H,t,J=7.1Hz,OCH2CH3).以上数据与文
献[16]报道一致,故鉴定化合物6为3,4-二羟基苯
甲酸乙酯.
4 结语
本实验首次对十雄角果木树皮的化学成分进
行了研究.从其95%乙醇提取物的氯仿萃取部位
共分离鉴定了6个化合物,包括2个木脂素类化合
物,2个甾体类化合物,1个脂肪酸和1个苯甲酸酯
衍生物.所有化合物均为首次从该属植物中分离
得到.
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Chemical constituents of the barks of Ceriops decandra
WANG Hui 1,ZOU Kun1,WU Jun2
(1.Hubei Key Laboratory of Natural Products Research and Development,
Colege of Chemistry and Life Science,China Three Gorges University,Yichang,Hubei 443002;
2.Marine Drugs Research Center,Colege of Pharmacy,Jinan University,Guangzhou 510632)
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818  华中师范大学学报(自然科学版)   第47卷
Discrete berth alocation problem with stochastic arrival and handling time
XIE Xin1,HU Zhihua1,2
(1.Logistics Research Center,Shanghai Maritime University,Shanghai 201306;
2.School of Economics and Management,Tongji University,Shanghai 200092)
Abstract:In the daily operation of the container terminal,due to the factors including
the change of the shipping speed,weather,mechanical failure,varying mechanical effi-
ciency and the staff schedules,the arrival and handling time wil be influenced.To stud-
y the impact which the uncertainty of the arrival and handling time imposed on the berth
alocation problem,this paper established a mixed integer linear programming model for
the discrete berth alocation problem.The model is solved by Cplex and demonstrated
by examples.When the stochastic characteristics of the fluctuation of the arrival and
handling time are considered,the total berthing times in port under different degree of
fluctuation are calculated.The influencing rules under two scenarios of uncertainty are
obtained by comparing to the values when the stochastic characteristics are not consid-
ered.
Key words:container terminal;discrete berth alocation problem;arrival time;handling
time;mixed integer linear programmin
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identified by means of spectroscopic data and physicochemical properties,and assigned
as(-)-syringaresinol(1),(-)-pinoresinol(2),β-sitosterol(3),stigmasterol(4),
palmitic acid(5),and 3,4-dihydroxybenzoic acid ethyl ester(6).Al the above com-
pounds were obtained from this plant for the first time.
Key words:Ceriops decandra;(-)-syringaresinol;(-)-pinoresinol;palmitic acid;3,
4-dihydroxybenzoic acid ethyl ester