Bioactive steroids from the whole herb of Euphorbia chamaesyce

Three new ergostane-type steroids, 3beta-hydroxy-4alpha, 14alpha-dimethyl-5alpha-ergosta-8,24(28)-dien-11 -one (1); 3beta, 11alpha-dihydroxy-4alpha,14alpha-dimethyl-5alpha -ergosta-8, 24(28)-dien-7-one (2); and 3beta,7alpha-dihydroxy-4alpha, 14alpha-dimethyl-5alpha-ergosta-8,24(28)-dien-11 -one (3), were isolated, together with two known triterpenoids, wrightial and lup-20(30)-ene-3beta,29-diol from the whole herb of Euphorbia chamaesyce. Compound 3 showed a potent inhibitory effect on Epstein-Barr virus early antigen activation induced by the tumor promoter 12-O-tetradecanoylphorbol 13-acetate (TPA).     

乳香醋酸乙酯部位的化学成分研究

目的 研究乳香中醋酸乙酯部位的化学成分。方法 采用正反相硅胶柱色谱和重结晶等技术对其醋酸乙酯部位中的化学成分进行分离和纯化,并根据波谱数据鉴定化合物的结构。结果 分离得到9个化合物,分别鉴定为3α-乙酰氧基-甘遂-7,24-二烯-21-酸（1）、3α-乙酰氧基-羊毛甾-8,24-二烯-21-酸（2）、3-羰基-甘遂-8,24-二烯- 21-酸（3）、3β-羟基-羊毛甾-8,24-二烯-21-酸（4）、3-乙酰基-11-羰基-β-乳香酸（5）、3-乙酰基-α-乳香酸（6）、3-乙酰基-β-乳香酸（7）、incencole oxide acetate（8）、棕榈酸（9）。结论 化合物1是首次从天然资源中分离得到,化合物9为首次从乳香中分离得到。     

Oculatol, oculatolide, and A-nor sterols from the sponge Haliclona oculata

Chemical investigation of the marine sponge Haliclona oculata resulted in the isolation of eight new compounds including oculatol (1) and oculatolide (2) and six unusual A-nor steroids, 2-ethoxycarbonyl-2beta-hydroxy-A-nor-ergosta-5,24(28)-dien-4-one (3), 2-ethoxycarbonyl-24-ethyl-2beta-hydroxy-A-nor-cholesta-5-en-4-one (4), 2-ethoxycarbonyl-2beta,7beta-dihydroxy-A-nor-ergosta-5,24(28)-dien-4-one (5), 2-ethoxycarbonyl-2beta,7beta-dihydroxy-A-nor-cholesta-5-en-4-one (6), 2-ethoxycarbonyl-2beta,7beta-dihydroxy-24-methyl-A-nor-cholesta-5,22(E)-dien-4-one (7), and 2-ethoxycarbonyl-2beta,7beta-dihydroxy-A-nor-cholesta-5,22(E)-dien-4-one (8), along with 16 known steroids and indole derivatives. Their structures were unambiguously determined on the basis of extensive spectroscopic analyses.     

乳香的化学成分

目的：研究乳香提取物的化学成分。方法：超临界萃取乳香有效部位,采用硅胶柱层析,制备薄层层析等色谱方法,分离乳香提取物的化学成分。采用四甲基偶氮唑蓝（MTT）法观察化合物3、4对肿瘤细胞的抑制增殖作用。结果：分离得到9个化合物,经波谱方法鉴定为西松烯A（1）,verticilla-4（20）,7,11-triene（2）,11-羰基-β-乙酰乳香酸（3）,3-羰基-甘遂烷名,24-二烯．21-酸（4）,花生酸（5）,棕榈酸（6）,硬脂酸（7）,1,2-二羟基十九酮-3（8）,单棕桐酸甘油酯（9）。结论：化合物7～9为首次从该属植物中分离得到。化合物3对lgel-7402细胞有抑制增值作用,化合物4对MCF．7,SMMC．7721,K562Hela细胞右抑制增殖作用．     

透骨草提取物对人肝癌SMMC-7721细胞凋亡及凋亡相关因子的影响

[目的]观察透骨草提取物对人肝癌SMMC-7721细胞凋亡的影响,探讨透骨草提取物诱导SMMC-7721细胞凋亡的分子机制。[方法]流式细胞术检测透骨草提取物诱导SMMC-7721细胞凋亡的影响;免疫组化法检测透骨草提取物对SMMC-7721细胞caspase-9、-3、-7和x连锁凋亡抑制蛋白（XIAP）表达的影响。[结果]40．91μg／mL透骨草提取物处理的SMMC-7721细胞凋亡率为（26．84±1．23）％,明显高于对照组（P〈0．05）。40．9μg／mL透骨草提取物处理的SMMC-7721细胞Caspase-9、-3、-7蛋白表达明显低于与对照组（P〈0．05）,而XIAP蛋白表达明显高于对照组（P〈0．05）。瞄论]透骨草提取物能通过XIAP／Caspase信号通路抑制SMMC-7721细胞凋亡。关键词：透骨草提取物;SMMC-7721细胞;凋亡;Caspase-9中图分类号：R285．5文献标识码：A文章编号：1672—1519（2013）10—0612—03     

Novel cytotoxic principles of Formosan Ganoderma lucidum.

Two new steryl esters, ergosta-7,22-dien-3 beta-yl linoleate [1] and 5 alpha,8 alpha-epidioxyergosta-6,22-dien-3 beta-yl linoleate [3], and a novel steroid, ergosta-7,22-diene- 3 beta,3 alpha,9 alpha-triol [5], have been isolated from the fruiting bodies of Formosan Ganoderma lucidum and characterized. A new lanostanoid, 3 beta-hydroxy-26-oxo-5 alpha-lanosta- 8,24-dien-11-one, and the new steroid exhibited potent inhibition of KB cells and human PLC/PRF/5 cells in vitro.     

New cytotoxic oxygenated fucosterols from the brown alga Turbinaria conoides

Fucosterol (1), 24xi-hydroperoxy-24-vinylcholesterol (2), 29-hydroperoxystigmasta-5,24(28)-dien-3beta-ol (3), 24-ethylcholesta-4,24(28)-dien-3-one (4), 24xi-hydroperoxy-24-ethylcholesta-4,28(29)-dien-3-one (5), 24-ethylcholesta-4,24(28)-dien-3,6-dione (6), 24xi-hydroperoxy-24-ethylcholesta-4,28(29)-dien-3,6-di one (7), 6beta-hydroxy-24-ethylcholesta-4,24(28)-dien-3-one (8), and 24xi-hydroperoxy-6beta-hydroxy-24-ethylcholesta-4,28(2 9)-dien-3-one (9) were isolated from the marine brown alga Turbinaria conoides. The structures of these compounds were established by spectral analysis. Isolated for the first time from a natural source, the oxygenated fucosterols 4-9 exhibit cytotoxicity against various cancer cell lines.     

杭白菊中黄酮类化合物及其抑制人源肿瘤细胞增殖活性的研究

 目的 分离和鉴定杭白菊中黄酮类化合物并对其进行抗肿瘤活性研究。方法 利用系统溶剂萃取法、聚酰胺柱色谱、半制备型高效液相色谱法分离。通过理化性质和IR、UV、MS、¹H-NMR、¹³C-NMR等光谱数据鉴定化合物。采用MTT法测定化合物对人肿瘤细胞增殖的影响, 并以氟尿嘧啶（5-FU）作为阳性对照,比较其对正常细胞的毒性作用。流式细胞术检测细胞周期分布的改变。结果 分离得到8个黄酮化合物单体,分别鉴定为木犀草素(Ⅰ),木犀草素7-O-β-D-葡萄糖苷(Ⅱ),木犀草素7-O-β-D (6″-O-丙二酸单酰) -葡萄糖苷(Ⅲ),芹菜素(Ⅳ),芹菜素 7-O-β-D-葡萄糖苷(Ⅴ),芹菜素 7-O-β-D-(6″-O-丙二酸单酰)-葡萄糖苷(Ⅵ),香叶木素(Ⅶ),香叶木素 7-O-β-D-葡萄糖苷(Ⅷ)。MTT法测定木犀草素抑制乳腺癌MDA-MB-231细胞 和肝癌SMMC-7721细胞的IC₅₀分别为56.67和72.92 μmol·L^-1。结论 化合物Ⅲ和Ⅵ首次从杭白菊中分离得到。木犀草素能抑制MDA-MB-231和SMMC-7721增殖,阻滞其细胞周期于G2/M期,且对正常细胞无毒性。     

Triterpenoids and steroids from the fruits of Melia toosendan and their cytotoxic effects on two human cancer cell lines

Ten new triterpenoids, named meliasenins I-R (1-10), one new steroid (11), and 11 related known compounds (12-22) were isolated from fruits of Melia toosendan. The structures of the new compounds were established on the basis of spectroscopic methods, including 2D NMR techniques and mass spectrometry. The relative configuration of 1, (20R*,23E)-25-hydroperoxyeupha-7,23-diene-3β,16β-diol (meliasenin I), was confirmed by single-crystal X-ray diffraction analysis. All isolated triterpenoids (1-10, 12-15) and two steroids (11, 20) were tested for their cytotoxicity against U20S human osteosarcoma and MCF-7 human breast cancer cells using the MTT assay, and some of them were significantly cytotoxic (IC(50) <10 μg/mL). The insecticidal properties of compounds 1-15 and 20 were also briefly evaluated.     

牛膝中新蜕皮甾酮类成分的研究

 目的研究中药牛膝中蜕皮甾酮类成分。方法采用大孔树脂、硅胶、ODS柱色谱分离纯化,经理化常数、光谱学方法鉴定结构。结果分离得到了3种蜕皮甾酮类成分,其结构分别为:2β,3β,5β,14α,20β,22α,25-七羟基-7-烯-胆甾-6-酮(polypo-dineB,1);2β,3β,14α,20β,22α,25-六羟基-7-烯-胆甾-6-酮(β-蜕皮甾酮,2);2β,3β,20β,22α,25-五羟基-8,14-二烯-胆甾-6-酮(3)。结论化合物3是新化合物。     

Antitubercular sterols from Thalia multiflora Horkel ex Koernicke

Bioassay guided isolation of an antitubercular extract of the aerial parts of Thalia multiflora led to the isolation of nine stigmast-5-ene and stigmasta-5,22-dien steroids, four isorhamnetin and quercetin flavonoid glycosides, two ceramides, an indole alkaloid and two simple phenolic compounds. Stigmast-5-en-3beta-ol-7-one (2), stigmast-4-ene-6beta-ol-3-one (3), stigmast-5,22-dien-3beta-ol-7-one (7) and stigmast-4,22-dien-6beta-ol-3-one (8) were found to be the most active compounds with MIC values of 1.98 +/- 0.02, 4.2 +/- 0.17, 1.0 +/- 0.06 and 2.2 +/- 0.3 microg/mL, respectively. Compounds 2, 3, 7 and 8 were not cytotoxic to Vero cells at 102 microg/mL. This investigation constitutes the first report of a chemical study of a species of the genus Thalia.     

Cyclopeptide Alkaloids from Ziziphus apetala

Six novel Ia?-type cyclopeptide alkaloids (1-6) were isolated from stems of Ziziphus apetala. Compound 5 and the known compounds mauritine A (7) and mauritine F (8) were isolated from the roots. Their structures were determined by spectroscopic analyses and chemical methods. The total alkaloids from the roots and the isolated cyclopeptide alkaloids were tested for antidepressant behavior on mice, cytotoxicity, and 11β-hydroxysteroid dehydrogenase (11β-HSD) inhibition in vitro. Only mauritine A (7) showed inhibitory activity on 11β-HSD1, with IC?? values of 52.0 (human) and 31.2 μg/mL (mouse).     

红缘拟层孔菌子实体中抗肿瘤活性成分研究

目的对红缘拟层孔菌Fomitopsis pinicola子实体的石油醚提取物、氯仿提取物、水层提取物和氯仿提取物中获得的化合物A(3-乙酰氧基-8,24-羊毛甾二烯-21-酸)进行了体内外抗肿瘤活性和细胞凋亡实验研究。方法通过测定脾脏指数、胸腺指数以及血清中白介素-2(IL-2)的含量,检测了各提取物对荷瘤小鼠免疫功能的影响。结果氯仿提取物和化合物A对H22荷瘤小鼠具有较高的抑瘤率,当氯仿提取物剂量为200 mg.kg-1.d-1时,抑瘤率为52.97%,胸腺指数明显高于对照组和环磷酰胺(CTX)组(P<0.05),而接近于正常组(P>0.05);脾脏指数接近于对照组和CTX组而明显高于正常组(P<0.01);IL-2的含量明显升高;化合物A具有较好的抗肿瘤作用,各剂量组之间存在良好的剂量关系;且同对照组相比存在显著性差异(P<0.01);在剂量为10mg.kg-1.d-1时,抑瘤率最高可达到52.31%。体外实验研究结果表明化合物A对人肝癌细胞SMMC-7721和人乳腺癌细胞MCF-7均具有良好的抑制作用,其抑制率最大分别为77.63%和90.29%,IC50分别为213.80μg/ml和123.03μg/ml。化合物A作用后的细胞凋亡率仅为23.2%,接近阴性对照组的20.9%,促进细胞凋亡效果不明显。结论结合体内外实验可推断化合物A(3-乙酰氧基-8,24-羊毛甾二烯-21-酸)为红缘拟层孔菌抗肿瘤活性成分之一,提高机体免疫活性可能是其抗肿瘤作用的机理之一。     

红豆杉细胞提取物对癌细胞的抑制作用研究

目的：了解红豆杉细胞提取物对肝癌细胞系SMMC—7721生长的影响。方法：运用MTT比色法测定癌细胞的存活率和流式细胞仪分析细胞周期。结果：红豆杉细胞二氯甲烷提取物对癌细胞SMMC—7721的抑制作用远大于甲醇提取物，IC50值分别为0．0834mgDCWW．m1^-1和0．8002mgDCW．m1^-1；流式细胞仪分析发现外加红豆杉细胞二氯甲烷提取物后肝癌细胞G2／M期含量增加。结论：红豆杉细胞提取物在体外对肝癌细胞SMMC—7721的生长通过诱导凋亡而具有抑制作用。     

沙蟾毒精诱导人肝癌SMMC-7721细胞凋亡及其机制的研究

目的观察沙蟾毒精诱导人肝癌SMMC-7721细胞凋亡的作用。方法用M,rr法观察沙蟾毒精对人肝癌SMMC-7721细胞增殖的影响：通过荧光染色、流式细胞分析等方法观察沙蟾毒精对细胞凋亡的影响：RT—PCR和Westernblot分析沙蟾毒精对Bcl-2、Bax、p53和p21等基因和蛋白表达的影响。结果沙蟾毒精对人肝癌SMMC-7721细胞的生长有明显的抑制作用,24h半数抑制剂量（IC50）为0．415μg／mL。细胞周期结果显示,人肝癌SMMC-7721细胞经不同浓度的沙蟾毒精处理后,G／M期细胞数量增加,而Go／G,期细胞数明显减少。RT—PCR和Westernblot结果显示,人肝癌SMMC-7721细胞经沙蟾毒精处理后,Bax的表达升高,而bcl-2的表达降低（P〈0．05）。结论沙蟾毒精可能通过线粒体凋亡途径诱导人肝癌SMMC-7721细胞凋亡。     

Structure and cytotoxicity of diterpenoids from Isodon adenolomus

Twelve new diterpenoids, isoadenolins A-L (1-12), and 24 known ones were isolated from the aerial parts of Isodon adenolomus. Their structures were identified using spectroscopic data, and the absolute configurations of 1 and 14 were determined by single-crystal X-ray diffraction. Selected compounds were evaluated for their in vitro cytotoxicity against human tumor HL-60, SMMC-7721, A-549, MCF-7, and SW-480 cell lines. Compounds 9, 13-16, and 21 showed significant inhibitory effects on all five cells, with IC50 values in the range 0.7-9.7 μM.     

马肾果叶的化学成分及其细胞毒活性

[目的]研究马肾果叶的化学成分,寻找新的具有抗肿瘤作用的先导化合物。[方法]采用硅胶、RP-18反相硅胶柱色谱及重结晶等方法进行分离纯化,依据核磁共振、质谱等波谱数据进行结构鉴定,通过二甲基四氮唑盐(MTT)法测定细胞毒活性。[结果]从马肾果叶的乙醇提取物中分离纯化了18个化合物,分别鉴定为aglain C(1),aglaxiflorin D(2),10-O-acetylaglain(3),rocaglaol(4),odorine(5),odorinol(6),(2R,3R)-2,3-di-(3,4-dimethoxybenzyl)-butyrolactone(7),secoisolariciresinol dimethyl ether(8),pinoresinol(9),richenone(10),richenol(11),ursolic acid(12),eichlerianic acid(13),shoreic acid(14),3β-hydroxy-5α,8α-epidioxyergosta-6,22-diene(15),stimast-5-en-3β,7α-diol(16),4β,10α-dihydroxy aromadendrane(17),3-hydroxy-4’,6,8-trimethoxyflavon(18)。化合物4对人肺癌细胞AGZY 83-a和人肝癌细胞SMMC-7721的IC50值分别为0.013μg/mL和1.571μg/mL。[结论]化合物1,3-5,7,9-12,17,18系首次从该植物中分离得到,化合物4对两种细胞株均表现出显著的细胞毒活性。     

Four new eudesmanes from Caragana intermedia and their biological activities

Four new eudesmanes, namely, 4(15)-eudesmene-1beta,7alpha-diol (1), 4(15)-eudesmene-1beta,7beta-diol (2), 7-trinoreudesma-4(15),8-dien-1beta-ol-7-one (3), and eudesma-4(15),7-dien-1beta-ol (4), as well as three known compounds, 5-epi-eudesma-4(15)-ene-1beta,6beta-diol (5), 4(15)-eudesmene-1beta,6alpha-diol (6), and 4(15)-eudesmene-1beta,5alpha-diol (7), were isolated from the aerial part of Caragana intermedia. The structures were elucidated by spectroscopic and spectrometric analyses including 1D, 2D NMR, HRMS, and IR. The structures of compounds 1, 5, 6, and 7 were confirmed by X-ray crystallographic analysis. Compound 7 showed glucose consumption activity with an IC value of 10.7 microg/mL in a C2C12 muscle cell assay. The MIC value of this compound (100 mg/kg) in a db/db mice model is equivalent to that of metformin in vivo.     

New antimycobacterial and antimalarial 8,9-secokaurane diterpenes from Croton kongensis

Two new 8,9-secokaurane diterpenes, ent-8,9-seco-7alpha,11beta-diacetoxykaura-8(14),16-dien-9,15-dione (1) and ent-8,9-seco-8,14-epoxy-7alpha-hydroxy-11beta-acetoxy-16-kauren-9,15-dione (2), together with two known compounds, ent-8,9-seco-7alpha-hydroxy-11beta-acetoxykaura-8(14),16-dien-9,15-dione (3) and ent-7beta-hydroxy-15-oxokaur-16-en-18-yl acetate, were isolated from Croton kongensis. This is the first report on the presence of 8,9-secokauranes in the plant genus Croton. Diterpenes 1-3 exhibited antimycobacterial activity with minimum inhibitory concentrations (MICs) of 25.0, 6.25, and 6.25 microg/mL, respectively, and possessed antimalarial activity with IC(50) ranges of 1.0-2.8 microg/mL. They also demonstrated comparable cytotoxicity toward the Vero (IC(50) ranged from 0.9 to 3.2 microg/mL), KB (IC(50) from 1.2 to 13.8 microg/mL), and BC cell lines (IC(50) from 1.1 to 2.2 microg/mL, except for compound 1, which was inactive against BC cells).     

Trypanocidal diarylheptanoids from Aframomum letestuianum

Three new diarylheptanoids, (4Z,6E)-5-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-7-(4-hydroxyphenyl)hepta-4,6-dien-3-one, letestuianin A (1), (4Z,6E)-5-hydroxy-1,7-bis(4-hydroxy-3-methoxyphenyl)hepta-4,6-dien-3-one, letestuianin B (2), and 1,7-bis(4-hydroxyphenyl)heptan-3,5-dione, letestuianin C (3), as well as the known (4Z,6E)-5-hydroxy-1,7-bis(4-hydroxyphenyl)hepta-4,6-dien-3-one (5) were isolated from Aframomum letestuianum. The known flavonoids 3-acetoxy-5,7,4'-trihydroxyflavanone, 3-acetoxy-7-methoxy-5,4'-dihydroxyflavanone, 7-methoxy-3,5,4'-trihydroxyflavone, and 3,3',4',5,7-pentahydroxyflavan were also obtained from this plant. Their structures were determined using a combination of 1D and 2D NMR techniques. The four diarylheptanoids were tested for growth inhibitory activity in vitro versus bloodstream forms of African trypanosomes. IC(50) values in the range of 1-3 microg/mL were found for compounds 3 and 5.