麻疯树种子二萜类化学成分的研究

为深入了解麻疯树种子的化学成分,有必要对其具有生物活性的二萜类成分进行研究。该研究利用正相硅胶、ODS、制备液相等色谱分离方法,从麻疯树种子的乙醇提取物中共分离得到了6个二萜类化合物,并采用荧光偏振技术对化合物进行蛋白激酶C (PKC)抑制活性的测定。结果表明:根据化合物的理化性质、MS和NMR,并参考相关文献,这6个二萜类化合物分别鉴定为3β-acetoxy-12-methoxy-13-methylpodocarpa-8,11,13-trien-7-one (1)、4-epi-dehydroabietic acid (2)、3β-hydroxy-19-O-acetyl-pimara-8 (9),15-dien-7-one (3)、Jatrophodione A (4)、14-O-acetyl-5,6-epoxy-(14E)-jatrogrossidentadion (5)、2-Hydroxy jatrophone (6)。其中,化合物2、3、6均为首次从该植物中分离得到,且化合物2对PKCβ具有一定的抑制作用。     

龙眼独活中的一个新二萜成分

从四川产木属(Aralia)草本植物龙眼独活(Aralia fargesii Franch.)根茎的石油醚提取部分分离得到4个二萜化合物,根据理化性质测定和各种光谱(IR、EI-MS、HREI-MS、1H-NMR、13C-NMR和HMQC)数据分析,它们的结构分别鉴定为17-acetoxy-16α-ent-kauran-19-oic acid (1), ent-pimara-8(14),15-dien-19-oic acid (2), 16α-hydroxy-(-)-kauran-19-oic acid (3) 和16α-17-dihydroxy-ent-kauran-19-oic acid (4).化合物1为新化合物,3为首次从该属植物中分离得到,2～4为首次从龙眼独活中分离得到.     

大瑶山甜茶正丁醇部位化学成分研究

目的:研究大瑶山甜茶正丁醇部位中的二萜类化学成分,为探索其活性物质奠定基础。方法:采用95%乙醇提取药材,提取液回收至无醇味后溶于水中,依次用石油醚、乙酸乙酯和正丁醇萃取,减压干燥后获得相应萃取物,综合运用各种色谱技术对正丁醇萃取物进行分离纯化,获取二萜类化合物,通过NMR对得到的化合物进行结构鉴定。结果:从大瑶山甜茶中分离得到10个二萜类化合物,分别鉴定为7β, 17-dihydroxy-16β-ent-kauran-19-oic acid 19-O-β-D-glucopyranoside ester (1), 7β, 17-dihydroxy-entkaur-15-en-19-oic acid 19-O-β-D-glucopyranoside ester (2), 13-[(O-β-D-glucopyranosyl)oxy]ent-kaur-16-en-19-oic acid 2-O-β-Dglucopyranosyl-β-D-glucopyranosyl ester (3), 12-α-[(2-O-β-D-glucopyranosyl-β-Dglucopyranosyl)oxy]ent-kaur-16-en-19-oic acidβ-Dglucopyranosyl ester (4), glaucocalyxin G (5),β-D-glucopyranosyl 17-hydroxy-ent-kauran-19-oate-16-O-β-D-glucopyranoside (6),cussoracosides E (7), 17-O-β-D-glucopyranosyl-16α-ent-kauran-19-oic acid (8),cussovantoside A (9),cussovantoside C (10)。结论:化合物1-10首次从大瑶山甜茶中分离得到。     

宽叶金粟兰的化学成分研究

为研究宽叶金粟兰(Chloranthus henryi Hemsl)的化学成分及部分化合物体外抗炎活性。本研究采用反复硅胶、ODS、Sephadex LH-20凝胶等色谱技术进行分离纯化,通过NMR以及高分辨质谱等现代波谱学技术鉴定化合物的结构,并对部分化合物进行抑制脂多糖诱导RAW 264.7细胞释放NO活性的测定。从宽叶金粟兰的二氯甲烷部位中分离得到19个化合物,分别鉴定为:atractylenolid III(1)、(1E,4Z)-8-hydroxy-6-oxogermacra-1(10),4,7(11)-trieno-12,8-lactone(2)、curcuzederone(3)、curcolonol(4)、(1R,3S,5S,8S,10R)-14-acetylshizukanolide(5)、ent-8(9)-pimarene-20-hydroxy-16-nor-15-oic acid(6)、labda-8(17),13-dien-15,12R-olid-19-oic acid(7)、(11E)-(4S,5R,9S,10S)-15,16-bisnor-13-oxo-8(17),11-labdadien-19-ol(8)、14(15)-bisnor-13-oxolabd-8(17),11(E)-dien-19-oic acid(9)、guaianediol(10)、N-trans-cinnamoyltyramine(11)、N-benzoyl-L-phenylalaninyl-N-benzoyl-L-phenylalaninate(12)、N(N′-benzoyl-S-phenylala ninyl)-S-phenylalaninol benzoate(13)、N-2-phenylethylcinnamamide(14)、N-trans-cumaroiltiramina(15)、5,7,4′-trimethoxyflavanone(16)、2-propenoic acid-3-phenyl-methyl ester(17)、trans-cinnamic acid(18)、trans-p-hydroxycinnamic acid ethyl ester(19)。其中化合物5～19为首次从该种植物中分离得到,化合物7～10、12和13为首次从金粟兰属植物中分离得到。在体外NO生成抑制活性测试发现,当浓度为10μmol/L时,化合物2的NO抑制率为58.74%±8.17%,表现出较好的抗炎活性。     

黄桐枝叶的化学成分研究

为研究黄桐(Endospermum chinense Benth.)的化学成分,运用柱层析等分离纯化方法从黄桐枝叶中分离得到13个化合物:pubinernoid A(1)、(E)-linalool-1-oic acid(2)、(+)-去氢催吐萝芙木醇(3)、3α-hydroxy-5,6-epoxy-7-megastigmen-9-one(4)、齐墩果酸(5)、3-羰基齐墩果酸(6)、3-oleana-9(11),12-dien-28-oic acid(7)、甘五酸(8)、altissimanin C(9)、7-羟基-β-谷甾醇(10)、丁香脂素(11)、ficusesquilignan A(12)、ficusesquilignan B(13)。其中化合物7为新天然产物,化合物1~4、8~13为首次从该属植物中分离得到。     

毛姜花的降二萜成分研究

从毛姜花(Hedychium villosum Wall.)中分离得到3个降二萜化合物,通过波谱学方法分别鉴定为14,15,16-trinorlabda-8(17),11-(E)dien-13-carboxylic acid (1),13,14,15,16-tetranorlabda-8(17)-en-12-carboxylic acid (2),(E)-15,16-dinorlabda-8(17),11-dien-13-one (3),其中1为新化合物,本文首次报道了化合物2的波谱数据.     

肋果茶中的萜类化学成分研究

从肋果茶(Sladenia celastrifolia)95％乙醇提取物的乙酸乙酯部位中分离得到15个萜类化合物,经波谱学方法分别鉴定为sladeniafolin A(1),grasshopper ketone (2),(3S,5R,6S,7E,9R) -7-megastigmene-3,6,9-triol (3),hedytriol (4),(3S,5R,6R,7E,9R) -3,5,6,9-tetrahydroxy-7-megastigmene(5),1′S*,4′R*-8-(4′-hydroxy-2′,6′,6′-trimethylcyclohex-2-enyl)-6-methyloct-3E,5E,7E-trien -2-one (6),2α,3α,19α,23-tetrahydroxyurs-12-en-28-oic acid (7),2α,3β,19α,23-tetrahydroxyurs-12-en-28-oic acid(8),pomolic acid(9),3-O-acetyl pomolic acid(10),ursaldehyde (11),camarolide (12),3β-hydroxyurs-11-en-13β(28) -olide (13),3β-hydroxy -11α,12α-epoxy-urs-13β,28-olide (14)和28-0-β-D-glucopyranosyl euscaphic acid (15).以上化合物均首次从该植物中分离得到,其中1为新的C9裂环烯醚萜.     

中药王不留行化学成分的研究

从河北产麦蓝菜(Vaccaria segetalis(Neck)Garcke.)的种子王不留行中分离得到5个化合物,经波谱分析和化学方法分别鉴定为:Tetracosanoic acid(1),E-3-phenyl-2-Propenoic acid(2),stigmast-7,22-dien-3-ol(3),stigmast-7,22-dien-3-ol 3β-O-[β-D-glucopy-ranoside](4),9,12-octadecadienoic acid N-(2-hydroxyethyl)(5)。以上各化合物都是首次从该植物中分得。化合物5为首次从天然界分得。     

离舌橐吾中艾里莫酚烷型倍半萜类化学成分的研究

为分析菊科橐吾属植物离舌橐吾Ligularia veitchiana(Hemsl.)Greenm中艾里莫酚烷型倍半萜类的化学成分,并对其进行抗肿瘤活性研究,实验综合运用硅胶柱色谱、反相硅胶柱色谱以及制备型高效液相等色谱方法,从其根茎的95%乙醇提取物的乙酸乙酯部位中分离得到了13个艾里莫酚烷型倍半萜类化合物,根据化合物的理化性质及其波谱学数据鉴定为:eremophilenolide(1),eremophila-7(11),9-dien-8-one(2),eremophil-6-en-11-ol(3),8-oxo-eremophil-6-en-11-one(4),(6α,8α)-6-hydroxyeremophil-7(11)-en-12,8-olide(5),8β-hydroxyeremophil-7(11)-en-12,8α-olide(6),6β-hydroxy-8α-methoxyeremophil-7(11)-12,8β-olide(7),2α-hydroxyeremophil-11-en-9-one(8),6β-methoxy-8β-hydroxyeremophil-7(11)-en-12,8α-olide(9),6β-hydroxyeremophil-7(11)-en-12,8β-olide(10),6β-hydroxy-8β-methoxyeremophil-7(11)-12,8α-olide(11), 6β,8β-dihydroxyeremophil-7(11)-en-12,8α-olide(12)和6β,8α-dihydroxyeremophil-7(11)-en-12,8β-olide(13)。其中,化合物5和10、7和11～13为三对非对映异构体。除化合物3和5外,所有化合物均为首次从该植物中分离得到。运用MTT法对所有化合物进行体外抗肿瘤细胞活性的筛选,结果表明其对胃癌细胞HGC-27和宫颈癌细胞Caski均未显示细胞毒作用。     

大叶桃花心木根的化学成分研究

为了解大叶桃花心木(Swietenia macrophylla King)的化学成分,从其根的乙醇提取物中共分离得到13个化合物,经理化性质和波谱分析,分别鉴定为1,5-dihydroxyxanthone(1)、1,6-dihydroxy-5-methoxyxanthone(2)、euxanthone(3)、1,2-dimethoxyxanthone(4)、(+)儿茶素(5)、(+)sesamin(6)、bis-(2-ethylhexyl)phthalate(7)、3-oxotirucalla-7,24-dien-21-oic acid(8)、(20S)-3β-acetoxy-24-methylenedam-maran-20-ol(9)、cycloeucalenol(10)、β-谷甾醇(11)、7-deacetoxy-7-oxogedunin(12)和7-deacetoxy-7α-hydroxygedunin(13),其中化合物1~4、6~10和13为首次从桃花心木属植物中分离得到,且化合物4对乙酰胆碱酯酶具有一定的抑制活性。     

Diterpenoids from the pericarp of Platycladus orientalis

Eight labdane-type diterpenes, 7beta,13S-dihydroxylabda-8(17),14-dien-19-oic acid (1), 12R,15-dihydroxylabda-8(17),13E-dien-19-oic acid (3c), 12R,15-dihydroxylabda-8(17),13Z-dien-19-oic acid (3d), 12R,13R,14S-trihydroxylabda-12,15-epoxy-8(17)-en-19-oic acid (4a), 12S,13S,14R-trihydroxylabda-12,15-epoxy-8(17)-en-19-oic acid (4b), 15-hydroxy-12-oxolabda-8(17),13E-dien-19-oic acid (5), 14R,15-dihydroxylabda-8(17),12Z-dien-19-oic acid (7a) and 14S,15-dihydroxylabda-8(17),12Z-dien-19-oic acid (7b), along with 20 known diterpenoids, were isolated from the pericarp of Platycladus orientalis. Their structures were unambiguously elucidated by NMR spectroscopic and single crystal X-ray diffraction analyses, as well as via chemical correlation conversion. NMR spectroscopic data of known isomers 8c and 8d were reported as a supplement to existing data.     

石山巴豆枝叶的化学成分研究

石山巴豆( Croton euryphyllus)为大戟科( Euphorbiaceae)巴豆属( Croton)植物,主要分布于西南各省的岩溶石山地区,民间用于杀虫和治疗跌打损伤。为了阐明其化学物质基础,该研究采用硅胶柱层析、Sephadex LH-20、HPLC等方法对石山巴豆枝叶醇提物进行分离纯化。结果表明：共分离得到16个化合物,分别鉴定为异毛叶巴豆萜(1), jatrophoidin (2),山藿香定(3),异山藿香素(4),山藿香素(5),赖百当-13-烯-8,15-二醇(6),7-酮基-β-谷甾醇(7),(22E)-5α,8β-表二氧麦角甾-6,22-二烯-3β-醇(8),豆甾烷-4-烯-6β-醇-3-酮(9),齐墩果烷-12-烯-2α,3β-二醇(10),东莨菪内酯(11),催吐萝芙木醇(12), lyratol F (13),罗布麻酚A (14),芹菜素(15),金色酰胺醇酯(16)。所有化合物均为首次从该植物中分离得到,其中化合物8－16为首次从巴豆属中发现。     

Triterpenoids from Sanguisorba officinalis

Seven triterpenoids, i.e., 3beta-[(alpha-L-arabinopyranosyl)oxy]-19beta-hydroxyurs-12,20(30)-dien-28-oic acid (1), 3beta-[(alpha-L-arabinopyranosyl)oxy]-urs-11,13(18)-dien-28-oic acid beta-D-glucopyranosyl ester (2), 2alpha,3alpha,23-trihydroxyurs-12-en-24,28-dioic acid 28-beta-D-glucopyranosyl ester (3), 3beta-[(alpha-L-arabinopyranosyl)oxy]-urs-12,19(20)-dien-28-oic acid (4), 3beta-[(alpha-L-arabinopyranosyl)oxy]-urs-12,19(29)-dien-28-oic acid (5), 3beta-[(alpha-L-arabinopyranosyl)oxy]-19alpha-hydroxyolean-12-en-28-oic acid (6), 2alpha,3beta-dihydroxy-28-norurs-12,17,19(20),21-tetraen-23-oic cid (7), together with three known ones (8-10), were isolated from the roots of Sanguisorba officinalis. Their structures were determined by spectroscopic and chemical methods. Compounds 7 and 10 showed marginal inhibition activity against the growth of tumor cell lines.     

Diterpenoids and triterpenoids from Euphorbia guyoniana

Two new compounds with tigliane and cycloartane skeletons: 4,12-dideoxy(4alpha)phorbol-13-hexadecanoate (1) and 24-methylenecycloartane-3,28-diol (2), respectively, in addition of four known diterpenoids and 13 triterpenoids: 3-benzoyloxy-5,15-diacetoxy-9,14-dioxojatropha-6(17),11-diene (4), ent-abieta-8(14),13(15)-dien-16,12-olide (5), ent-8alpha,14alpha-epoxyabieta-11,13(15)-dien-16,12-olide (6), ent-3-hydroxyatis-16(17)-ene-2,14-dione (7), 3beta-hydroxytaraxer-14-en-28-oic acid (8), beta-sitosteryl-3beta-glucopyranoside-6'-O-palmitate (9), multiflorenyl acetate (10), multiflorenyl palmitate (11), peplusol (12), 24-methylenecycloartanol (3), lanosterol (13), euferol (14), butyrospermol (15), cycloartenol (16), obtusifoliol (17), cycloeucalenol (18) and beta-sitosterol (19), were isolated from the roots of Euphorbia guyoniana. Their structures were established on the basis of physical and spectroscopic analysis, including 1D and 2D homo- and heteronuclear NMR experiments (COSY, HSQC, HMBC and NOESY) and by comparison with the literature data.     

Novel antibacterial diterpenoids from Larix chinensis Beissn

Two novel labdane-type diterpenoids, butanedioic acid mono[(13S)-13-hydroxylabda-8(17),14-dien-19-yl] ester (1) and butanedioic acid bis[(13S)-13-hydroxylabda-8(17),14-dien-19-yl] ester (2), along with the eleven known diterpenoids 3-13 and three other known compounds, were isolated from the bark of Larix chinensis. Their structures were elucidated both spectroscopically and chemically. The major diterpenoids 1-9, 11, and 13, as well as the very abundant phenolic compound 16, were subjected to antibacterial and cytotoxic bioassays. Compounds 7 and 9 showed remarkable in vitro inhibition of Staphylococcus aureus and S. epidermidis (MIC = 37-73 microM).     

Anti-tumor promoting diterpenes from the stem bark of Thuja standishii (Cupressaceae).

Three new labdane-type diterpenoids, labda-8(17),13-dien-15,12R-olid-19-oic acid (1), 12S-hydroxylabda-8(17),13(16),14-trien-19-oic acid (2) and 13-ethoxylabda-8(17),11,14-trien-19-oic acid (3), along with known diterpenoids, trans-communic acid (4), totarol (5), 12-methoxyabieta-8,11,13-trien-11-ol (6), and 7 alpha,8 alpha-epoxy-6 alpha-hydroxyabieta-9(11),13-dien-12-one (7) were isolated from the stem bark of Thuja standishii. The structures of 1--3 were established by spectroscopic methods and chemical conversion. These compounds together with standishinal (8), 12-hydroxy-6,7-seco-abieta-8,11,13-trien-6,7-dial (9) and 6 alpha-hydroxysugiol (10) were tested for their inhibitory effects on Epstein--Barr virus early antigen (EBV-EA) activation induced by 12-O-tetradecanoylphorbol-13-acetate (TPA), as a test for potential cancer chemopreventive agents. Compound 10 showed strong inhibitory effect on EBV-EA induction (100% inhibition at 1000 mol ratio/TPA), and compounds 2 and 6 showed moderate inhibitory effects on EBV-EA induction. In addition, 15-oxolabda-8(17),11Z,13E-trien-19-oic acid (11) was found to exhibit the anti-tumor promoting activity in two-stage mouse skin carcinogenesis test using 7,12-dimethylbenz[a]anthracene and TPA.     

ent-Clerodane diterpenes and other constituents from the liverwort Adelanthus lindenbergianus (Lehm.) Mitt

Eleven ent-clerodanes, 13-hydroxy-cis-ent-cleroda-3,14-diene, 15-hydroxy-cis-ent-cleroda-3,13(E)-diene, 1beta,12:15,16-diepoxy-cis-ent-cleroda-13(16),14-dien-18alpha,6alpha-olide, 8beta,12:15, 16-diepoxy-cis-ent-cleroda-13(16),14-dien-18alpha,6alpha-olide, 1beta,16:15,16-diepoxy-cis-ent-cleroda-12,14-dien-18alpha,6alpha-olide, 7beta,12:8beta,12-diepoxy-15-hydroxy-cis-ent-cleroda-13-en-16,15:18alpha,6alpha-diolide, 7beta,12:8beta,12-diepoxy-16-hydroxy-cis-ent-cleroda-13-en-15,16:18alpha,6alpha-diolide, 1alpha-acetoxy-8beta,12-epoxy-15-hydroxy-cis-ent-cleroda-13-en-16,15:18alpha,6alpha-diolide, 1beta,12-epoxy-16-hydroxy-cis-ent-cleroda-13-en-15,16:18alpha,6alpha-diolide, 8beta,12-epoxy-15-hydroxy-trans-cleroda-13-en-16,15:18alpha,6alpha-diolide, 8beta,12-epoxy-16-hydroxy-trans-cleroda-13-en-15,16:18alpha,6alpha-diolide along with the known clerodane diterpenes anastreptin and orcadensin have been isolated from the liverwort Adelanthus lindenbergianus (Lehm.) Mitt. Furthermore, three eudesmane sesquiterpenes together with the known (-)-1beta,10-epoxyaristolan, 3,4-seco-4(23),20(29)-lupadien-3,28-dicarboxylic acid dimethyl ester and two acetophenone derivatives were identified by spectroscopic methods, essentially MS and NMR experiments.     

Differential metabolism of diastereoisomeric diterpenes by Preussia minima,found as endophytic fungus in Cupressus lusitanica

The plant diastereoisomeric diterpenes ent-pimara-8(14)-15-dien-19-oic acid, obtained from Viguiera arenaria, and isopimara-8(14)-15-dien-18-oic acid, isolated from Cupressus lusitanica, were distinctly functionalized by the enzymes produced in whole cell cultures of the fungus Preussia minima, isolated from surface sterilized stems of C. lusitanica. The ent-pimaradienoic acid was transformed into the known 7β-hydroxy-ent-pimara-8(14)-15-dien-19-oic acid, and into the novel diterpenes 7-oxo-8 β-hydroxy-ent-pimara-8(14)-15-dien-19-oic and 7-oxo-9β-hydroxy-ent-pimara-8(14)-15-dien-19-oic acids. Isopimara-8(14)-15-dien-18-oic acid was converted into novel diterpenes 11α-hydroxyisopimara-8(14)-15-dien-18-oic acid, 7β,11α-dihydroxyisopimara-8(14)-15-dien-18-oic acid, and 1β,11α-dihydroxyisopimara-8(14)-15-dien-18-oic acid, along with the known 7β-hydroxyisopimara-8(14)-15-dien-18-oic acid. All compounds were isolated and fully characterized by 1D and 2D NMR, especially ¹³C NMR. The diterpene bioproduct 7-oxo-9β-hydroxy-ent-pimara-8(14)-15-dien-19-oic acid is an isomer of sphaeropsidin C, a phytotoxin that affects cypress trees produced by Shaeropsis sapinea, one of the main phytopathogen of Cupressus. The differential metabolism of the diterpene isomers used as substrates for biotransformation was interpreted with the help of computational molecular docking calculations, considering as target enzymes those of cytochrome P450 group.     

类芒齿黄芪地下部分化学成分研究

为了解类芒齿黄芪( Astragalus camptodontoides)主要化学成分,从其地下部分甲醇提取物的乙酸乙酯部位分离出19个单体化合物,通过现代波谱分析及理化性质等手段分别鉴定为异补骨脂黄酮(1),4′-hydroxy-isolonchocarpin (2),5-去氧山豆根黄酮(3),shinflavanone (4),khonklonginols H (5),4′-O-methylpreglabridin (6),3′-hydroxy-4′-O-methylglabridin (7),4′-O-methylglabridin (8),8-prenyl-phaseollinisoflavan (9),xambioona (10),光甘草酚(11),粗毛甘草素H (12),methylnissolin (13),邻苯二甲酸异丁酯(14),邻苯二甲酸丁酯异丁酯(15),β-谷甾醇(16),胡萝卜苷(17),齐墩果酸(18),(2S,3S,4R,9E)-1,3,4-trihydroxy-2-[(2′R)-2′- hydr-oxytetraco-sanoylamino]-9-octadecene (19)。化合物1~19均为首次从该植物中获得,化合物1~7为首次从黄芪属(Astraga-lus)植物中分离得到。     

New natural diterpene acids from Juniperus communis

Three new diterpene acids have been isolated from the leaves of Juniperus communis and their structures, elucidated by spectroscopic methods, were identified as 7-oxo-13-epi- pimara-8,15-dien-18-oic acid, 7α-hydroxysandaracopimaric acid and (14 S)-14,15-dihydroxylabda- 8(17),13(16)-dien-19-oic acid. Biflavonyls, fatty acids and diterpenoids with known structures were also isolated.