四瓣崖摩化学成分研究

从楝科崖摩属植物四瓣崖摩的树枝中分离得到14个化合物,运用波谱学方法分别鉴定为:22ξ-hydroxytirucalla-7,24-dien-3,23-dione(1)、dymacrin D(2)、泽屋萜(3)、α-菠菜甾醇(4)、8-hydroxy-6-methoxy-3-pentylisocoumarin(5)、ichenxanthone(6)、10-oxo-isodauc-3-en-15-al(7)、(+)-ent-ficusol(8)、3-甲氧基-4-羟基苯甲酸甲酯(9)、香草醛(10)、2,4-二羟基-3,6-二甲基苯甲酸甲酯(11)、2-羟基-4-甲氧基-6-丙基苯甲酸甲酯(12)、2,4-二羟基-6-甲基苯甲酸甲酯(13)和琥珀酸甲酯(14),以上化合物均为首次从崖摩属植物中分离得到。采用Elman比色法对全部化合物进行活性测试,结果表明化合物11对乙酰胆碱酯酶具有抑制活性。     

糙叶五加正丁醇萃取部位抗炎活性成分研究

本文对糙叶五加果实正丁醇萃取物的抗炎活性成分进行研究。采用硅胶柱色谱、C_(18)柱色谱、LH-20型羟丙基葡聚糖凝胶(Sephadex LH-20)柱色谱、半制备液相及重结晶等方法进行分离纯化,利用波谱分析结合理化性质鉴定化合物的结构。从糙叶五加果实正丁醇萃取部位中分离鉴定出17个化合物,分别为槲皮素-3-O-β-D-吡喃葡萄糖苷(1)、槲皮素-3-O-β-D-吡喃半乳糖苷(2)、芦丁(3)、1,3-双咖啡酰奎宁酸(4)、1,4-双咖啡酰奎宁酸(5)、1,5-双咖啡酰奎宁酸(6)、3,4-双咖啡酰奎宁酸(7)、3,5-双咖啡酰奎宁酸(8)、4,5-双咖啡酰奎宁酸(9)、绿原酸甲酯(10)、(2E,6S)-1-羟基-2,6-二甲基-2,7-辛二烯-6-β-D-吡喃葡萄糖苷(11)、(2Z,6R)-6-羟基-2,6-二甲基-2,7-辛二烯-1-β-D-吡喃葡萄糖苷(12)、(2Z,6R)-1-羟基-2,6-二甲基-2,7-辛二烯-6-β-D-吡喃葡萄糖苷(13)、(2E,6R)-6-羟基-2,6-二甲基-2,7-辛二烯-1-β-D-吡喃葡萄糖苷(14)、(2E,6R)-1-羟基-2,6-二甲基-2,7-辛二烯-6-β-D-吡喃葡萄糖苷(15)、(-)-(3S,4S,6R)-3,6-二羟基-1-薄荷烯6-O-β-D-吡喃葡萄糖苷(16)、(-)-(3S,4S,6R)-3,6-二羟基-1-薄荷烯3-O-β-D-吡喃葡萄糖苷(17)。化合物11、16、17为首次从五加科植物中分离得到;化合物13～15为首次从五加属植物中分离得到;除化合物1～9之外,其他化合物均为首次从该种植物中分离得到。其中,在0～80μM的浓度范围内,被测试化合物均无明显的细胞毒性,化合物10和16具有较好的NO抑制活性且呈剂量相关;化合物6和17表现出了适度的NO抑制活性;其它被测试化合物具有微弱的或者无NO抑制效果。     

钩藤化学成分的研究

从钩藤(Uncaria rhynchophylla(Miq.)Jacks.)带钩茎枝分离得到18个化合物,通过波谱学等方法鉴定为乌苏酸(1),27,28-二羧基乌苏酸(2),3β,6β,19α-三羟基乌苏酸(3),noreugenin(4),单棕榈酸甘油酯(5),3-酮-6β,19α-二羟基乌苏酸(6),sumresinolic(7),scopoletin(8),3β,6β,19α,24-四羟基乌苏酸(9),6-酮-3β,19α,23-三羟基齐墩果酸(10),3β,19α,24-三羟基乌苏酸(11),23-醛-3β,6β,19α-三羟基乌苏酸(12),钩藤苷元C(13),β-谷甾醇(14),胡萝卜苷(15),丁香酸(16),cleomiscosin D(17),cleomiscosin B(18).其中化合物4,7,9～11,17,18为首次从该植物中分离得到.     

光叶兔儿风的化学成分研究

利用正反相硅胶、凝胶(Sephadex LH-20)等多种柱色谱法,对光叶兔儿风化学成分进行分离纯化,并根据理化性质和波谱数据进行结构鉴定。结果表明:已分离得到17个化合物,分别鉴定为蒲公英甾醇乙酸酯(1),三十二碳烯(2),β-谷甾醇(3),大黄酚(4),扇醇棕榈酸酯(5),亚麻酸甲酯(6),亚油酸(7),植物醇(8),[24S]-豆甾-4烯-3-酮(9),植物烯醛(10),白桦脂酸(11),13-羰基-十八碳二烯酸(12),E-7,9-11-羰基-棕榈酸(13),蒲公英酸(14),3β-羟基-胆甾-5-烯(15),环氧树脂烯(16),28-O-月桂酸酯白桦醇(17)。化合物1～17均为首次从该植物中分离得到。     

密花荚蒾中两个新的环烯醚萜

利用现代色谱分离手段,从荚蒾属植物密花荚蒾(Viburnum congestum)枝叶的95%乙醇提取物中分离得到15个化合物,根据理化性质及现代波谱技术鉴定其结构为密花荚蒾甲素(1)、密花荚蒾乙素(2)、adoxoside(3)、2'-(E)-p-coumaroyldihydropenstemide(4)、3β,23-二羟基-乌苏烷-12-烯-28-酸(5)、ilelatifol A(6)、11-oxoerythrodiol(7)、花旗松素(8)、儿茶素(9)、表儿茶素(10)、表儿茶素-[7,8-bc]-4β-(4-羟基苯)-二氢-2(3H)-吡喃酮(11)、东莨菪素(12)、对羟基苯甲酸甲酯(13)、(E)-对香豆酸乙酯(14)、(E)-对香豆酸(15)。其中,化合物1和2为新化合物,化合物5、6、11、12为首次从荚蒾属植物中分离得到。     

棉毛橐吾根茎中化学成分研究

采用硅胶、Sephadex LH-20凝胶、Toyopearl HW-40凝胶及Diaion HP-20树脂等色谱方法从云南丽江棉毛橐吾中分离得到化合物18个,通过理化手段及波谱技术分别鉴定为:呋喃艾里莫芬-14β,6α-内酯(1)、β-谷甾醇(2)、惕格酸(3)、棕榈酸(4)、十九烷酸甲酯(5)、艾里莫芬-7(11)-烯-12,8α(14β,6α)-二内酯(6)、8β-甲氧基艾里莫芬-7(11)-烯-12,8α(14β,6α)-二内酯(7)、1-O-十六烷酰基甘油酯(8)、8β-羟基艾里莫芬-7(11)-烯-12,8α(14β,6α)-二内酯(9)、对羟基桂皮酸甲酯(10)、对羟基苯乙酮(11)、伞形花内酯(12)、3,4-二羟基苯乙酮(13)、胡萝卜苷(14)、1,5-二咖啡酰奎宁酸(15)、对羟基桂皮酸(16)、咖啡酸(17)及七叶内酯(18),其中化合物4~5,8,10,13,15及17,18为首次从该植物中分离得到。     

荫生鼠尾草植物中的三萜类化学成分研究

从采自陕西省太白山的唇形科(Labiatae)鼠尾草属(Salvia Linn.)植物荫生鼠尾草(Salvia umbratica Hance)丙酮提取物中分离得到14个五环三萜类化合物,并用现代波谱技术(MS、1H NMR、13C NMR、DEPT)和化学方法进行结构鉴定.结果显示:14个化合物分别为β-香树脂醇(1)、α-香树脂醇(2)、2α,3α-二羟基齐墩果-12-烯-28-酸(3)、3-氧-乌苏-12-烯-28-酸(4)、2α,3β-二羟基齐墩果-12-烯-28-酸(5)、3β,19-二羟基齐墩果-12-烯-28-酸(6)、齐墩果酸(7)、2α,3β-二羟基乌苏-12-烯-28-酸(8)、3β-羟基-11α-甲氧基-齐墩果-12-烯(9)、3β-羟基-11α-甲氧基-乌苏-12-烯(10)、3β,11α-二羟基-齐墩果-12-烯(11)、3β,11α-二羟基-乌苏-12-烯(12)、乌苏酸(13)、3β-羟基齐墩果-10,12-二烯(14).实验结果表明五环三萜类化合物是该植物中的主要成分.     

药囊花茎叶的化学成分研究

药囊花（Cyphotheca montana Diels）茎叶的乙醇提取物具有抗菌活性,进一步的活性追踪表明活性成分在乙酸乙酯和正丁醇萃取物中,我们从这两种萃取物中共分离鉴定出9个化合物,其结构通过波谱分析等分别鉴定为：槲皮素-3-O-α-L-鼠李糖甙（1）,杨梅素-3-O-α-L鼠李糖甙（2）,山萘酚-3-（2″,6″-二-O-（E）-p-羟基苯丙烯酰-β-D-吡喃葡萄糖甙（3）,3,3′-O-二甲基逆没食子酸-4-O-β-D-吡喃葡萄糖甙（4）,槲皮素（5）,2α,3β,19α,23-四羧基乌苏-12-烯-28-酸-28-0-β-D吡喃葡萄糖甙（6）,乌苏酸（7）,β-谷甾醇（8）和胡萝卜甙（9）,这些化合物均为首次从我国该特有单种属植物中分离得到。     

绿槽枝衣的化学成分

从地衣绿槽枝衣（Sulcaria virens）中分离得到一个新的亚油酸异丙叉衍生物,通过波谱学方法包括2D-NMR确定其化学结构为：9,10-O-异丙叉基-（12Z）-十八碳烯酸（1）。同时还得到其它12个已知化合物：（9Z,12Z）-十八碳二烯酸（2）,扁枝衣二酸（3）,（R）-松萝酸（4）,枕酸甲酯（5）,黑茶渍素（6）,virensic acid（7）,abieslactone（8）,3α-羟基羊毛甾-7,24-二烯-26,23R-内酯（9）,蒲公英赛醇（10）,蒲公英赛酮（11）,（22E,24R）-5α,8α-过氧麦角甾-6,22-二烯-3β-醇（12）和2,2′-四氢角鲨烯（13）。     

望谟崖摩枝叶的化学成分及其抗炎活性研究

为寻找传统药用植物望谟崖摩Amoora ouangliensis中的活性成分,采用色谱分离方法进行化合物分离,并通过波谱数据分析方法鉴定化合物的结构。从望谟崖摩枝叶中分得9个化合物,分别鉴定为cabralealactone(1)、cabraleahydroxylactone(2)、eichlerialactone(3)、金色酰胺醇酯(aurantiamide acetate)(4)、金色酰胺醇(benzenepropanamide)(5)、xylogranatinin(6)、丁香醛(7)、cycloartane-3β,24,25-triol(8)和24(R)-19-cyclolanost-3-one-24,25-diol(9)。在脂多糖诱导的RAW264.7细胞炎症模型中,化合物2~4和9显示出一定的活性。上述化合物均为首次从该植物中分得,化合物2~8为首次从该属植物中分得。     

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.     

ent-Labdane diterpenes from the aquatic plant Potamogeton pectinatus

Four new ent-labdane diterpenes were isolated from the freshwater aquatic plant Potamogeton pectinatus, together with two known furano-ent-labdanes. The new compounds were assigned the structures methyl-15,16-epoxy-12(R)-acetoxy- 8(17), 13(16),14-ent-labdatrien-19-oate,15,16-epoxy-12(R)-acetoxy-8(17), 13(16),14-ent-labdatrien-19-oic acid, 8(17),13-ent-labdadien-15 --> 16-lactone-19-oic acid and 16-hydroxy-8(17),13-ent-labdadien-15,16-olid-19-oic acid by spectroscopic means. Some of these labdanes showed a strong algicidal activity against Raphidocelis subcapitata.     

Plant growth regulation activity of steviol and derivatives

This work describes the preparation of tetracyclic diterpenoids and determination of their plant growth regulator properties. Stevioside (2) was used as starting material and the derivatives 13-hydroxy-ent-kaur-16-en-19-oic acid (steviol, 3), ent-7alpha,13-dihydroxy-kaur-16-en-19-oic acid (4), 13-hydroxy, ent-kaur-16,17-epoxi-19-oic acid (steviol epoxide, 5), 17-hydroxy-16-ketobayeran-19-oic acid (17-hydroxyisosteviol, 6), 17-hydroxy-16-hydroxyiminobayeran-19-oic acid (7), 16-ketobayeran-19-oic acid (isosteviol, 9), 16,17-dihydroxybeyeran-19-oic acid (8), and 16-hydroxyiminobayeran-19-oic acid (isosteviol oxime, 10) were obtained by simple chemical procedures. Another derivative, ent-7alpha,13-dihydroxycaur-15-en-19-oic acid (4), was obtained by biotransformation of steviol (3) by Penicillium citrinum. In order to determine the plant growth regulator activity the compounds were submitted to the lettuce hypocotyl and barley aleurone bioassays. All compounds showed significant activities in both bioassays. Steviol (3) and isosteviol (9) were also tested in field-grown grapes resulting in an increase in berry weight and size.     

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.     

Microbial transformation of neoandrographolide by Mucor spinosus (AS 3.2450)

Microbial transformation of neoandrographolide (1), was performed by Mucor spinosus (AS 3.2450). Ten metabolites were obtained and identified as 14-deoxyandrographolide (2), 17,19-dihydroxy-8,13-ent-labdadien-16,15-olide (3), 3,14-dideoxyandrographolide (4), 7β-hydroxy-3,14-dideoxyandrographolide (5), 17,19-dihydroxy-7,13-ent-labdadien-16,15-olide (6), 8(17),13-ent-labdadien-16,15-olid-19-oic acid (7), 8α,17β-epoxy-3,14-dideoxyandrographolide (8), 8β,17,19-trihydroxy-ent-labd-13-en-16, 15-olide (9), phlogantholide-A (10), 19-[(β-d-glucopyranosyl)oxy]-19-oxo-ent-labda-8(17),13-dien-16,15-olide (11) by spectroscopic and chemical means. Among them, products 3, 5, 6, 8 and 9 were characterized as new compounds. The inhibitory effects of compounds 1–11 on nitric oxide production in lipopolysaccharide-activated macrophages were evaluated and their preliminary structure–activity relationships (SAR) were discussed.     

Terpenes with antimicrobial activity from Cretan propolis

Five terpenes, the diterpenes: 14,15-dinor-13-oxo-8(17)-labden-19-oic acid and a mixture of labda-8(17),13E-dien-19-carboxy-15-yl oleate and palmitate as well as the triterpenes, 3,4-seco-cycloart-12-hydroxy-4(28),24-dien-3-oic acid and cycloart-3,7-dihydroxy-24-en-28-oic acid were isolated from Cretan propolis. Moreover, 18 known compounds were also isolated, seven of them for the first time as propolis components. All structures were established on the basis of spectroscopic analysis and chemical evidence. All isolated compounds were tested for antimicrobial activity against some Gram-positive and Gram-negative bacteria as well as against some human pathogenic fungi showing a broad spectrum of antimicrobial activity.     

Clerodane and labdane diterpenoids from Nuxia sphaerocephala

Seven diterpenoids including four clerodane and three labdane derivatives, (13S)-ent-7beta-hydroxy-3-cleroden-15-oic acid (1), ent-7beta-hydroxy-2-oxo-3-cleroden-15-oic acid (2), ent-2,7-dioxo-3-clero-den-15-oic acid (3), ent-18-(E)-caffeoyloxy-7beta-hydroxy-3-cleroden-15-oic acid (4) (13S)-ent-18-(E)-coumaroyloxy-8(17)-labden-15-oic acid (5), ent-18-(E)-caffeoyloxy-8(17)-labden-15-oic acid (6), ent-15-(E)-caffeoyloxy-8(17)-labden-18-oic acid (7), have been isolated from an ethyl acetate extract of the leaves of Nuxia sphaerocephala, together with 17 known compounds. 3-Oxolup-20(29)-en-30-al (3-oxolupenal) (8) and 3beta-hydroxylup-20(29)-en-30-al (3beta-hydroxy-lupenal) (9) showed the best inhibitory activity against Plasmodium falciparum with the IC(50) values between 1.55 and 4.67 microg/ml in vitro, respectively. The structure and the relative stereochemistry of the compounds were established on the basis of their spectroscopic properties. The absolute configuration at C-13 of 1 and 5 was determined by the PGME amide procedure.     

Microbial metabolism of steviol and steviol-16alpha,17-epoxide

Steviol (2) possesses a blood glucose-lowering property. In order to produce potentially more- or less-active, toxic, or inactive metabolites compared to steviol (2), its microbial metabolism was investigated. Incubation of 2 with the microorganisms Bacillus megaterium ATCC 14581, Mucor recurvatus MR 36, and Aspergillus niger BCRC 32720 yielded one new metabolite, ent-7alpha,11beta,13-trihydroxykaur-16-en-19-oic acid (7), together with four known related biotransformation products, ent-7alpha,13-dihydroxykaur-16-en-19-oic acid (3), ent-13-hydroxykaur-16-en-19-alpha-d-glucopyranosyl ester (4), ent-13,16beta,17-trihydroxykauran-19-oic acid (5), and ent-13-hydroxy-7-ketokaur-16-en-19-oic acid (6). The preliminary testing of antihyperglycemic effects showed that 5 was more potent than the parent compound (2). Thus, the microbial metabolism of steviol-16alpha,17-epoxide (8) with M. recurvatus MR 36 was continued to produce higher amounts of 5 for future study of its action mechanism. Preparative-scale fermentation of 8 yielded 5, ent-11alpha,13,16alpha,17-tetrahydroxykauran-19-oic acid (10), ent-1beta,17-dihydroxy-16-ketobeyeran-19-oic acid (11), and ent-7alpha,17-dihydroxy-16-ketobeyeran-19-oic acid (13), together with three new metabolites: ent-13,16beta-dihydroxykauran-17-acetoxy-19-oic acid (9), ent-11beta,13-dihydroxy-16beta,17-epoxykauran-19-oic acid (12), and ent-11beta,13,16beta,17-tetrahydroxykauran-19-oic acid (14). The structures of the compounds were fully elucidated using 1D and 2D NMR spectroscopic techniques, as well as HRFABMS. In addition, a GRE (glucocorticoid responsive element)-mediated luciferase reporter assay was used to initially screen the compounds 3-5, and 7 as glucocorticoid agonists. Compounds 4, 5 and 7 showed significant effects.     

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.     

Diterpenoids from Calceolaria inamoena

Four 9-epi-ent-labdanes were isolated from the aerial parts of Calceolaria inamoena. Their structures, 2beta-hydroxy-9-epi-ent-labda8(17)-13(E)dien-15-oic acid, 2beta-hydroxy-9-epi-ent-labda8(17)-13(Z)dien-15-oic acid, 2beta-hydroxy-9-epi-ent-labda8(17)-13(E)dien-15-al and 2beta-hydroxy-9-epi-ent-labda-8(17)-13(Z)dien-15-al, were established by spectroscopic methods including by analysis of 2 dimensional heteronuclear correlation experiments 1H/13C (normal and long range), and NOE and gs-sel-1D-NOESY and TOCSY of their methyl ester or acetyl derivatives.