Iridoids from Kigelia pinnata DC. fruits

From the fruits of Kigelia pinnata DC., a new furanone derivative formulated as 3-(2'-hydroxyethyl)-5-(2"-hydroxypropyl)-dihydrofuran-2(3H)-one (1), and four new iridoids named; 7-hydroxy viteoid II (2), 7-hydroxy eucommic acid (3), 7-hydroxy-10-deoxyeucommiol (4) and 10-deoxyeucommiol (5) have been isolated together with seven known iridoids, jiofuran (6), jioglutolide (7), 1-dehydroxy-3,4-dihydroaucubigenin (8), des-p-hydroxybenzoyl kisasagenol B (9), ajugol (10), verminoside (11) and 6-trans-caffeoyl ajugol (12). The structures of the isolated compounds were characterized by different spectroscopic methods.     

The potential of Cyathus africanus for transformation of terpene substrates

The insecticidal sesquiterpenes cadina-4,10(15)-dien-3-one and aromadendr-1(10)-en-9-one were administered to the fungus Cyathus africanus ATCC 35853. Biotransformation of the former produced (4R)-9α-hydroxycadin-10(15)-en-3-one, while the latter gave 2β-hydroxyaromadendr-1(10)-en-9-one, 2α-hydroxyaromadendr-1(10)-en-9-one and 10α-hydroxy-1β,2β-epoxyaromadendran-9-one. The bioconversion of santonin led to the production of two analogues, 11,13-dihydroxysantonin and the hitherto unreported 8α,13-dihydroxysantonin, while cedrol yielded 3β,8β-dihydroxycedrane and 3α,8β-dihydroxycedrane. Stemod-12-ene, a diterpene, was transformed to 2-oxostemar-13-ene, a hitherto unknown analogue with a rearranged carbon framework. When methyl betulonate, a triterpenoid belonging to the lupane family, was supplied to the fungus 18α-ursane and 18α-oleanane derivatives, namely 19β-hydroxy-3-oxo-18α-oleanan-28-oic acid and 19α-hydroxy-3-oxo-18α-ursan-28-oic acids, were generated. There are no previous reports of fungal transformation of a triterpene in which a skeletal rearrangement occurred. All substrate administration experiments were done in the presence of the terpene cyclase inhibitor chlorocholine chloride (CCC), using the single phase – pulse feed method.     

Diarylheptanoids from the rhizomes of Zingiber officinale

Seven new diarylheptanoids, i.e., (3S,5S)-3,5-diacetoxy-1,7-bis(4-hydroxy-3-methoxyphenyl)heptane, (3R,5S)-3-acetoxy-5-hydroxy-1,7-bis(4-hydroxy-3-methoxyphenyl)heptane, (3R,5S)-3,5-dihydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-7-(4-hydroxy-3-methoxyphenyl)heptane, (5S)-5-acetoxy-1,7-bis(4-hydroxy-3-methoxyphenyl)heptan-3-one, 5-hydroxy-1-(3,4-dihydroxy-5-methoxyphenyl)-7-(4-hydroxy-3-methoxyphenyl)heptan-3-one, 5-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-7-(3,4-dihydroxy-5-methoxy-phenyl)heptan-3-one and 1,5-epoxy-3-hydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-7-(4-hydroxy-3-methoxyphenyl)heptane were isolated from the rhizomes of Chinese ginger (Zingiber officinale Roscoe), along with 25 known compounds, i.e., 8 diarylheptanoids, 14 gingerol analogs, a diterpene and 2 steroids. Their structures were elucidated by spectroscopic and chemical methods.     

Alkaloids from Toddalia aculeata

Two alkaloids N-methyl-4-hydroxy-7-methoxy-3-(2,3-epoxy-3-methylbutyl)-1H-quinolin-2-one (1) and 3-(2,3-dihydroxy-3-methylbutyl)-4,7-dimethoxy-1-methyl-1H-quinolin-2-one (2a) have been isolated from CH(2)Cl(2):methanol (1:1) and methanol extracts of leaves and stems of Toddalia aculeata. Their structures along with that of 15 other compounds, of which three are isolated for the first time from genus Toddalia, were established by their detailed spectral studies including 2D NMR viz. (1)H-(1)H COSY, (1)H-(13)C COSY, and HMBC.     

马尾伸筋草化学成分及抗骨质疏松活性研究

为研究马尾伸筋草(Lycopodium fargesii Hert.)的化学成分及其抗骨质疏松活性,采用硅胶、MCI、RP-18、Sephadex LH-20柱色谱及半制备高效液相色谱对马尾伸筋草的乙醇提取物进行系统分离,从乙酸乙酯部位中得到18个化合物,综合利用NMR、HR-ESI-MS等技术,分析鉴定化合物的结构,分别鉴定为α-芒柄蜡素(1)、26-去甲-8-氧化-α-芒柄蜡素(2)、serrat-14-en-3β,21α,24-triol(3)、serrat-14-en-3β,21β,24-triol(4)、1,20-eicosanediol(5)、二十三烷(6)、glycerolmonolinoleate(7)、glyceryl linolentate(8)、3-(4′-formylphenoxy)-4-methoxybenzaldehyde(9)、芹菜素(10)、对羟基苯甲醛(11)、香草酸(12)、3-羟基-4-甲氧基苯甲酸(13)、2-羟基-1-(4-羟基-3-甲氧基-苯基)-丙基-1-酮(14)、3-甲氧基-4-羟基桂皮醛(15)、8-acetoxy-5-hydroxyumbelliprenin(16)、trans-4-hydroxy-2-nonenoic acid(17)和正十烷硫醇(18)。化合物1~18均为首次从马尾伸筋草中分离得到,其中化合物16对破骨细胞活性具有显著的抑制作用,其IC₅₀为1.98μM。     

Microbial transformation of mesterolone

The microbial transformation of mesterolone (= (1alpha,5alpha,17beta)-17-hydroxy-1-methylandrostan-3-one; 1), by a number of fungi yielded (1alpha,5alpha)-1-methylandrostane-3,17-dione (2), (1alpha,3beta,5alpha,17beta)-1-methylandrostane-3,17-diol (3), (5alpha)-1-methylandrost-1-ene-3,17-dione (4), (1alpha,5alpha,15alpha)-15-hydroxy-1-methylandrostane-3,17-dione (5), (1alpha,5alpha,6alpha,17beta)-6,17-dihydroxy-1-methylandrostan-3-one (6), (1alpha,5alpha,7alpha,17beta)-7,17-dihydroxy-1-methylandrostan-3-one (7), (1alpha,5alpha,11alpha,17beta)-11,17-dihydroxy-1-methylandrostan-3-one (8), (1alpha,5alpha,15alpha, 17beta)15,17-dihydroxy-1-methylandrostan-3-one (9), and (5alpha,15alpha,17beta)-15,17-dihydroxy-1-methylandrost-1-en-3-one (10). Metabolites 5-10 were found to be new compounds. All metabolites, except 2, 3, 6, and 7, exhibited potent anti-inflammatory activity. The structures of these metabolites were characterized on the basis of spectroscopic studies, and the structure of 5 was also determined by single-crystal X-ray-diffraction analysis.     

Metabolites from the endophytic fungus Xylaria sp. PSU-D14

Glucoside derivatives, xylarosides A (1) and B (2), were isolated from the broth extract of the endophytic fungus Xylaria sp. PSU-D14 along with two known compounds, sordaricin (3) and 2,3-dihydro-5-hydroxy-2-methyl-4H-1-benzopyran-4-one (4). The structures were assigned by spectroscopic methods. Sordaricin (3), one of the known metabolites, exhibited moderate antifungal activity against Candida albicans ATCC90028 with a MIC value of 32 microg/ml.     

Laurentixanthones A and B, antimicrobial xanthones from Vismia laurentii

A phytochemical investigation of the constituents of the roots of Vismia laurentii has resulted in the isolation of two xanthone derivatives named laurentixanthone A (1) (6-hydroxy-3,3-dimethyl-11-(3-methylbut-2-enyl)pyrano[2,3-c]xanthen-7(3H)-one) and laurentixanthone B (2) (1-hydroxy-5,6,7,8-tetramethoxyxanthone), along with 11 known compounds: 1,7-dihydroxyxanthone, vismiaquinone, vismiaquinone B, bivismiaquinone, 3-geranyloxy-6-methyl-1,8-dihydroxyanthraquinone, O(1)-demethyl-3',4'-deoxypsorospermin-3',4'-diol, 6-deoxyisojacareubin, 1,8-dihydroxy-6-methoxy-3-methylanthraquinone, kaempferol, friedelin and stigmasterol. The structures of compounds were established by means of spectroscopic methods. Furthermore, the compounds were screened for antimicrobial activities in vitro.     

鹿蹄草化学成分研究

从鹿蹄草(Pyrola callianthaH.Andres)中分离得到11个化合物,经光谱分析确定其结构为(4R)-1-四氢萘酮(1),(4S)-1-四氢萘酮(2),夹竹桃麻素(3),没食子酸(4),3,4-二羟基苯甲酸(5),鹿蹄草素(6),5-羟甲基糠醛(7),金丝桃苷(8),2″-O-没食子酰基金丝桃苷(9),鹿蹄草苷B(10),4-羟基-2,7-二甲基萘基-1-O-β-D-吡喃葡萄糖苷(11)。其中化合物1,2,3,5,6,11为首次从该植物中分离得到,化合物7为首次从该属中分离得到。     

Indole alkoloids from Nauclea officinalis with weak antimalarial activity

Five indole alkaloids (naucleofficines A-E) were isolated from the stems (with bark) of Nauclea officinalis: (E)-2-(1-beta-d-glucopyranosyloxybut-2-en-2-yl)-3-(hydroxymethyl)-6,7-dihydro-indolo[2,3-a]quinolizin-4(12H)-one (1), (E)-1-propenyl-12-beta-d-glucopyranosyloxy-2,7,8-trihydro-indolo[2,3-a]pyran[3,4-g]quinolizin-4,5(13H)-dione (2), (E)-2-(1-hydroxybut-2-en-2-yl)-11-beta-d-glucopyranosyloxy-6,7-dihydro-indolo[2,3-a]quinolizin-4(12H)-one (3), (E)-1-propenyl-4-hydroxy-2,4a,7,8,13b,14,14a-hepthydro-(4alpha,4abeta,13balpha,14abeta)indolo[2,3-a]pyran[3,4-g]quinolizin-5(13H)-one (4) and 1-(1-hydroxyethyl)-10-hydroxy-7,8-dihydro-indolo[2,3-a]pirydine[3,4-g]quinolizin-5(13H)-one (10-hydroxyangustoline) (5), together with two known compounds, naucleidinal (6) and angustoline (7). All of the structures of the seven compounds above were elucidated by spectroscopic methods including use of 1D- and 2D-NMR spectroscopic analyses. Compounds 2 and 3 are rare examples of monoterpene indole alkaloids with a glucopyranosyloxy group attached to position C-12. In vitro activity screening of the above seven compounds showed weak to moderate inhibitory activity against Plasmodium falciparum.     

Alkaloids from Portulaca oleracea L

Five alkaloids (oleraceins A, B, C, D and E) were isolated from Portulaca oleracea L., and their structures determined by spectroscopic methods as 5-hydroxy-1-p-coumaric acyl-2,3-dihydro-1H-indole-2-carboxylic acid-6-O-beta-D-glucopyranoside, 5-hydroxy-1-ferulic acyl-2,3-dihydro-1H-indole-2-carboxylic acid-6-O-beta-D-glucopyranoside, 5-hydroxy-1-(p-coumaric acyl-7'-O-beta-D-glucopyranose)-2,3-dihydro-1H-indole-2-carboxylic acid-6-O-beta-D-glucopyranoside, 5-hydroxy-1-(ferulic acyl-7'-O-beta-D-glucopyranose)-2,3-dihydro-1H-indole-2-carboxylic acid-6-O-beta-D-glucopyranoside and 8,9-dihydroxy-1,5,6,10b-tetrahydro-2H-pyrrolo[2,1-a]isoquinolin-3-one, respectively.     

Synthesis,characterization, anticancer evaluation and mechanisms of cytotoxic activity of novel 3-hydroxy-3-pyrrolin-2-ones bearing thenoyl fragment: DNA,BSA interactions and molecular docking study

In order to make a progress in discovering a new agents for chemotherapy with improved properties and bearing in mind the fact that substituted 3-hydroxy-3-pyrrolin-2-ones belong to a class of biologically active compounds, series of novel 1,5-diaryl-4-(2-thienylcarbonyl)-3-hydroxy-3-pyrrolin-2-ones were synthesized and characterized by spectral (UV–Vis, IR, NMR, ESI-MS), X-ray and elemental analysis. All compounds were examined for their cytotoxic effect on human cancer cell lines HeLa and MDA-MB 231 and normal fibroblasts (MRC-5). Four compounds, 3-hydroxy-1-(p-tolyl)-4-(2-thienylcarbonyl)-5-(4-chlorophenyl)-2,5-dihydro-1H-pyrrol-2-one (D10), 3-hydroxy-1-(3-nitrophenyl)-4-(2-thienylcarbonyl)-5-(4-(benzyloxy)phenyl)-2,5-dihydro-1H-pyrrol-2-one (D13), 3-hydroxy-1-(4-nitrophenyl)-4-(2-thienylcarbonyl)-5-(4-(benzyloxy)phenyl)-2,5-dihydro-1H-pyrrol-2-one (D14), and 3-hydroxy-1-(4-chlorophenyl)-4-(2-thienylcarbonyl)-5-(4-(benzyloxy)phenyl)-2,5-dihydro-1H-pyrrol-2-one (D15), that showed the highest cytotoxicity against malignant cells and the best selectivity towards normal cells were selected for further experiments. Results obtained by investigating mechanisms of cytotoxic activity suggest that selected 3-hydroxy-3-pyrrolin-2-one derivatives in HeLa cells induce apoptosis that is associated with S phase arrest (D13, D15, and D10) or unrelated to cell cycle distribution (D14). Additionally, to better understand their suitability for potential use as anticancer medicaments we studied the interactions between biomacromolecules (DNA or BSA) and D13 and D15. The results indicated that D13 and D15 have great affinity to displace EB from the EB-DNA complex through intercalation [K_sv = (3.7 ± 0.1) and (3.4 ± 0.1) × 10³ M⁻¹, respectively], an intercalative mode also confirmed through viscosity measurements. K_a values, obtained as result of fluorescence titration of BSA with D13 and D15 [K_a = (4.2 ± 0.2) and (2.6 ± 0.2) × 10⁵ M, respectively], support the fact that a significant amount of the tested compounds could be transported and distributed through the cells. In addition, by DNA and BSA molecular docking study for D13, D14 and D15 is determined and predicted the binding mode and the interaction region.     

ent-Beyerane diterpenoids from the heartwood of Excoecaria parvifolia

Chromatographic fractionations of the toluene extract of the heartwood of Excoecaria parvifolia collected in Australia resulted in the isolation of 12 beyerane diterpenes (1-12), and the triterpene, lupeol. Four of the isolated diterpenoids (5-7 and 12) have unusual structures: ent-3-oxa-beyer-15-en-2-one, (5); ent-15,16-epoxy-2-hydroxy-19-norbeyer-1,4-dien-3-one (6); methyl ent-2,4-seco-15,16-epoxy-4-oxo-3,19-dinorbeyer-15-en-2-oate (7); and ent-2,17-dihydroxy-19-norbeyer-1,4,15-trien-3-one (12). The structures were established by spectroscopic analyses, NMR data comparisons with similar diterpenes, and chemical correlations. All the diterpenes are assumed to have the same absolute configuration as the co-occurring (+)-stachenol (4). Diosphenol 2 and nor-lactone 5 exhibited significant potency in bioassays for cytotoxic activity against leukemia cells (L1210). Plausible biosynthetic pathways are proposed to explain the origin of the diterpene metabolites.     

生姜中6个姜辣素类成分的抗菌活性研究

为了探究生姜化学成分的抗菌活性及初步构效关系,采用色谱法从生姜中分离得到6个姜辣素类化合物,采用波谱法对这6个成分进行鉴定,分别为5-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-4-decen-3-one(1)、5-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-4-dodecen-3-one(2)、5-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-4-tetradecane-3-one(3)、[6]-姜酚(4)、[8]-姜酚(5)和[10]-姜酚(6)。采用抗菌纸片扩散法测定6个化合物对15株病原菌株的抗菌活性。结果表明化合物1和4抗菌活性最好,而6对所有菌株均无活性。初步构效关系分析表明:烯醇型化合物对革兰氏阳性菌的抗菌活性优于姜酚型化合物;而姜酚型化合物对革兰氏阴性菌的抗菌活性优于烯醇型化合物。此外,姜辣素类成分脂肪链的长度增加,可能导致抗菌活性降低。     

Homoisoflavonoids from Ophiopogon japonicus Ker-Gawler

From the ethyl acetate extract of the tuberous roots of Ophiopogon japonicus (Liliaceae) eight known and five new homoisoflavonoidal compounds were isolated. The new compounds are 5,7-dihydroxy-8-methoxy-6-methyl-3-(2'-hydroxy-4'-methoxybenzyl)chroman-4-one (1), 7-hydroxy-5,8-dimethoxy-6-methyl-3-(2'-hydroxy-4'-methoxybenzyl)chroman-4-one (2), 5,7-dihydroxy-6,8-dimethyl-3-(4'-hydroxy-3'-methoxybenzyl)chroman-4-one (3), 2,5,7-trihydroxy-6,8-dimethyl-3-(3',4'-methylenedioxybenzyl)chroman-4-one (4) and 2,5,7-trihydroxy-6,8-dimethyl-3-(4'-methoxybenzyl)chroman-4-one (5). Their structures have been elucidated by mass and NMR spectroscopy. Compounds 4 and 5 are the first isolated homoisoflavonoids with a hemiacetal function at position 2.     

Anti-adipogenic chromone glycosides from Cnidium monnieri fruits in 3T3-L1 cells

Seven new chromone glycosides, monnierisides A (3), B (10), C (11), D (12), E (13), F (15) and G (16) were isolated from Cnidium. monnieri, together with ten known chromone derivatives, undulatoside A (1), cnidimol C (2), saikochromoside A (4), cnidimoside A (5), cnidimoside B (6), 2-methyl-5-hydroxy-6-(2-butenyl-3-hydroxymethyl)-7-(β-d-glucopyranosyloxy)-4H-1-benzopyran-4-one (7), cnidimol D (8), hydroxycnidimoside A (9), umtatin (14) and 6'-hydroxylangelicain (17). The structures of isolated compounds were determined on the basis of spectroscopic analysis including 1D, 2D NMR and HR-MS. Among the compounds isolated, compounds 5, 6, 9 and 10 significantly inhibited adipocyte differentiation as measured by fat accumulation in 3T3-L1 cells using Oil Red O staining.     

Chromones from the tubers of Eranthis cilicica and their antioxidant activity

Chemical studies on the constituents of Eranthis cilicica led to isolation of ten chromone derivatives, two of which were previously known. Comprehensive spectroscopic analysis, including extensive 1D and 2D NMR data, and the results of enzymatic hydrolysis allowed the chemical structures of the compounds to be assigned as 8,11-dihydro-5-hydroxy-2,9-dihydroxymethyl-4H-pyrano[2,3-g][1]benzoxepin-4-one, 5,7-dihydroxy-8-[(2E)-4-hydroxy-3-methylbut-2-enyl]-2-methyl-4H-1-benzopyran-4-one, 5,7-dihydroxy-2-hydroxymethyl-8-[(2E)-4-hydroxy-3-methylbut-2-enyl]-4H-1-benzopyran-4-one, 7-[(β-d-glucopyranosyl)oxy]-5-hydroxy-8-[(2E)-4-hydroxy-3-methylbut-2-enyl]-2-methyl-4H-1-benzopyran-4-one, 7-[(β-d-glucopyranosyl)oxy]-5-hydroxy-2-hydroxymethyl-8-[(2E)-4-hydroxy-3-methylbut-2-enyl]-4H-1-benzopyran-4-one, 9-[(O-β-d-glucopyranosyl-(1→6)-β-d-glucopyranosyl)oxy]methyl-8,11-dihydro-5,9-dihydroxy-2-methyl-4H-pyrano[2,3-g][1]benzoxepin-4-one, 8,11-dihydro-5,9-dihydroxy-9-hydroxymethyl-2-methyl-4H-pyrano[2,3-g][1]benzoxepin-4-one, and 7-[(O-β-d-glucopyranosyl-(1→6)-β-d-glucopyranosyl)oxy]methyl-4-hydroxy-5H-furo[3,2-g][1]benzopyran-5-one, respectively. The isolated compounds were evaluated for their antioxidant activity.     

美花石斛化学成分及其护肤活性研究

本文研究美花石斛(Dendrobium loddigesii)的化学成分及其护肤活性。采用色谱法从美花石斛粗提物中分离得到12个化合物,利用波谱学方法分别鉴定为拖鞋状石斛素(1)、2,4,7-三羟基-9,10-二氢菲(2)、3,6,9-三羟基-3,4-二氢蒽-1(2H)-酮(3)、3,5′-二甲氧基-3′,4,9′-三羟基-7′,9-环氧-8,8′-木酚素(4)、5-(4-羟基-3-甲氧基苯乙基)-2-(4-羟基-3-甲氧基苯基)苯并二氢呋喃-3,7-二醇(5)、5-(4′′-羟基-3′′-甲氧基苯乙基)-2-(4′-羟基-5′-甲氧基苯基)-7-甲氧基苯并二氢吡喃-3-醇(6)、丁香脂素(7)、异香草醛(8)、松柏醛(9)、2-甲氧基-5-羟甲基苯酚(10)、二氢松柏醇(11)、4-羟基-3-甲氧基苯乙醇(12)。其中化合物3～5、7～12为首次从美花石斛中分离得到;化合物1、2、6(100μg/mL)有一定的自由基清除活性(>80%);化合物2(10μg/mL)有一定促胶原蛋白分泌活性(>20%)。结果显示从美花石斛的茎中分离得到了12个化合物,3个表现出良好的护肤活性。     

New polyoxygenated steroids from the Antarctic octocoral Dasystenella acanthina

The chemical study of the Antarctic octocoral Dasystenella acanthina has led to the isolation of the new polyoxygenated steroids (24R,22E)-24-hydroxycholest-4,22-dien-3-one (1), 23-acetoxy-24,25-epoxycholest-4-en-3-one (2), 12beta-acetoxycholest-4-en-3,24-dione (3), 12beta-acetoxy-24,25-epoxycholest-4-en-3-one (4), (22E)-25-hydroxy-24-norcholest-4,22-dien-3-one (5), 3alpha-acetoxy-25-hydroxycholest-4-en-6-one (6), and 3alpha,11alpha-diacetoxy-25-hydroxycholest-4-en-6-one (7), whose structures have been established by spectroscopic analysis. The absolute stereochemistry at C-24 in compound 1 has been determined through the 1H NMR study of the corresponding (R)- and (S)-MPA esters. All the new compounds showed significant activities as growth inhibitors of several human tumor cell lines. In addition, cytostatic and cytotoxic effects were also observed on selected tumor cell lines.     

Biotransformation of terpenes from Stemodia maritima by Aspergillus niger ATCC 9142.

Incubation of stemodin (1) in cultures of Aspergillus niger ATCC 9142 resulted in the production of 2alpha,3beta,13-trihydroxystemodane (2), 2alpha,7beta,13-trihydroxystemodane (3) and 2alpha,13,16beta-trihydroxystemodane (4), while stemodinone (5) afforded 13,18-dihydroxystemodan-2-one (6) and 13,16beta-dihydroxystemodan-2-one (7). Four novel metabolites were obtained from the bioconversion of stemarin (8) by the fungus, namely 18-hydroxystemaran-19-oic acid (9), 7beta,18-dihydroxystemaran-19-oic acid (10), 7alpha,18,19-trihydroxystemarane (11) and 1beta-hydroxystemaran-19-oic acid (12). 19-N,N-Dimethylcarbamoxy-13-hydroxystemarane (13) was also transformed to afford 19-N,N-dimethylcarbamoxy-13,17xi,18-trihydroxystemarane (14).