p-coumaric acid esters from Tanacetum longifolium

Two new long chain alkyl p-coumaric acid esters (2-3) along with eicosanyl trans-p-coumarate (1) were isolated from chloroform extract of the roots of Tanacetum longifolium. The structures of new compounds were assigned as 21'-hydroxyheneicosanyl-4-hydroxy-(cis and trans) p-coumarate (2a, 2b) and 27'-hydroxy heptacosanyl-cis-p-coumarate (3) by extensive chromatographic and spectroscopic analysis and by comparison with literature data of known compounds.     

Fuscoside E: a strong anti-inflammatory diterpene from Caribbean octocoral Eunicea fusca

The screen of 10 soft coral extracts collected from the Colombian Caribbean Sea in the TPA-induced ear edema model allowed us to identify Eunicea fusca extract among others as an interesting source of active compounds. The new diterpene, fuscoside E (1), along with the known fuscoside B (2), fuscol (3), (+)-germacrene D (4) and a mixture of six sterols (5-10), were isolated from this soft coral. Their structures were elucidated by 1D and 2D NMR spectroscopy techniques. Fuscoside E (1) absolute stereochemistry was determined by chiroptical methods. Fuscoside E (1) and B (2) showed strong anti-inflammatory in the above mentioned bioassay. Additionally, fuscoside E (1) and the sterol mixture (5-10) presented antifouling activity against bacterial strains involved in surface colonization.     

Antifungal amides from Piper arboreum and Piper tuberculatum

In continuation of our study of the Piperaceae we have isolated several amides, mainly those bearing isobutyl, pyrrolidine, dihydropyridone and piperidine moieties. Bioactivity-guided fractionation of extracts from leaves of Piper arboreum yielded two new amides, N-[10-(13,14-methylenedioxyphenyl)-7(E),9(Z)-pentadienoyl]-pyrrolidine (1), arboreumine (2) together with the known compounds N-[10-(13,14-methylenedioxyphenyl)-7(E)-pentaenoyl]-pyrrolidine (3) and N-[10-(13,14-methylenedioxyphenyl)-7(E),9(E)-pentadienoyl]-pyrrolidine (4). Catalytic hydrogenation of 3 yielded the amide N-[10-(13,14-methylenedioxyphenyl)-pentanoyl]-pyrrolidine (5). We also have isolated six amides (6-11) and two antifungal cinnamoyl derivatives (12, 13) from seeds and leaves of Piper tuberculatum. Compounds 1-11 showed antifungal activity as determined by direct bioautography against Cladosporium sphaerospermum while compounds 3-4 and 6-13 also showed antifungal activity against C. cladosporioides.     

Three New Constituents with Anti-Inflammatory and Antimicrobial Activities in Vitro from the Roots of Capsicum annuum L.

Three new compounds, including two new sesquiterpenes ( 1–2 ), named Annuumine E−F, and one new natural product, 3-hydroxy-2,6-dimethylbenzenemethanol ( 3 ), together with seventeen known compounds ( 4–20 ) were isolated from the ethanol extract of the roots of Capsicum annuum L. Among them, five compounds ( 4 , 5 , 9 , 10 and 20 ) were isolated from this plant for the first time. The structures of new compounds ( 1–3 ) were determined via detailed analysis of the IR, HR-ESI-MS and 1D and 2D NMR spectra. The anti-inflammatory activities of the isolated compounds were evaluated by their ability to reduce NO release by LPS-induced RAW 264.7 cells. Notably, compound 11 exhibited moderate anti-inflammatory activity (IC₅₀=21.11 μM). Moreover, the antibacterial activities of the isolated compounds were also evaluated.     

Isolation and structure elucidation of cytotoxic polyacetylenes and polyenes from Echinacea pallida

Bioassay-guided fractionation of n-hexane extracts of Echinacea pallida (Asteraceae) roots led to the isolation and structure elucidation of two polyacetylenes (1, 3) and three polyenes (2, 4, 5). Two are known hydroxylated compounds, namely 8-hydroxy-pentadeca-(9E)-ene-11,13-diyn-2-one (1) and 8-hydroxy-pentadeca-(9E,13Z)-dien-11-yn-2-one (2). Two dicarbonylic constituents, namely pentadeca-(9E)-ene-11,13-diyne-2,8-dione (3) and pentadeca-(9E,13Z)-dien-11-yne-2,8-dione (4), were isolated and characterized for the first time. Furthermore, the structure elucidation of pentadeca-(8Z,13Z)-dien-11-yn-2-one (5) is described. The structure of the compounds isolated was determined on the basis of UV, IR, NMR (including 1D and 2D NMR experiments, such as 1H-1H gCOSY, gHSQC-DEPT, gHMBC, gNOESY) and MS spectroscopic data. The cytotoxic activity of the isolated constituents against MIA PaCa-2 human pancreatic adenocarcinoma cells was evaluated in the concentration range 1-100 microg/ml. Results show that the hydroxylated compounds (1, 2) have low cytotoxicity, while the more hydrophobic polyacetylenes (3) and polyenes (4, 5) displayed moderate activity.     

Sesquiterpene coumarins from Ferula szowitsiana and in vitro antileishmanial activity of 7-prenyloxycoumarins against promastigotes

Two new sesquiterpene coumarins, named szowitsiacoumarin A (1) and szowitsiacoumarin B (2), and a phenylpropanoid derivative, 2-epihelmanticine (3), together with nine known compounds, auraptene (4), umbelliprenin (5), galbanic acid (6), methyl galbanate (7), farnesiferol B (8), farnesiferol C (9), persicasulfide A (10), beta-sitosterol and stigmasterol were isolated from the roots of Ferula szowitsiana. The structures of these compounds were elucidated by extensive spectroscopic methods including 1D-((1)H and (13)C) and 2D-NMR experiments (DQF-COSY, HSQC, HMBC, and ROESY) as well as HR-MALDI-MS analysis. Since the configuration of 2-epihelmanticine was previously only partly determined, a relative configurational analysis of its four stereocenters was carried out on the basis of the recently reported J-based method. The inhibiting activity of prenylated coumarins, auraptene (4) and umbelliprenin (5), in addition to galbanic acid (6), as major component, and of the Me(2)CO extract of Ferula szowitsiana (Apiaceae) roots has been evaluated against promastigotes of Leishmania major. Umbelliprenin and auraptene showed significant activity with IC(50) values of 4.9microg/ml (13.3microM) and 5.1microg/ml (17.1microM) after 48h incubation, respectively.     

Leishmanicidal cycloartane-type triterpene glycosides from Astragalus oleifolius

Two new cycloartane-type glycosides oleifoliosides A (1) and B (2) were isolated from the lower stem parts of Astragalus oleifolius. Their structures were identified as 3-O-[beta-xylopyranosyl-(1 --> 2)-alpha-arabinopyranosyl]-6-O-beta-xylopyranosyl-3beta,6alpha,16beta,24(S),25-pentahydroxycycloartane and 3-O-[beta-xylopyranosyl-(1 --> 2)-alpha-arabinopyranosyl]-6-O-beta-glucopyranosyl-3beta,6alpha,16beta,24(S),25-pentahydroxycycloartane, respectively, by means of spectroscopic methods (IR, 1D and 2D NMR, ESI-MS). Three known cycloartane glycosides cyclocanthoside E (3), astragaloside II (4) and astragaloside IV (5) were also isolated and characterized. All five compounds were evaluated for in vitro trypanocidal, leishmanicidal and antiplasmodial activities as well as their cytotoxic potential on primary mammalian (L6) cells. Except for the compound 5, all compounds showed notable growth inhibitory activity against Leishmania donovani with IC50 values ranging from 13.2 to 21.3 microg/ml. Only weak activity against Trypanosoma brucei rhodesiense was observed with the known compounds astragaloside II (4, IC50 66.6 microg/ml) and cyclocanthoside E (3, IC50 85.2 microg/ml), while all compounds were inactive against Trypanosoma cruzi and Plasmodium falciparum. None of the compounds were toxic to mammalian cells (IC50's > 90 microg/ml). This is the first report of leishmanicidal and trypanocidal activity of cycloartane-type triterpene glycosides.     

Cycloartane type triterpenoids from the rhizomes of Polygonum bistorta

Two new compounds, 24(E)-ethylidenecycloartanone (1) and 24(E)-ethylidenecycloartan-3alpha-ol (2) were isolated from the rhizomes of Polygonum bistorta, together with seven known compounds viz., cycloartane-3,24-dione (3), 24-methylenecycloartanone (4), gamma-sitosterol (5), beta-sitosterol (6), beta-sitosterone (7), friedelin (8) and 3beta-friedelinol (9). All the cycloartane type triterpenoids, compounds 7 and 8 are reported for the first time from this plant. A combination of 1D and 2D NMR spectroscopy and MS were mainly used to elucidate the structures of the new compounds 1 and 2.     

三七环二肽成分和人参内酰胺成分

From the roots of Panax notoginseng fourteen cyclodipeptides 1-14 were isolated including one new compound (1),seven new natural compounds (4-10) and six known compounds (2-3,11-14) together with one known other compound 15.The chemical structure of 1 was elucidated as cyclo-(Leu-Thr) based on spectral methods.From the roots of Panax ginseng five known lactams (16-20) includingpyrng lutamic acid were isolated together with butyric diacid,daucosterol and sucrose.The primary binactivity test showed that pyroglutamic acid and its n-butyl derivative have weak Ca^2 antagonistic activity.     

Plocoralides A-C, polyhalogenated monoterpenes from the marine alga Plocamium corallorhiza

Three new polyhalogenated monoterpenes, plocoralides A-C (1-3) along with three known compounds (4-6) have been isolated from the organic extract of the red alga P. corallorhiza. Structures of the new compounds were characterized as 4,8-dibromo-1,1-dichloro-3,7-dimethyl-2E,6E-octadiene (1), 4,6-dibromo-1,1-dichloro-3,7-dimethyl-2E,7-octadiene (2) and 4,8-dibromo-1,1,7-trichloro-3,7-dimethyl-2E,5Z-octadiene (3) on the basis of one- and two-dimensional NMR spectroscopic data and MS analyses. Compounds 2-6 show moderate cytotoxicity toward esophageal cancer cells.     

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.     

Rare trisubstituted sesquiterpenes daucanes from the wild Daucus carota

Phytochemical and biological investigation of the roots of the wild Daucus carota ssp. carota afforded three new and four known compounds, including four sesquiterpenes daucane esters (1-3 [new], and 4), one polyacetylene (5), one sesquiterpene coumarin (6), and sitosterol glucoside. The structures of the new compounds were determined by comprehensive NMR studies, including DEPT, COSY, NOESY, HMQC and HMBC analyses. Based on an agar diffusion assay, 1, 2 and 4-6 were screened and found to contain a range of low antibacterial activities against four gram positive (Staphylococcus aureus, Streptomyces scabies, Bacillus subtilus, Bacillus cereus) and two gram negative species (Pseudomonas aeruginosa, Escherichia coli) as well as antifungal against Fusarium oxysporum and Aspergillus niger using cup agar diffusion assay.     

Two new steryl esters from the basidiomycete Tricholomopsis rutilans

Two new steryl esters with a polyhydroxylated ergostane-type nucleus, 3beta,5alpha-dihydroxy-(22E,24R)-ergosta-7,22-dien-6beta-yl oleate (1) and 3beta,5alpha-dihydroxy-(22E,24R)-ergosta-22-en-7-one-6beta-yl oleate (2), were isolated from the fruiting bodies of the basidiomycete Tricholomopsis rutilans along with three known sterols (3, 4, and 5). The structures of compounds 1 and 2 were established on the basis of spectroscopic means and chemical methods.     

Insect growth regulatory effects of some extracts and sterols from Myrtillocactus geometrizans (Cactaceae) against Spodoptera frugiperda and Tenebrio molitor

A methanol extract from the roots and aerial parts of Myrtillocactus geometrizans (Cactaceae) yielded peniocerol 1, macdougallin 2, and chichipegenin 3. The natural products 1, 2 their mixtures, MeOH and CH(2)Cl(2) extracts showed insecticidal and insect growth regulatory activity against fall armyworm [Spodoptera frugiperda J. E. Smith (Lepidoptera: Noctuidae)], an important insect pest of corn, and [Tenebrio molitor (Coleoptera)], a pest of stored grains in Mexico. The most active compounds were 1, 2, and a mixture (M(2)) of 1 and 2 (6:4). All these extracts, compounds and the mixture had insect growth regulating (IGR) activity between 5.0 and 50.0 ppm and insecticidal effects between 50 and 300 ppm in diets. The extracts were insecticidal to larvae, with lethal doses between 100 and 200 ppm. These compounds appear to have selective effects on the pre-emergence metabolism of Coleoptera, because in all treatments of the larvae of T. molitor, pupation were shortened and this process show precociousness in relation to controls. In contrast to S. frugiperda larvae, onset of pupation was noticeably delayed. Emergence in both cases was drastically diminished. In both pupae and in the few adults that were able to emerge, many deformations were observed. The results of these assays indicated that the compounds were more active than other known natural insect growth inhibitors such as gedunin and methanol extracts of Cedrela salvadorensis and Yucca periculosa. Peniocerol, macdougallin and chichipegenin, as well as mixtures of these substances, may be useful as natural insecticidal agents.     

Aromatic compound glucosides,alkyl glucoside and glucide from the fruit of anise

From the polar portion of the methanolic extract of the fruit of anise (Pimpinella anisum L.), which has been used as a spice and medicine since antiquity, four aromatic compound glucosides, an alkyl glucoside and a glucide were isolated together with 24 known compounds. The structures of the new compounds were clarified as (E)-3-hydroxyanethole beta-D-glucopyranoside, (E)-1'-(2-hydroxy-5-methoxyphenyl)propane beta-D-glucopyranoside, 3-hydroxyestragole beta-D-glucopyranoside, methyl syringate 4-O-beta-D-glucopyranoside, hexane-1,5-diol 1-O-beta-D-glucopyranoside and 1-deoxy-L-erythritol 3-O-beta-D-glucopyranoside by spectral investigation.     

Secondary metabolites from two species of Pulicaria and their cytotoxic activity

Two new compounds, the sesquiterpene (1E,5E)-8β-acetoxy-4α-hydroxy-7βH-germacra-1(10),5-dien-14-oic acid (2), and a nor-sesquiterpene, (5E)-8β-acetoxy-4α-hydroxy-7βH-germacr-5-en-10-one (3), were isolated from Pulicaria canariensis ssp. lanata, along with ten known compounds, including the flavonoid 5,3'-dihydroxy-3,7,4'-trimethoxyflavone (4). From Pulicaria burchardii, we isolated seven known compounds; the physical and spectroscopic data of the triterpenoid 3β-hydroxytaraxaster-20-en-30-al (1) are reported. The structures of compounds 1-3 were determined on the basis of HR-MS, and 1D- and 2D-NMR studies. The structure of 2 was corroborated by X-ray crystal diffraction. Cell viability experiments revealed that the semisynthetic flavonoid 4b was the most cytotoxic compound against human leukemia cells, and the cytotoxicity was caused by induction of apoptosis, as determined by microscopy of nuclear changes.     

Ceriopsins F and G,diterpenoids from Ceriops decandra

Chemical examination of the ethyl acetate solubles of the CH(3)OH:CH(2)Cl(2) (1:1) extract of the roots of Ceriops decandra collected from Kauvery estuary resulted in the isolation of two more diterpenoids, ceriopsins F and G (1-2) and five known compounds, ent-13-hydroxy-16-kauren-19-oic acid (steviol, 3), methyl ent-16beta,17-dihydroxy-9(11)-kauren-19-oate (4), ent-16beta,17-dihydroxy-9(11)-kauren-19-oic acid (5), ent-16-oxobeyeran-19-oic acid (isosteviol, 6), 8,15R-epoxypimaran-16-ol (7). The structures of the new diterpenoids were elucidated by a study of their physical and spectral data as methyl ent-13,17-epoxy-16-hydroxykauran-19-oate (1) and ent-16-oxobeyeran-19-al (2).     

Isoquinoline and isoindole alkaloids from Menispermum dauricum

Three isoquinoline alkaloids and an isoindole alkaloid, along with eight known compounds, were isolated from the roots of Menispermum dauricum (Menispermacese). The alkaloids were characterized as 7-hydroxy-6-methoxy-1(2H)-isoquinolinone, 6,7-dimethoxy-N-methyl-3,4-dioxo-1(2H)-isoquinolinone, 1-(4-hydroxybenzoyl)-7-hydroxy-6-methoxy-isoquinoline and 6-hydroxy-5-methoxy-N-methylphthalimide, on the basis of spectral evidence including 1D- and 2D-NMR and MS analyses.     

Antimycobacterial flavonoids from Derris indica

Flavonoids (1-4), together with ten known compounds (5-14) were isolated from the stems and roots of the mangrove plant Derris indica. Their chemical structures were elucidated by analysis of their spectroscopic data. All compounds except compounds 2 and 6 exhibited antimycobacterial activity with minimum inhibitory concentrations (MIC) between 6.25 and 200 microg/mL.     

Allelochemicals from Stauranthus perforatus, a Rutaceous tree of the Yucatan Peninsula, Mexico

Aqueous leachates and a CHCl3-MeOH (1:1) extract of roots of Stauranthus perforatus showed a significant phytotoxic effect on Amaranthus hypochondriacus and Echinochloa crus-galli. Bioassay-directed fractionation of the active organic extract led to the isolation and characterization of ten secondary metabolites, which included two pyranocoumarins [xanthyletin (1) and 3-(1',1'-dimethylallyl)-xanthyletin (2)], four furanocoumarins [chalepensin (3), ammirin (4), chalepin (5) and 2'-isopropyl-psoralene (6)], two lignans [asarinin (7) and fargesin (8)], one sesquiterpene [4,5-epoxi-beta-caryophyllene (9)], and one alkamide [pellitorine (10)]. From these compounds, 2'-isopropyl-psoralene (6) or anhydromarmesin, is reported for the first time as a natural product, whereas compounds 4-10 are now reported as being present in S. perforatus. Metabolites 1, 3-5 and 10 caused significant inhibition of radicle growth of A. hypochondriacus and E. crus-galli. Furthermore, in a greenhouse experiment the decomposition of the leaves and roots in the soil had a significant inhibitory effect on the growth of weeds. The allelopathic action of the decomposition of roots was evident up to the sixth week of the experiment. The effect of leaves was comparable to that of DPCA (dimethyl tetrachloroterephthalate), a commercial herbicide. Finally different concentrations of Stauranthus root powder were combined with maize kernels and used to feed corn weevil. The treatments resulted in high mortality of this insect.