New 19-oxygenated steroid from the South China Sea gorgonian Dichotella gemmacea

A new 19-oxygenated steroid, 25-acetate-nebrosteroid K (1), and five known steroids (2–6), along with one known 19-hydroxy steroidal glycoside (7) were obtained from the gorgonian Dichotella gemmacea collected from the South China Sea. The structure and relative configuration of 1 were elucidated by using comprehensive spectroscopic data including NOESY spectra. Compound 1 represents the first example of 19-oxygenated steroid with a 19-oic acid methyl ester group isolated from gorgonians. All of the isolated compounds were evaluated for lethal activity to brine shrimp Artemia salina and cytotoxicity against A549 and HL-60 cell lines. Among them, 1 showed strong lethality towards A. salina.     

Chemical constituents and biological activities of Viburnum macrocephalum f. keteleeri

Three new compounds (1–3) and seven known compounds (4–10) have been isolated from the ethanolic extract of Viburnum macrocephalum f. keteleeri using bioactivity-guided fractionation and identified as methyl (2-α-L-rhamnopyranosyloxy)acetate (1), methyl (2R-3-α-L-rhamnopyranosyloxy)glycerate (2), methyl (3R-4-α-L-rhamnopyranosyloxy-3-hydroxy)butanoate (3), bridelionoside B (4), (6S,7E,9R)-roseoside (5), linarionoside A (6), 3,7,11-trimethyl-1,6-dodecadien-3,10,11-triol (7), (+)-8-hydroxylinalool (8), β-sitosterol (9) and daucosterol (10). The structures of 1–3, including absolute configurations, were determined by spectroscopic data (¹H and ¹³C NMR, HSQC, HMBC and ORD) and chemical methods. In addition, compounds 1–8 were assayed for their insecticidal and antimicrobial activities. Compounds 7 and 8 exhibited moderately insecticidal effects against Mythimna separata with LD₅₀ values of 180 and 230 μg g^?1, respectively. Compounds 2, 3, 7 and 8 showed varying antimicrobial activities with IC₅₀ values ranging from 125 to 529 μM.     

(3R,4S)-isostreptenol III from Penicillium purpurogenum MM

Abstract

In continuation of the search for new compounds from the terrestrial fungus Penicillium purpurogenum MM, (3R,4S)-isostreptenol III (1), a further new natural compound is reported. The chemical structure of 1 was confirmed by extensive 1D and 2D NMR and ESI HR mass measurements, and by comparison with literature data. The absolute configuration was determined by ab initio calculations of ECD, ORD, and NMR data. The antimicrobial and cytotoxic activities of the crude extract and 1 were reported using a set of microorganisms and by the brine shrimp assay, respectively.     

Marcanine G,a new cytotoxic 1-azaanthraquinone from the stem bark of Goniothalamus marcanii Craib

The ethanolic extract from the stem bark of Goniothalamus marcanii Craib was shown in preliminary brine shrimp lethality data having good cytotoxic activity. Further bioassay guided isolation was done by means of solvent partition, chromatography and precipitation to provide four isolated compounds: a novel compound 1 with the core structure of 1-azaanthraquinone moiety referred as marcanine G; as well as compounds 2–4 with known aristolactam structures namely, piperolactam C, cepharanone B and taliscanine. These compounds were characterised by spectroscopic techniques. The assessment of cytotoxicity was established on an SRB assay using doxorubicin as a positive control. Marcanine G (1) was considered the most active compound indicating the IC₅₀ values of 14.87 and 15.18 μM against human lung cancer cells (A549) and human breast cancer cells (MCF7), respectively. However, 2 showed mild activity with the IC₅₀ values of 83.72 and 82.32 μM against A549 and MCF7 cells, respectively.     

A new dihydrobenzofuran lignan and potential α-glucosidase inhibitory activity of isolated compounds from Mitrephora teysmannii

A new dihydrobenzofuran lignan, (2R,3S)-2-(3′,4′-dimethoxyphenyl)-5-(3-hydroxypropyl)-7-methoxy-2,3-dihydrobenzofuran-3-methyl acetate, named as mitredrusin (1), was isolated from the leaves of Mitrephora teysmannii (Annonaceae) together with 12 known compounds including a related dihydrobenzofuran lignan: (?)-3′,4-di-O-methylcedrusin (2), four polyacetylenic acids: 13(E)-octadecene-9,11-diynoic acid (3), 13(E),17-octadecadiene-9,11-diynoic acid (4), octadeca-9,11,13-triynoic acid (5) and octadeca-17-en-9,11,13-triynoic acid (6), five lignans: (?)-eudesmin (7), (?)-epieudesmin (8), (?)-phillygenin (9), magnone A (10) and forsythialan B (11) and two megastigmans: (3S,5R,6S,7E,9R)-7-megastigmene-3,6,9-triol (12) and annoionol A (13). The chemical structures of these compounds were established on the basis of their 1-D and 2-D NMR spectroscopic data. All compounds were evaluated for their α-glucosidase inhibitory activity. Among these isolates, polyacetylenic acids 3 and 4 showed more than 20-fold much higher activity compared with that of the antidiabetic drug acarbose.     

Antiangiogenic phenylpropanoid glycosides from Gynura cusimbua

A new phenylpropanoid glycoside, named α-L-rhamnopyranosyl-(1?2)-β-D-[4″-(8E)-7-(3,4-dihydroxyphenyl)-8-propenoate, 1″-O-(7S)-7-(3,4-dihydroxyphenyl)-7-methoxy-ethyl]-glucopyranoside (1), together with nine known compounds (2–10) were isolated from the active fraction (n-Butanol fraction) of Gynura cusimbua for the first time. The known compounds (2–10) were identified as phenylpropanoid glycosides on the basis of extensive spectral data and references. The antiangiogenic activities of compounds (1–10) were evaluated by MTT assay on HUVECs and wild-type zebrafish in vivo model assay. As a result, compounds 1, 6, 7, 8 and 10 exhibited certain antiangiogenic activities.     

Comparative evaluation of two Trichoderma harzianum strains for major secondary metabolite production and antifungal activity

This investigation was undertaken to identify the major secondary metabolite, produced by two Trichoderma harzianum strains (T-4 and T-5) with their antifungal activity against phytopathogenic fungi using poison food technique. The ethyl acetate extract was subjected to column chromatography using n-hexane, ethyl acetate and methanol gradually. Chromatographic separation of ethyl acetate extract of T. harzianum (T-4) resulted in the isolation and identification of palmitic acid (1), 1,8-dihydroxy-3-methylanthraquinone (2), 6-pentyl-2H-pyran-2-one (3), 2(5H)-furanone (4), stigmasterol (5) and β-sitosterol (6), while T. harzianum (T-5) gave palmitic acid (1), 1-hydroxy-3-methylanthraquinone (7), δ-decanolactone (8), 6-pentyl-2H-pyran-2-one (3), ergosterol (9), harzianopyridone (10) and 6-methyl-1,3,8-trihydroxyanthraquinone (11) as major metabolites. Among compounds screened for antifungal activity, compound 10 was found to be most active (EC₅₀ 35.9–50.2 μg mL^? 1). In conclusion, the present investigation provided significant information about antifungal activity and compounds isolated from two different strains of T. harzianum obtained from two different Himalayan locations.     

A bioactive cycloartane triterpene from Garcinia hombroniana

The dichloromethane bark extract of Garcinia hombroniana yielded one new cycloartane triterpene; (22Z,24E)-3β-hydroxycycloart-14,22,24-trien-26-oic acid (1) together with five known compounds: garcihombronane G (2), garcihombronane J (3), 3β acetoxy-9α-hydroxy-17,14-friedolanostan-14,24-dien-26-oic acid (4), (22Z, 24E)-3β, 9α-dihydroxy-17,14-friedolanostan-14,22,24-trien-26-oic acid (5) and 3β, 23α-dihydroxy-17,14-friedolanostan-8,14,24-trien-26-oic acid (6). Their structures were established by the spectral techniques of NMR and ESI-MS. These compounds together with some previously isolated compounds; garcihombronane B (7), garcihombronane D (8) 2,3’,4,5’-tetrahydroxy-6-methoxybenzophenone (9), volkensiflavone (10), 4’’-O-methyll-volkensiflavone (11), volkensiflavone-7-O-glucopyranoside (12), volkensiflavone-7-O-rhamnopyranoside (13), Morelloflavone (14), 3’’-O-methyl-morelloflavone (15) and morelloflavone-7-O-glucopyranoside (16) were evaluated for cholinesterase enzymes inhibitory activities using acetylcholinesterase and butyrylcholinesterase. In these activities, compounds 1–9 showed good dual inhibition on both the enzymes while compounds 10–16 did not reasonably contribute to both the cholinesterases inhibitory effects.     

Synthesis and investigation of antibacterial activities and carbonic anhydrase and acetyl cholinesterase inhibition profiles of novel 4,5-dihydropyrazol and pyrazolyl-thiazole derivatives containing methanoisoindol-1,3-dion unit

Novel 4,5-dihydropyrazole derivatives (3a–i), 3-(4-((3aR,4S,7R,7aS)-1,3-dioxo-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindol-2(3H)-yl)phenyl)-5-phenyl-4,5-dihydro-1H-pyrazole-1-carbothio amide, were obtained by the addition of thiosemicarbazide (2) to the chalcones (1a–i). The addition–cyclization of 2,4′-dibromoacetophenone (4) to pyrazole derivatives (3a–i) gave the new pyrazolyl-thiazole derivatives (5a–i), (3aR,4S,7R,7aS)-2-(4-(1-(4-(4-bromophenyl)thiazol-2-yl)-5-phenyl-4,5-dihydro-1H-pyrazol-3-yl)phenyl)-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione. Antibacterial and acetylcholinesterase (AChE) enzyme and human carbonic anhydrase (hCA) I, and II isoform inhibitory activities of the compounds 3a–i and 5a–i were investigated. Some of the compounds showed promising antibacterial activity. In addition, the hCA II and I were effectively inhibited by the lately synthesized derivatives, with K_i values in the range of 18.90?±?2.37 ?58.25?±?13.62?nM for hCA II and 5.72?±?0.98 ?37.67?±?5.54?nM for hCA I. Also, the K_i parameters of these compounds for AChE were obtained in the range of 25.47?±?11.11???255.74?±?82.20?nM. Also, acetazolamide, clinical molecule, was used as a CA standard inhibitor that showed K_i value of 70.55?±?12.30?nM against hCA II, and 67.17?±?9.1?nM against hCA I, and tacrine inhibited AChE showed K_i value of 263.67?±?91.95.     

Phenolic compounds from the aerial parts of Clematis viticella L. and their in vitro anti-inflammatory activities*

Phytochemical investigations on the EtOH extract of Clematis viticella led to the isolation of six flavonoid glycosides, isoorientin (1), isoorientin 3′-O-methyl ether (2), quercetin 7-O-α-L-rhamnopyranoside (3), quercetin 3,7-di-O-α-L-rhamnopyranoside (4), manghaslin (5) and chrysoeriol 7-O-β-D-glucopyranoside (6), one phenylethanol derivative, hydroxytyrosol (7), along with three phenolic acids, caffeic acid (8), (E)-p-coumaric acid (9) and p-hydroxybenzoic acid (10). The structures of the isolates were elucidated on the basis of NMR and HR-MS data. All compounds were isolated from C. viticella for the first time. Compounds 7 and 8 showed significant anti-inflammatory activity at 100 μM by reducing the release of NO in LPS-stimulated macrophages comparable to positive control indomethacin. Compounds 3 and 7 exhibited anti-inflammatory activity through lowering the levels of TNF-α while 1, 3 and 5 decreased the levels of neopterin better than the positive controls.     

Two new phenolic compounds from the leaves of Alnus sibirica Fisch. ex Turcz.

Two new phenolic compounds, 4-O-glucopyranosyl-5-O-caffeoylshikimic acid (1) and 2,3-digalloyl oregonin (2), were isolated along with eight known phenolic compounds (3–10) from an 80% acetone extract of Alnus sibirica leaves. The chemical structures of these compounds were elucidated using 1D/2D nuclear magnetic resonance and high resolution-MS. The anti-oxidative activities of these compounds were determined by assaying their 1,1-diphenyl-2-picrylhydrazyl radical and nitroblue tetrazolium superoxide anion scavenging activity. All of the isolated phenolic compounds (1–10) exhibited potent anti-oxidative activities. In particular, 2 and 4, which are diarylheptanoids, and 10 which is ellagitannin exhibited excellent anti-oxidative activities with almost the same potency as that of the positive controls L-ascorbic acid and allopurinol.     

A new norisoprenoid from the leaves of Ficus pumila

One new norisoprenoid 3,9-dihydroxy dihydro actinidiolide (1), together with eleven known compounds (2–12), were isolated from ethanol extract of the leaves of Ficus pumila collected in Hainan Province, China. Their structures were elucidated by the detailed analysis of comprehensive spectroscopic data. Compounds 1, 2, 4, 5, 8 and 10–12 were isolated from the F. pumila for the first time. All compounds were evaluated for their cytotoxic activity. Compounds 3 and 9 showed weak cytotoxic activity against Hela, MCF-7 and A549 cell lines.     

Hepatoprotective phenylethanoid glycosides from Cirsium setosum

Two new phenylethanoid glycosides, namely β-D-glucopyranoside, 1″-O-(7S)-7-(3-methoxyl-4-hydroxyphenyl)-7-methoxyethyl-3″-α-L-rhamnopyranosyl-4″-[(8E)-7-(3-methoxyl-4-hydroxyphenyl)-8-propenoate] (1) and β-D-glucopyranoside, 1″-O-(7S)-7-(3-methoxyl-4-hydroxyphenyl)-7-methoxyethyl-3″-α-L-rhamnopyranosyl-4″-[(8E)-7-(4-hydroxyphenyl)-8-propenoate] (2), together with six phenylethanoid glycosides were isolated from Cirsium setosum. Their structures were elucidated by their spectroscopic data and references. Compounds 2, 4, 5, 7 and 8 (10 μM) exhibited moderate hepatoprotective activities. Compounds (3–8) were obtained from this plant for the first time.     

Asperpyrone F,a new dimeric naphtho-γ-pyrone from the edible fungus Pleurotus ostreatus

A new dimeric naphtho-γ-pyrone, asperpyrone F (1), along with six known ones, asperpyrones B (2) and C (3), fonsecinones A (4) and B (5), aurasperones A (6) and E (7), have been isolated from the solid culture of the edible fungus Pleurotus ostreatus. The structures of 1–7 were determined mainly by NMR and MS experiments. The absolute configuration of compound 1 was assigned via the circular dichroism (CD) data analysis. Compounds 1–7 showed modest antioxidant and immunomodulatory activities. All compounds were isolated from the fungus P. ostreatus for the first time.     

Isolation,structural elucidation and cytotoxicity evaluation of a new pentahydroxy-pimarane diterpenoid along with other chemical constituents from Aerva lanata

Aervalanata possesses various useful medicinal and pharmaceutical activities. Phytochemical investigation of the plant has now led to the isolation of a new 2α,3α,15,16,19-pentahydroxy pimar-8(14)-ene diterpenoid (1) together with 12 other known compounds identified as β-sitosterol (2), β-sitosterol-3-O-β-D-glucoside (3), canthin-6-one (4), 10-hydroxycanthin-6-one (aervine, 5), 10-methoxycanthin-6-one (methylaervine, 6), β-carboline-1-propionic acid (7), 1-O-β-D-glucopyranosyl-(2S,3R,8E)-2-[(2′R)-2-hydroxylpalmitoylamino]-8-octadecene-1,3-diol (8), 1-O-(β-D-glucopyranosyl)-(2S,3S,4R,8Z)-2-[(2′R)-2′-hydroxytetracosanoylamino]-8(Z)-octadene-1,3,4-triol (9), (2S,3S,4R,10E)-2-[(2′R)-2′-hydroxytetracosanoylamino]-10-octadecene-1,3,4-triol (10), 6′-O-(4″-hydroxy-trans-cinnamoyl)-kaempferol-3-O-β-D-glucopyranoside (tribuloside, 11), 3-cinnamoyltribuloside (12) and sulfonoquinovosyldiacylglyceride (13). Among these, six compounds (8–13) are reported for the first time from this plant. Cytotoxicity evaluation of the compounds against five cancer cell lines (CHO, HepG2, HeLa, A-431 and MCF-7) shows promising IC₅₀ values for compounds 4, 6 and 12.     

A new antimicrobial sesquiterpene isolated from endophytic fungus Cytospora sp. from the Chinese mangrove plant Ceriops tagal

Abstract

Chemical examination of Chinese mangrove Ceriops tagal endophytic Cytospora sp., yielded a new biscyclic sesquiterpene seiricardine D (1), and eight known metabolites, xylariterpenoid A (2a), xylariterpenoid B (2b) and regiolone (3) 4-hydroxyphenethyl alcohol (4), (22E, 24R)5, 8-epidioxy-5α, 8α-ergosta-6,22E-dien-3ß-ol (5), (22E, 24R)5, 8-epidioxy-5α, 8α-ergosta-6,9(11), 22-trien-3 ß-ol (6), ß-sitosterol (7) and stigmast-4-en-3-one (8). These structures were unambiguously elucidated on the basis of extensive NMR spectroscopic and mass spectrometric analyses. The antimicrobial activities of compounds 1–8 and their effects on a panel of plant and human pathogens were evaluated.     

Chemical constituents and their bioactivities from the fruits of Vitex negundo var. cannabifolia

Phytochemical investigation of the fruits of Vitex negundo var. cannabifolia led to the isolation of 22 compounds (1–22). Their structures were elucidated mainly by spectroscopic analysis and comparison with the literature data. Among them, compounds 1 and 2 were two new artificial lignans. Primary bioassay showed that the polymethoxyflavones 9–12 displayed moderate-to-weak cytotoxicity against human HepG2 and rat C6 cell lines, while the triterpenoids 13–17 exhibited significant brine shrimp lethality with LC₅₀values of 7.5–29.4 μM.     

Two new sesquiterpenes from Chloranthus japonicus Sieb

Two new sesquiterpenes, namely, 1β,10β-dihydroxy-eremophil-7(11), 8-dien-12,8-olide (1) and 8,12-epoxy-1β-hydroxyeudesm-3,7,11-trien-9-one (2), together with three known sesquiterpenoids, shizukolidol (3), 4α-hydroxy-5α(H)-8β-methoxy-eudesm-7(11)-en-12,8-olide (4), and neolitacumone B (5), and two known monoterpenes, (3R,4S,6R)-p-menth-1-en-3,6-diol (6) and (R)-p-menth-1-en-4,7-diol (7), were isolated from the whole plant of Chloranthus japonicus Sieb. Their structures were elucidated on the basis of spectroscopic data analysis and comparison with those of related known compounds. Compounds 4–7 were isolated from this plant for the first time.     

Eremophilane sesquiterpenes from the endophytic fungus Xylaria sp. GDG-102

A new eremophilane sesquiterpene, xylareremophil (1), together with five known eremophilanes, 1α,10α-epoxy-3α-hydroxyeremophil-7(11)-en-12,8β-olide (2), 1,10α,13-trihydroxyeremophil-7(11)-en-12,8-olide (3), 1α,10α-epoxy-13-hydroxyeremophil-7(11)-en-12,8β-olide (4), mairetolides B (5) and G (6) were isolated from the endophytic fungus Xylaria sp. GDG-102 cultured from Sophora tonkinensis. Their structures were elucidated on the basis of spectroscopic data analysis. The absolute configurations of 1 was determined by comparing computed electronic circular dichroism (ECD) and optical rotation (OR) with experimental results. Compounds 1, 5 and 6 showed antibacterial activities against Proteus vulgaris, Micrococcus luteus, Micrococcus lysodeikticus and Bacillus subtilis with MIC values of 25–100 μg/mL.     

A bicyclo[3.2.1]octanoid neolignan and toxicity of the ethanol extract from the fruit of <Emphasis Type="Italic">Ocotea heterochroma</Emphasis>

A new bicyclo[3.2.1]octanoid neolignan rel-(7S,8R,1′S,2′R,3′S)-Δ8′-2′-hydroxy-5,1′,3′-trimethoxy-3,4methylenedioxy-7,3′,8,1′-neolignan (1) was isolated from ethanol extract from the fruit of Ocotea heterochroma Mez & Sodiro ex Mez as well as the known compounds β-friedelanol (2), meso-dehydroguaiaretic acid (3), and yangambin (4), whose structures were elucidated on the basis of their comprehensive spectroscopic analysis including 2D NMR data. Lethality bioassay using brine shrimp (Artemia salina Leach) was evaluated with the ethanol extract from the Ocotea heterochroma’s fruit. The toxicity of this extract was greater than the toxicity of those fractions obtained in a first solvent partition (benzene, ethyl acetate, and butanol subfractions) and that of a mixture of acetylated 2′-epimers from the new neolignan 1. Published in Khimiya Prirodnykh Soedinenii, No. 2, pp. 158–160, March–April, 2009.