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.     

Structure determination and quantification of a new flavone glycoside with anti-acetylcholinesterase activity from the herbs of Elsholtzia ciliata

Three acacetin triglycosides (compounds 1, 2 and 3) were isolated from the herbs of Elsholtzia ciliata (Labiatae). The structure were identified as 7-O-β-D-glucopyranosyl-(1 → 2)[α-L-rhamnopyranosyl-(1 → 6)]-β-D-glucopyranoside (compound 1), 7-O-(6-O-acetyl)-β-D-glucopyranosyl-(1 → 2)[α-L-rhamnopyranosyl-(1 → 6)]-β-D-glucopyranoside (compound 2) and 7-O-(6-O-acetyl)-β-D-glucopyranosyl-(1 → 2)[(4-O-acetyl)-α-L-rhamnopyranosyl-(1 → 6)]-β-D-glucopyranoside (compound 3) of acacetin. The structures of these compounds were determined on the basis of 2D-NMR spectroscopic data. Compound 3 has not been isolated from a natural source. In addition, the three compounds were quantitatively analysed by HPLC. Acetylcholinesterase (AChE) inhibition activity was assayed to find anti-Alzheimer’s activity, since this enzyme increases the concentration of acetylcholine (ACh), a neurotransmitter, responsible for brain’s memory. Acacetin, the aglycone of the three compounds, exhibited a potent anti-cholinesterase activity (IC₅₀, 50.33 ± 0.87), though its glycosides (1, 2 and 3) were less active. HPLC analysis demonstrated that the three compounds were contained in the MeOH extract in the order of compounds 2 (12.63 mg/g extract) > 3 (3.10 mg/g) > 1 (2.92 mg/g).     

Two new noroleanane-type triterpenoid saponins from the stems of Stauntonia chinensis

Two new noroleanane-type triterpenoid saponins, 3β,20α,24-trihydroxy-29-norolean-12-en-28-oic acid 24-O-β-L-fucopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucopyranoside (1) and 3β,20α,24-trihydroxy-29-norolean-12-en-28-oic acid 24-O-β-D-glucopyranosyl-(1→2)-[α-L-arabinopyranosyl-(1→3)]-β-D-glucopyranoside (2) were isolated from the stems of Stauntonia chinensis DC., together with three known compounds, brachyantheraoside B₂ (3), eupteleasaponin Ⅷ (4) and fargoside B (5). Their structures were elucidated by spectroscopic and chemical methods. The cytotoxic activities of compounds 1 and 2 were evaluated against five human tumor cell lines (HCT-116, HepG2, BGC-823, NCI-H1650, and A2780). Compounds 1 and 2 showed moderate cytotoxic activities toward the tested cell lines with IC₅₀ values ranging from 12.71 to 32.04 μM.     

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.     

Three new oleanane-type triterpenoid saponins from the seeds of Celosia cristata L.

Phytochemical investigation of the 1-butanol soluble fraction of 60% ethanol extract of the seeds of Celosia cristata L. led to the identification of three new oleanane-type triterpenoid saponins. Using ¹D and ²D NMR experiment methods, ESI-MS analysis and acid hydrolysis, their structures were identified as 3-O-[β-D-xylopyranosyl-(1 → 3)-β-D-glucuronopyranosyl]-2β-hydroxy-oleanolic acid-28-O-β-D-glucopyranoside (1), 3-O-[β-D-xylopyranosyl-(1 → 3)-β-D-glucuronopyranosyl]-2β, 23-dihydroxy-oleanolic acid-28-O-β-D-glucopyranoside (2) and 3-O-[β-D-glucopyranosyl-(1 → 4)-β-D-glucopyranosyl]-2-hydroxyl-medicagenic acid-28-O-β-D-glucopyranosyide (3), respectively.     

Acetylcholinesterase inhibitory active metabolites from the endophytic fungus Colletotrichum sp. YMF432

An endophytic fungus, Chaetomium sp. YMF432, was isolated from Huperzia serrata (Thunb. ex Murray) Trev. and subjected to phytochemical investigation based on its special environment. From the extracts of fermentation solid of strain YMF 432, eight compounds including 1-O-methylemodin (1), 5-methoxy-2-methyl-3-tricosyl-1,4-benzoquinone (2), 4,8-dihydroxy-1-tetralone (3), (3β,5α,6α, 22E)-3-hydroxy-5,6-epoxy-7-one-8(14),22-dien-ergosta (4), ergosta-4,6,8(14),22-tetraen-3-one (5), β-sitostenone (6), β-sitosterol (7) and (22E,24R)-ergosta-5,7,22 -trien-3β-ol (8) were obtained. Their structures were elucidated on the basis of their spectroscopic data. These compounds were evaluated for acetylcholinesterase inhibitory activities in vitro. Compounds 1, 2, and 4 showed moderate acetylcholinesterase inhibitory activities (IC₅₀ from 37.7 ± 1.5 to 370.0 ± 2.9 μM).     

Three new flavonoid glycosides from Smilax glabra and their anti-inflammatory activity

Three new flavonoid glycosides, 2(S)-5-hydroxy-6,8-dimethoxyflavonone-7-O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranoside (1), 5-hydroxy-3,8-dimethoxyflavone-7-O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranoside (2) and 3,7-dihydroxy-8-methoxyflavone-6-O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranoside (3), together with five known flavonoids (4–8) were isolated from the roots of Smilax glabra Roxb. Their structures were elucidated on the basis of chemical and spectral evidence, as well as by comparison with literature data. Three new flavonoids were subjected to evaluate anti-inflammatory activity. Compounds 1–3 inhibited the NF κB induction by 32.2, 55.8 and 61.7%, respectively.     

New lipoxygenase and cholinesterase inhibitory sphingolipids from Carthamus oxyacantha

Two new sphingolipids: oxyacanthin A [(2S,3S,4R)-2-{[(2R,5E)-2-hydroxyoctadec-5-enoyl]amino}hexaeicosane-1,3,4-triol; 1] and B [(2S,3S,4R)-2-{[(2R,5E)-2-hydroxyoctadec-5-enoyl]amino}hexaeicosane-1,3,4-triol-1-O-β-D-glucopyranoside; 2], together with 1-octacosanol, β-sitosterol, β-sitosterol 3-O-β-D-glucopyranoside and luteolin 7-O-β-glucopyranoside were isolated from the methanolic extract of the whole plant of Carthamus oxyacantha. Their structures were elucidated using ¹H and ¹³C NMR spectra and 2D NMR analyses (HMQC, HMBC and COSY) in combination with mass spectrometry (EI-MS, HR-EI-MS, FAB-MS and HR-FAB-MS) experiments and in comparison with the literature data of the related compounds. Both the compounds 1 and 2 showed inhibitory potential against lipoxygenase (LOX) in a concentration-dependent manner with IC₅₀ values 83.3 ± 1.3 and 245.7 ± 1.1 µM, whereas compound 2 showed inhibition against enzymes acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) with IC₅₀ values 65.3 ± 0.1 and 93.6 ± 0.1 µM, respectively.     

Chemical composition and antioxidant activity of aerial parts of Ferula longipes Coss. ex Bonnier and Maury

This is the first study on the phytochemistry and antioxidant activity of Ferula longipes Coss. ex Bonnier and Maury (Apiaceae). A new flavonoid quercetin-3-O-α-L-rhamnopyranoside-7-O-ß-D-[2-O-caffeoyl]-glucopyranoside (1), along with 10 known compounds kaempferol-3-O-α-L-rhamnopyranoside (2), quercetin-3-O-α-L-rhamnopyranoside (3), kaempferol-3-O-ß-D-glucopyranoside-7-O-α-L-rhamnopyranoside (4), isorhamnetin-3-O-α-L-rhamnopyranoside-7-O-ß-D-glucopyranoside (5), quercetin-3-O-α-L-rhamnopyranoside-7-O-ß-D-glucopyranoside (6), isorhamnetin-3,7-di-O-β-D-glucopyranoside (7), apigenin (8), apigenin-7-O-ß-D-glucopyranoside (9), 3,5-dicaffeoylquinic acid (10), deltoin (11) were isolated from the aerial parts of Ferula longipes Coss. Structures elucidation was performed by comprehensive 1D and 2D NMR analyses, mass spectrometry and by comparison with literature data. The compounds 1, 3, 4, 6, 7 and 10 were evaluated for their antioxidant activity, compound 1 exhibited the best antiradical activity potential and showed IC₅₀ and A_0.5 values 5.70, 7.25, 5.00, and 2.63 μg/mL towards DPPH free radical-scavenging, ABTS, CUPRAC, and reducing power assays, respectively compared with BHA, BHT and ascorbic acid which were used as positive controls.     

New flavonoid glycosides and other chemical constituents from Clerodendrum phlomidis leaves: isolation and characterisation

Phytochemical investigation of the plant Clerodendrum phlomidis Linn. F. (Lamiaceae) has now led to the isolation of two new flavonoid glycosides (1, 2) together with six known compounds identified as pectolinaringenin (3), pectolinaringenin-7-O-β-d-glucopyranoside (4), 24β-ethylcholesta-5,22E,25-triene-3β-ol (5), 24β-ethylcholesta-5,22E,25-triene-3β-O-β-D-glucopyranoside (6), (2S,3S,4R,10E)-2-[(2′R)-2′-hydroxytetracosanoylamino]-10-octadecene-1,3,4-triol (7) and andrographolide (8) mainly by spectroscopic analysis. Compounds 4 and 6–8 are reported for the first time from C. phlomidis.     

A novel dimeric flavonol glycoside from Cynanchum acutum subsp. sibiricum

A novel dimeric flavonol glycoside, Cynanflavoside A (1), together with six analogues, kaempferol-3-O-α-L-rhamnopyranosyl-(1→2)-β-D-glucopyranoside (2), quercetin-3-O-α-L-rhamnopyranosyl-(1→2)-β-D-glucopyranoside (3), kaempferol-3-O-α-L-rhamnopyranosyl-(1→2)-β-D-xylopyranoside (4), quercetin-3-O-α-L-rhamnopyranosyl-(1→2)-β-D-xylopyranoside (5), kaempferol-3-O-β-D-glucopyranosyl-7-O-α-L-rhamnopyranoside (6), and quercetin-3-O-galactoside (7) were isolated from the n-butyl alcohol extract of Cynanchum acutum subsp. sibiricum. Their structures were determined spectroscopically and compared with previously reported spectral data. All compounds were evaluated for their anti-complementary activity in vitro, and only compound 5 exhibited anti-complement effects with CH₅₀ value of 0.33 mM.     

Microbial transformation of quercetin and its prenylated derivatives

The microbial transformation studies of 7-O-prenylquercetin (1), 4′-O-prenylquercetin (2) and quercetin (3) were investigated with 20 different microbial strains to discover new metabolites. It was revealed that the fungus Mucor hiemalis was the most appropriate micro-organism which was capable of transforming these flavonoids. Structures of the three new (4–6) and one known (7) metabolites were elucidated as 7-O-prenylquercetin 3-O-β-D-glucopyranoside (4), 4′-O-prenylquercetin 3-O-β-D-glucopyranoside (5), 4′-O-prenylquercetin 3′-O-β-D-glucopyranoside (6) and quercetin 5-O-β-D-glucopyranoside (7) by the spectroscopic methods.     

A new proline-containing flavonol glycoside from Caragana leucophloea Pojark

One new proline-containing flavonol glycoside, namely kaempferol-3-O-methyl-7-O-β-d-glucopyranosyl-8-(1-methyleneproline)-4′-O-β-d-glucopyranoside (1), together with 15 known flavonoids, 3-O-methylkaempferol (2), 3-O-methylquercetin (3), quercetin (4), kaempferol (5), apigenin (6), rhamnazin (7), astragalin (8), alquds (9), quercitrin (10), rutin (11), isoquercitrin (12), apigetrin (13), myricitrin (14), hesperidin (15) and calycosin-7-O-β-d-glucopyranoside (16) were isolated from the aerial parts of Caragana leucophloea Pojark. (Leguminosae). Their structures were determined on the basis of spectroscopic analyses and by comparison with literature data. Compounds 2–4 revealed a strong antimicrobial activity with minimum inhibitory concentration values of 12.5–150 μg/mL and median inhibitory concentration (IC₅₀) values of 7.42–76.61 μg/mL. Compounds 3, 4, 6–8, 10–12 and 14 showed strong antioxidant activity. Compounds 2–7 exhibited moderate antinematodal activity on Caenorhabditis elegans with IC₅₀ values of 40.51–68.05 μg/mL.     

New coumarin from the roots of Prangos pabularia

The new coumarin 1, yuganin A (7-methoxy-8-((1S,2S)-1,2,3-trihydroxy-3-methylbutyl)-2H-chromen-2-one) along with nine known coumarins, heraclenol 3′-O-β-D-glucopyranoside (2), oxypeucedanin hydrate 3′-O-β-D-glucopyranoside (3), heraclenol (4), oxypeucedanin hydrate (5), osthole (6), oxypeucedanin (7), heraclenin (8), isoimperatorin (9), imperatorin (10) and the disaccharide sucrose (11), have been isolated from the roots of Prangos pabularia, and the structures of these isolated compounds were elucidated by spectroscopic means, especially, UV, HR-ESIMS, and 1D and 2D NMR spectroscopy. Furthermore, the anti-melanogenic effect of yuganin A and its inhibitory effect on B16 cells were evaluated. Yuganin A may be useful in the treatment of hyperpigmentation and as a skin-whitening agent in the cosmetics industry.     

Antimicrobial and allelopathic metabolites produced by Penicillium brasilianum

Six known compounds, isoroquefortine C (1), griseofulvin (2), ergosterol peroxide (3), 3β-hydroxy-(22E,24R)-ergosta-5,8,22-trien-7-one (4), cerevisterol (5) and (22E,24R)-6β-methoxyergosta-7,22-diene-3β,5α-diol (6), were produced by the fungus Penicillium brasilianum, and their structures were elucidated by spectroscopic methods. This is the first report on isoroquefortine C as naturally occurring compound. Their bioactivities against five phytopathogenic fungi (Gibeberalla saubinetti, Fusarium solani, Botrytis cinerea, Colletotrichum gloeosporioides and Alternaria solani) and four pathogenic bacteria (Escherichia coli, Bacillus subtilis, Staphyloccocus aureus and Bacillus cereus), as well as allelopathic activities on Raphanus sativus were tested. Compound 1 exhibited a remarkable antifungal activity with minimum inhibitory concentration (MIC) of 12.5 μM against C. gloeosporioides, in comparison with positive control hymexazol (MIC 25 μM). Compound 2 displayed strong inhibitory effects on the growth of A. solani and S. aureus with MIC of 3.13 μM for each. Compounds 2 and 3 displayed a significant growth-inhibition activity on R. sativus.     

New dammarane and ursane-type triterpenoids from the flower of Ixora coccinea Linn.

Two new esters of dammarane triterpenoids ixorene isovalerate (1), ixorene 3′,8′-dimethyloctanoate (2) and a new ursane-type triterpenoids Ixoroid acid (3) were isolated from the methanolic extract of flowers of Ixora coccinea Linn., along with the three known constituents. The structures of compounds 1 and 3 were elucidated on the basis of extensive 1D,2D NMR studies and mass spectrometry as 17β-dammara-12,20-diene-3β-isovelarate and 3β-hydroxy-18β-urs-12ene-29β-oic acid, respectively, whereas 2 was identified as 17β-dammara-12,20-diene-3β-3′,8′-dimethyloctanoate through ¹H NMR and mass spectral data. Compounds 1, 2, 4 and 5 were evaluated for their in vitro cytotoxic activity, which exhibited weak activity against the 3T3, PC3 and HeLa cell lines with the IC₅₀ value >30 μM. Antioxidant results of 1 – 5 revealed that only compound 5 showed antioxidant activity in DPPH radical scavenging inhibition with the IC₅₀ 1.31 × 10^? 6 ± 0.005 μm mL^? 1. Both activities are the first records of these isolated compounds from the flowers of Ixora coccinea Linn.     

Biotransformation of ursolic acid by Alternaria longipes AS3.2875

Microbial transformation of ursolic acid (1) was carried out by Alternaria longipes AS 3.2875. Six transformed products (2–7) from 1 were isolated and their structures were identified as 3-carbonyl ursolic acid 28-O-β-D-glucopyranosyl ester (2), ursolic acid 3-O-β-D-glucopyranoside (3), ursolic acid 28-O-β-D-glucopyranosyl ester (4), 2α, 3β-dihydroxy ursolic acid 28-O-β-D-glucopyranosyl ester (5), 3β, 21β dihydroxy ursolic acid 28-O-β-D-glucopyranosyl ester (6), and 3-O-(β-D-glucopyranosyl)- ursolic acid 28-O-(β-D-glucopyranosyl) ester (7) based on the analysis of 1D NMR, 2DNMR and MS data. The product 2 was a new compound among them and showed stronger antibacterial activity against S. aureu, MRSA and MRCA than substrate. In this study, we modified structure of ursolic acid through biotransformation to enhance its activities and preliminarily discussed the transformation way of the products.     

Ascomycotin A,a new citromycetin analogue produced by Ascomycota sp. Ind19F07 isolated from deep sea sediment

A new citromycetin analogue, ascomycotin A (1), together with eight known compounds, wortmannilactone E (2), orcinol (3), orsellinic acid (4), isosclerone (5), (3R,4S)-( ? )-4-hydroxymellein (6), diorcinol (7), chaetocyclinone B (8) and 2,5-dimethoxy-3,6-di(p-methoxypheny1)-1,4-benzoquinone (9), was isolated from the fungal strain Ascomycota sp. Ind19F07, which was isolated from the deep sea sediment of the Indian Ocean. The structures of the compounds were established by spectroscopic data including 1D and 2D NMR and HR-ESI-MS. Compounds (1–9) were evaluated for antibacterial activity.     

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.     

A new triterpenoid saponin from Clinopodium chinense (Benth.) O. Kuntze

A new triterpene saponin, 3β,16β,23α,28β,30β-pentahydroxyl-olean-11,13(18)-dien-3β-yl-[β-d-glucopyranosyl-(1→2)]-[β-d-glucopyranosyl-(1→3)]-β-d-fucopyranoside, was named Clinoposaponin D (1), together with six known triterpene saponins, buddlejasaponin IVb (2), buddlejasaponin IVa (3), buddlejasaponin IV (4), clinopodisides D (5), 11α,16β,23,28-Tetrahydroxyolean-12-en-3β-yl-[β-d-glucopyranosyl-(1→2)]-[β-d-glucopyranosyl-(1→3)]-β-d-fucopyranoside (6) and prosaikogenin A (7), and two known triterpenes, saikogenin A (8) and saikogenin F (9) were isolated from Clinopodium chinense (Benth.) O. Kuntze. Their structures were elucidated on the basis of 1D, 2D NMR and MS analysis. Meanwhile, the effects of all compounds on rabbit platelet aggregation and thrombin time (TT) were investigated in vitro. Compounds 4 and 7 had significant promoting effects on platelet aggregation with EC₅₀ value at 53.4 and 12.2 μM, respectively. In addition, the highest concentration (200 μM) of compounds 2 and 9 shortened TT by 20.6 and 25.1%, respectively.