Prolyl endopeptidase inhibitors from the underground part of Rhodiola sachalinensis

The methanolic extract of the underground part of Rhodiola sachalinensis was found to show inhibitory activity on prolyl endopeptidase (PEP, EC. 3.4.21.26), an enzyme that plays a role in the metabolism of proline-containing neuropeptidase which is recognized to be involved in learning and memory. From the MeOH extract, five new monoterpenoids named sachalinols A (24), B (25) and C (26) and sachalinosides A (23) and B (27) were isolated, together with twenty-two known compounds, gallic acid (1), trans-p-hydroxycinnamic acid (2), p-tyrosol (3), salidroside (4), 6n-O-galloylsalidroside (5), benzyl beta-D-glucopyranoside (6), 2-phenylethyl beta-D-glucopyranoside (7), trans-cinnamyl beta-D-glucopyranoside (8), rosarin (9), rhodiocyanoside A (10), lotaustralin (11), octyl beta-D-glucopyranoside (12), 1,2,3,6-tetra-O-galloyl-beta-D-glucose (13), 1,2,3,4,6-penta-O-galloyl-beta-D-glucose (14), kaempferol (15), kaempferol 3-O-beta-D-xylofuranosyl(1-->2)-beta-D-glucopyranoside (16), kaempferol 3-O-beta-D-glucopyranosyl(1-->2)-beta-D-glucopyranoside (17), rhodionin (18), rhodiosin (19), (-)-epigallocatechin (20), 3-O-galloylepigallocatechin-(4-->8)-epigallocatechin 3-O-gallate (21) and rosiridin (22). Among these, nineteen compounds other than 3, 4 and 9 have been isolated for the first time from R. sachalinensis, and six (6, 8, 13, 16, 17, 20) are isolated from Rhodiola plants for the first time. Among them, six compounds (13, 14, 18, 19, 21, 22) showed noncompetitive inhibition against Flavobacterium PEP, with an IC50 of 0.025, 0.17, 22, 41, 0.44 and 84 microM, respectively.     

Medicinal flowers. XXIII. New taraxastane-type triterpene, punicanolic acid, with tumor necrosis factor-alpha inhibitory activity from the flowers of Punica granatum

The methanolic extract from the flowers of Punica granatum L. (Punicaceae) was found to show inhibitory effect on tumor necrosis factor-alpha (TNF-alpha, 1 ng/ml)-induced cytotoxicity in L929 cells. By bioassay-guided separation, a new taraxastane-type triterpene, punicanolic acid (1), was isolated from the active fraction (ethyl acetate-soluble fraction) together with four triterpenes (2--5), two galloyl glucoses (6, 7), two flavones (8, 9), and beta-sitosterol. Among the constituents, 1, oleanolic acid (2), maslinic acid (4), 1,2,6-tri-O-galloyl beta-D-glucopyranoside (6), 1,2-di-O-galloyl-4,6-O-(S)-hexahydroxydiphenoyl beta-D-glucopyranoside (7), and luteolin (8) significantly inhibited TNF-alpha-induced cytotoxicity in L929 cells at 30 microM.     

Chemical constituents of the methanolic extract of leaves of Leiothrix spiralis Ruhland and their antimicrobial activity

Chemical fractionation of the methanolic extract of leaves of Leiothrix spiralis Ruhland afforded the flavonoids luteolin-6-C-β-D-glucopyranoside (1), 7-methoxyluteolin-6-C-β-D-glucopyranoside (2), 7-methoxyluteolin-8-C-β-D-glucopyranoside (3), 4'-methoxyluteolin-6-C-β-D-glucopyranoside (4), and 6-hydroxy-7-methoxyluteolin (5), and the xanthones 8-carboxymethyl-1,5,6-trihydroxy-3-methoxyxanthone (6), 8-carboxy-methyl-1,3,5,6-tetrahydroxyxanthone (7). Methanolic extract, fractions, and isolated compounds of the leaves of L. spiralis were assayed against Gram-positive (Staphylococcus aureus, Bacillus subtilis and Enterococcus faecalis) and Gram-negative bacteria (Escherichia coli, Pseudomonas aeruginosa, Salmonella setubal and Helicobacter pylori) and fungi (the yeasts Candida albicans, C. tropicalis, C. krusei and C. parapsilosis). We observed the best minimum inhibitory concentration values for the methanolic extract against Candida parapsilosis, for the fraction 5 + 6 against Gram-negative bacteria E. coli and P. aeruginosa, and compound 7 against all tested Candida strains. The methanolic extract contents suggest that this species may be a promising source of compounds to produce natural phytomedicines.     

Triterpene Acids from the Leaves of Planchonella Duclitan (Blanco) Bakhuizan

From the methanolic extract of the leaves of Planchonella duclitan, 2α,3α,19α,23‐tetrahydroxy‐13,27‐cyclours‐11‐en‐28‐oic acid (1), myrianthic acid (2), 2‐hydroxyursolic acid (3), ursolic acid (4), pomolic acid (5), rotundic acid (6), and jacoumaric acid (7) were isolated, and their structures were elucidated on the basis of their spectroscopic analysis. Among them, compound 1 was a new cyclopropyl ursane‐type triterpene acid. Additionally, compounds 4 and 7 showed significant cytotoxicity toward human colorectal carcinoma cell line HT29 and human breast carcinoma cell line MCF‐7 with IC₅₀ values ranging from 5.8 ± 1.4 to 6.5 ± 1.9 μM.     

A new cytotoxic acylated apigenin glucoside from Phyllanthus emblica L

A new acylated apigenin glucoside (apigenin-7-O-(6'-butyryl-beta-glucopyranoside) (1) was isolated from the methanolic extract of the leaves of Phyllanthus emblica L. (Euphorbiaceae) together with the known compounds; gallic acid (2), methyl gallate (3), 1,2,3,4,6-penta-O-galloylglucose (4) and luteolin-4'-O-neohesperiodoside (5). Their chemical structures were elucidated on the basis of spectroscopic studies ((1)H NMR, (13)C NMR, DEPT, HSQC, HMBC).     

Phenolics of Moringa oleifera leaves

Five flavonol glycosides characterised as kaempferide 3-O-(2',3'-diacetylglucoside), kaempferide 3-O-(2'-O-galloylrhamnoside), kaempferide 3-O-(2'-O-galloylrutinoside)-7-O-alpha-rhamnoside, kaempferol 3-O-[beta-glucosyl-(1 --> 2)]-[alpha-rhamnosyl-(1 --> 6)]-beta-glucoside-7-O-alpha-rhamnoside and kaempferol 3-O-[alpha-rhamnosyl-(1 --> 2)]-[alpha-rhamnosyl-(1 --> 4)]-beta-glucoside-7-O-alpha-rhamnoside together with benzoic acid 4-O-beta-glucoside, benzoic acid 4-O-alpha-rhamnosyl-(1 --> 2)-beta-glucoside and benzaldehyde 4-O-beta-glucoside have been isolated from methanolic extract of Moringa oleifera leaves. Also obtained from the same extract were known compounds, kaempferol 3-O-alpha-rhamnoside, kaempferol, syringic acid, gallic acid, rutin and quercetin 3-O-beta-glucoside. Their structures were determined using spectroscopic methods as well as comparison with data from known compounds.     

Marmenol: a 7-geranyloxycoumarin from the leaves of Aegle marmelos Corr

A new 7-geranyloxycoumarin [7-(2,6-dihydroxy-7-methoxy-7-methyl-3-octaenyloxy) coumarin] named marmenol (1) has been isolated from the leaves of methanolic extract of Aegle marmelos belonging to the family Rutaceae. In addition to marmenol, several known compounds have also been obtained for the first time from the same source. They include: praealtin D, trans-cinnamic acid, valencic acid, 4-methoxy benzoic acid, betulinic acid, N-p-cis- and trans-coumaroyltyramine, montanine, and rutaretin. The structures of marmenol and known constituents were established with the help of NMR spectroscopy. However, structure of 1 was further confirmed via 2-D NMR experiments.     

Glycosides of Atractylodes lancea

Five sesquiterpenoid glycosides (two guaiane-type glycosides and three eudesmane-type glucosides) and a glucoside of an acetylene derivative were newly isolated from the water-soluble portion of the methanolic extract of Atractylodes lancea rhizome together with 26 known compounds. Their structures were characterized as atractyloside A 14-O-beta-D-fructofuranoside, (1S,4S,5S,7R,10S)-10,11,14-trihydroxyguai-3-one 11-O-beta-D-glucopyranoside, (5R,7R,10S)-isopterocarpolone beta-D-glucopyranoside, cis-atractyloside I, (2R,3R,5R,7R,10S)-atractyloside G 2-O-beta-D-glucopyranoside, and (2E,8E)-2,8-decadiene-4,6-diyne-1,10-diol 1-O-beta-D-glucopyranoside on the basis of chemical and spectroscopic investigation. The presence of six characteristic guaiane-type glucosides in both rhizomes of A. lancea and Atractylodes japonica suggested a close chemotaxonomic relationship between them.     

An unusual sesquiterpenoid from Hypochaeris achyrophorus (Asteraceae)

The novel sesquiterpenoid 8alpha-hydroxyhypoglabric acid (1) was isolated from a methanolic extract of whole plants of Hypochaeris achyrophorus L. The compound was isolated by silica gel column chromatography (CC), repeated Sephadex LH-20 CC, and semi-preparative RP-HPLC. Structure elucidation was accomplished by high resolution mass spectrometry and by 1D- and 2D-NMR spectroscopy. The chemosystematic significance of the new compound is discussed in the context of sesquiterpenoids from other members of the Hypochaeridinae and in the light of recent molecular data on the phylogeny of this group.     

An antimicrobial compound isolated from Cinnamomum iners leaves with activity against methicillin-resistant Staphylococcus aureus

This study was designed to investigate the antimicrobial activity of Cinnamomum iners standardized leave methanolic extract (CSLE), its fractions and isolated compounds. CSLE and fractions were subjected to disc diffusion, minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) tests using different Gram positive and Gram negative bacteria and yeast. Within the series of fractions tested, the ethyl acetate fraction was the most active, particularly against methicillin resistant Staphylococcus aureus (MRSA) and Escherichia coli, with MIC values of 100 and 200 μg/mL, respectively. The active compound in this fraction was isolated and identified as xanthorrhizol [5-(1, 5-dimethyl-4-hexenyl)-2-methylphenol] by various spectroscopic techniques. The overall results of this study provide evidence that Cinnamomum iners leaves extract as well as the isolated compound xanthorrhizol exhibit antimicrobial activity for both Gram negative and Gram positive pathogens, especially against MRSA strains.     

Phenolic glycosides from Pyrola japonica

Five new phenolic glycosides, 2-beta-D-glucopyranosyloxy-5-hydroxyphenylacetic acid methyl ester (4), 4-hydroxy-2-[3-hydroxy-3-methylbutyl]-5-methylphenyl beta-D-glucopyranoside (5), 4-hydroxy-2-[(E)-4-hydroxy-3-methyl-2-butenyl]-5-methylphenyl beta-D-glucopyranoside (7), 4-hydroxy-2-[(2E,6Z)-8-beta-D-glucopyranosyloxy-3,7-dimethylocta-2,6-dien-1-yl]-5-methylphenyl beta-D-glucopyranoside (8), and 2,7-dimethyl-1,4-dihydronaphthalene-5,8-diol 5-O-beta-D-xylopyranosyl(1-->6)-beta-D-glucopyranoside (10), were isolated from the whole plants of Pyrola japonica (Pyrolaceae), together with androsin, (-)-syringaresinol glucoside, homoarbutin, pirolatin, hyperin, monotropein and chimaphilin.     

Ellagic acid glycosides from Turpinia ternata

Bioassay-guided fractionation of the methanolic extract of Turpinia ternata stems, has led to the isolation of the new ellagic acid derivative 3,4'-di-O-methylellagic acid-4-O-alpha-L-arabinofuranoside (1), and the known compounds ellagic acid (2), 3-O-methyl ellagic acid (3), 3-O-methylellagic acid-3'-O-alpha-L-rhamnopyranoside (4), and 3,3'-di-O-methylellagic acid-4'-O-alpha-D-glucopyranoside (5). Their structures were elucidated by extensive spectroscopic methods. Compounds 1, 3, and 4 showed moderate antioxidant activity against DPPH free radical, whereas compound 1 was found to be moderately cytotoxic against Artemia salina larvae.     

A new diterpene from the leaves of Andrographis paniculata Nees

Phytochemical investigation of the methanolic extract of the leaves of Andrographis paniculata Nees yielded a minor, new diterpene, 21-nor-3,19-isopropylidine-14-deoxy-ent-labda-8(17),13-dien-16,15-olide (1), together with five known labdane type diterpenes, andrographolide 3, 14-deoxyandrographolide 4, 14-deoxy-12-hydroxyandrographolide 5, 14-deoxy-11,12-dihydroandrographolide 6, neoandrographolide 7, and two acids, cinnamic acid 8, and ferulic acid 9. The chemical structures were established by spectroscopic analyses, including 1D- and 2D-NMR spectroscopic experiments, and on the basis of HR-ESI MS analyses. The methanolic extract of the leaves exhibited moderate antibacterial and antifungal activities at a dose of 200 microg/mL in comparison with the reference standards.     

Antihepatitis B virus constituents of Solanum erianthum

Eleven compounds were isolated from the methanolic extract of the leaves of Solanum erianthum D. Don, including five alpha-linolenic acid analogs, alpha-linolenic acid (1), 13S-hydroxy-9(Z),11(E)-octadecadienoic acid (2), 9S-hydroxy-10(E),12(Z), 15(Z)-octadectrienoic acid (3), 9(Z),11(E)-octadecadienoic acid (4), and octadecanoic acid (5); two benzofuran-type lactones, loliolide (6) and dihydroactinidiolide (7); two steroidal alkaloids, solasonine (8) and solamargine (9); a flavonol glycoside, camelliaside C (10); and a flavone, 5-methoxy-(3,4"-dihydro-3",4"-diacetoxy)-2",2'-dimethylpyrano-(7,8:5",6")-flavone (11). Among these isolated compounds, 9 showed the most potent activity against HBsAg, with an IC50 of 1.57 microM, followed by 8 (IC50 is 5.89 microM). In the testing against HBeAg, 11 was the only active compound with an IC50 of 36.11 microM. Compound 9 also revealed strong inhibition of DNA replication towards HBV and its IC50 was 2.17 microM. However, alpha-linolenic acid (1) showed a prominent selected index (SI), both in anti-HBsAg and inhibition of DNA replication with SI values of 7.75 and 7.18, respectively. This is the first report that unsaturated fatty acid 1, steroidal alkaloid glycoside 9 and flavone 11, all showed excellent activity against HBV. These results provide lead candidates in the development of anti-HBV drugs from natural sources.     

The coloring constituents of Scleroderma sinnamariense (Sclerodermaceae)

Two known coloring constituents, methyl 4,4'-dimethoxyvulpinate (1) and 4,4'-dimethoxyvulpinic acid (2) have been isolated from the fruit body of fungus Scleroderma sinnamariense Mont. The methanolic extract, its fractions and compound (2) showed moderate activity to inhibit the growth of some pathogenic testing microbes used.     

One new diphenylmethane glycoside from the leaves of Psidium guajava L

To investigate the chemical constituents of Psidium guajava L, the EtOH/H(2)O extract of the fresh leaves was subjected to various chromatography. One diphenylmethane, one benzophenone, and eight flavonoids were isolated and elucidated as 2,6-dihydroxy-3-formaldehyde-5-methyl-4-O-(6″-O-galloyl-β-D-glucopyranosyl)-diphenylmethane (1), 2,6-dihydroxy-3,5-dimethyl-4-O-(6″-O-galloyl-β-D-glucopyranosyl)-benzophenone (2), kaempferol (3), quercetin (4), quercitrin (5), isoquercitrin (6), guaijaverin (7), avicularin (8), hyperoside (9), reynoutrin (10) by spectroscopic methods, including 1D and 2D NMR and HR-ESI-MS spectrometry as well as by comparison with published data. Compounds 5 and 10 are obtained from P. guajava for the first time, and compound 1 is a new diphenylmethane compound.     

A new ethylene glycol triterpenoid from the leaves of Psidium guajava

One new pentacyclic triterpenoid psidiumoic acid (5) along with four known compounds beta-sitosterol (1), obtusol (2), oleanolic acid (3), and ursolic acid (4) have been isolated from the leaves of Psidium guajava. The new constituent 5 has been characterized as 2 alpha-glycolyl-3beta-hydroxyolean-12-en-28-oic acid through 2D NMR techniques. This is the first report of isolation of compound 2 from the genus Psidium.     

New coumarin-hemiterpene ether glucosides and a structurally related phenylpropanoic acid derivative from Artemisia armeniaca

Two new coumarin-hemiterpene ether glucosides, 4'-O-(beta-D-glucopyranosyl) desoxylacarol (1), and 5-O-(beta-D-glucopyranosyl) lacarol (2), were isolated from the methanolic extract of the aerial parts of Artemisia armeniaca Lam. Their structures were established by means of spectroscopic analysis including 1H- and 2D-NMR, HRESIMS, and acid hydrolysis. In addition, a structurally related phenylpropanoic acid derivative (3) was obtained in small amounts, and its structure tentatively assigned as 3-(4-hydroxy-3-methylbutoxy)-4-methoxy melilotic acid.     

Molluscicidal saponins from cornus florida L.

The molluscicidal principle of Cornus florida L. (Cornaceae) has been isolated from the methanolic bark extract by droplet counter-current chromatography (DCC). The structure of the active compounds has been determined as sarsapogenin-O-β-D-xylopyranosyl-(1 → 2)-β-D-galactopyranoside (2) and sarsapogenin-O-β-D-glucopyranosyl-(1 → 2)-β-D-galactopyranoside (3) .     

Two novel ravenelones from the edible mushroom Pulveroboletus ravenelii

Two novel butenolides, isoravenelone (1) and ravenelone (2), and a large amount of a known compound, vulpinic acid (3), were isolated from the methanolic extract of the Japanese fungus Pulveroboletus ravenelii (Boletales). These structures were elucidated by two dimensional (2D) NMR, MS, IR and UV spectra, and X-ray crystallographic analysis.