Chemical constituents from Dictamnus dasycarpus Turcz.

Fifteen compounds (1–15) were isolated from Dictamnus dasycarpus Turcz. The structures of all compounds were elucidated on the basis of spectroscopic data. Their structures were identified as dictamnine (1), skimmianine (2), haplopine (3), γ-fagarine (4), dasycarine (5), glycolone (6), 8,9-dimethoxygeibalansine (7), 7,8-dimethoxymyrtopsine (8), 8-methoxyflindersine (9), 3-formylindole (10), kihadanin A (11), fraxinellone (12), β-sitosterol (13), radicol (14), and magnolol (15). Among them, compounds 10 and 15 were isolated for the first time in the genus Dictamnus and this is the first report of the presence of compound 14 in the Dictamni dasycarpus Turcz.     

Microbial transformation of neoandrographolide by Mucor spinosus (AS 3.2450)

Microbial transformation of neoandrographolide (1), was performed by Mucor spinosus (AS 3.2450). Ten metabolites were obtained and identified as 14-deoxyandrographolide (2), 17,19-dihydroxy-8,13-ent-labdadien-16,15-olide (3), 3,14-dideoxyandrographolide (4), 7β-hydroxy-3,14-dideoxyandrographolide (5), 17,19-dihydroxy-7,13-ent-labdadien-16,15-olide (6), 8(17),13-ent-labdadien-16,15-olid-19-oic acid (7), 8α,17β-epoxy-3,14-dideoxyandrographolide (8), 8β,17,19-trihydroxy-ent-labd-13-en-16, 15-olide (9), phlogantholide-A (10), 19-[(β-d-glucopyranosyl)oxy]-19-oxo-ent-labda-8(17),13-dien-16,15-olide (11) by spectroscopic and chemical means. Among them, products 3, 5, 6, 8 and 9 were characterized as new compounds. The inhibitory effects of compounds 1–11 on nitric oxide production in lipopolysaccharide-activated macrophages were evaluated and their preliminary structure–activity relationships (SAR) were discussed.     

γ-Irradiation-induced ring-opening of polycrystalline cycloamylose hydrates

The chemical modifications induced in polycrystalline cycloamylose hydrates during γ-irradiation have been investigated by using g.l.c-m.s. to analyse the monosaccharide mixtures formed on hydrolysis. Unchanged substrate and material retaining the original cyclic structure were removed by precipitation prior to hydrolysis, and the products therefore reflect the effect of the radical-induced opening of the cycloamylose ring structure. The following products were identified: glucose and glucono-1, 5-lactone (1), 4-deoxy-xylo-hexose (2), arabinose (3), ribose (4), 2-deoxy-erythro-pentose (5), 3-deoxy-erythro-hexos-4-ulose (6), xylo-hexos-5-ulose (7), 6-deoxy-xylo-hexos-5-ulose (8), 5-deoxy-xylo-hexodialdose (9), 2,6-dideoxyhexos-5-ulose (10), xylose (11), 5-deoxypentose (12), 3-deoxypentulose (13), erythrose (14), and threose (15). Products 1-9 appear to be terminals of the “anhydroglucose” chain. Established free-radical reactions, typical for carbohydrates. are invoked to account for these products.     

Styrylpyrones from the medicinal fungus Phellinus baumii and their antioxidant properties

During the search for natural antioxidants from basidiomycetes, a new styrylpyrone, baumin (1), was isolated from the cultivated medicinal fungus Phellinus baumii, together with known compounds, davallialactone (2), hispidin (3), hypholomine B (4), interfungin A (5), inoscavin A (6), and phelligridin D (7), which were previously isolated from the medicinal fungi Phellinus ignarius, Phellinus linteus, and Inonotus xeranticus. Their structures were elucidated by extensive spectroscopic methods. These compounds exhibited antioxidant activity through Fenton reaction inhibition via iron chelation and free radical scavenging.     

Biotransformation of capsaicin by Penicillium janthinellum AS 3.510

Biocatalysis of capsaicin (1) was performed by Penicillium janthinellum AS 3.510. Nine metabolites including four new compounds were afforded, and their structures were elucidated as (8S)-trans-8-hydroxy-8-hydroxymethyl-N-vanillyl-6-nonenamide (2), 6-hydroxy-8-methyl-N-vanillyl-7-nonenamide (3), trans-8-methoxy-8-methyl-N-vanillyl-6-nonenamide (4), 6-methoxy-8-methyl-N-vanillyl-7-nonenamide (5), dihydrocapsaicin (6), ω-1-hydroxydihydrocapsaicin (7), ω-1-hydroxycapsaicin (8), ω-hydroxycapsaicin (9), N-(4-hydroxy-3-methoxybenzyl)-5-[3-(propan-2-yl)oxiran-2-yl]pentanamide (10) by 1D and 2D NMR and HRESIMS spectra. The biotransformation processes include hydroxylation, methylation, reduction, and epoxylation.     

Cassane-type diterpenoids from Caesalpinia latisiliqua (Cav.) Hattink

Three new cassane-type diterpenoids, namely caesalatic acids A–C (1 ‒3), and seven known compounds, resveratrol (4), piceatannol (5), aromadendrin (6), taxifolin (7), 3,4-dihydroxybenzaldehyde (8), methyl gallate (9), and loliolide (10) were isolated from the methanol extract of the Caesalpinia latisiliqua (Cav.) Hattink leaves. Their chemical structures were elucidated by 1D- and 2D-NMR, MS data, circular dichroism, and compared with NMR data in the literature.     

Triterpenoidal alkaloids from Buxus hyrcana and their enzyme inhibitory,anti-fungal and anti-leishmanial activities

From the aerial parts of Buxus hyrcana, three triterpenoidal alkaloids, 17-oxo-3-benzoylbuxadine (1), buxhyrcamine (2), and 31-demethylcyclobuxoviridine (3), along with 16 known compounds, cyclobuxoviridine (4), N_b-dimethylcyclobuxoviricine (5), E-buxenone (6), Z-buxenone (7), moenjodaramine (8), homomoenjodarmine (9), buxamine A (10), buxamine B (11), 31-hydroxybuxamine B (12), N₂₀-formylbuxaminol E (13), papillozine C (14), buxmicrophylline F (15), buxrugulosamine (16), cyclobuxophylline O (17), spirofornabuxine (18) and arbora-1,9(11)-dien-3-one (19) were isolated. Their structures were elucidated by using NMR spectroscopic methods. All of the compounds exhibited moderate to weak acetylcholinesterase, butyrylcholinesterase and glutathione S-transferase inhibitory activities. Compounds 1–19 also exhibited modest anti-fungal activities against Candida albicans. Compounds 1, 2, 8, 9 and 18 also exhibited weak anti-leishmanial activity.     

Sesquiterpene lactones and other secondary metabolites from Crepis commutata (Spreng.) Greuter – Asteraceae

Sesquiterpene lactones, especially guaianolides, are widespread in the genus Crepis L. We have undertaken the chemical investigation of Crepis commutata (Spreng.) Greuter, an edible plant in Crete. From the non-polar extract of the aerial flowering parts of C. commutata five sesquiterpene lactones: 8-epi-grosheimin (1), 8-epi-isoamberboin (2), 8-epi-isolipidiol (3), 3-acetyl-8-epi-isolipidiol (4), integrifolin 3-O-β-D-glucopyranoside (5), two flavonoids: luteolin (6), luteolin 7-O-β-D-glucuronide (7), and three phenolic acids: p-anisic acid (8), p-hydroxyphenylacetic acid (9) and E-caffeic acid (10) were isolated. The structures of the isolated compounds were elucidated by high-field NMR spectroscopy.     

Sesquiterpene lactones from the leaves of Magnolia sirindhorniae

Five sesquiterpene lactones, costunolide (1), santamarine (2), reynosin (3), parthenolide (4), and lipiferolide (5), were isolated from the leaves of Magnolia sirindhorniae. Their structures were identified by analysis of spectroscopic data and comparison with those reported in the literature. Compound 5 was isolated from the Magnolia for the first time, and this is the first report of the isolation of the sesquiterpene lactones from M. sirindhorniae.     

Flavonoids from the leaves and flowers of the Himalayan Cathcartia villosa (Papaveraceae)

Five flavonols, four flavones and one C-glycosylflavone were isolated from the leaves of Cathcartia villosa which is growing in the Himalayan Mountains. They were characterized as quercetin 3-O-vicianoside (1), quercetin 7,4′-di-O-glucoside (3), quercetin 3-O-rutinoside (4), quercetin 3-O-glucoside (5), quercetin 3-O-arabinosylarabinosylglucoside (6) (flavonols), luteolin (7), luteolin 7-O-glucoside (8), apigenin (9), chrysoeriol (10) (flavones), and vicenin-2 (11) (C-glycosylflavone) by UV, LC-MS, acid hydrolysis, NMR and/or HPLC and TLC comparisons with authentic samples. On the other hand, two flavonols 1 and kaempferol 3-O-vicianoside (2) were isolated and identified from the flowers of the species. Flavonoids were reported from the genus Cathcartia in this survey for the first time. Their chemical characters were chemotaxonomically compared with those of related Papaveraceous genera, Meconopsis and Papaver.     

Two new pyrazines from the parent roots of Aconitum carmichaelii

Two new pyrazines, aconicarpyrazine A (1) and aconicarpyrazine B (2), together with five known heterocyclic compounds: adenosine (3), uridine (4), hypoxanthine (5), nicotinamide (6), and uracil (7), were isolated from the parent roots of Aconitum carmichaelii. The structures of these alkaloids were elucidated by spectroscopic analysis, including 2D NMR techniques. This is the first report of pyrazines in a species of Aconitum.     

Phytochemical and chemotaxonomic study on Piper pleiocarpum Chang ex Tseng

The phytochemical study of Piper pleiocarpum Chang ex Tseng led to the isolation of eighteen compounds (1–18), including ten lignanoids, galbelgin (1), (+) sesamin (2), denudatin A (3), hancinone (4), (7S,8S, 3′R)-Δ^8'-3,3′,4-trimethoxy-3′,6′-dihydro-6′-oxo-7.0.4′,8.3′-lignan[(2S,3S,3aR)-2-(3,4-dimethoxyphenyl)-3,3a-dihydro-3a-methoxy-3-methyl-5-(2-propenyl)-6(2H))-benzofuranone] (5), (−)-(7R,8R)-machilin D (6), (1R,2R)-2-[2-methoxy-4-((E)-prop-1-enyl)phenoxy]-1-(3,4-dimethoxyphenyl)propyl acetate (7), piperbonin A (8), machilin D (9), 4-methoxymachilin D (10), one amide alkaloid, Δ^α,β-dihydropiperine (11), six polyoxygenated cyclohexenes, ent-curcuminol F (12), uvaribonol E (13), ellipeiopsol A (14), 1S,2R,3R,4S-1-ethoxy-2-[(benzoyloxy)methyl]cyclohex-5-ene-2,3,4-triol, 3-acetate (15), (+)-crotepoxide (16), (+)-senediol (17), and one benzoate derivative, 2-acetoxybenzyl benzoate (18). Their structures were established by spectroscopic data and by comparison with the literature. All the compounds were firstly isolated from P. pleiocarpum, while ten compounds 6–7, 9–10, 12–15, 17–18 were isolated from the genus Piper and the family Piperaceae for the first time. The chemotaxonomic significance of these compounds was also discussed. The isolation of compounds 6–7, 9–10 may be used as chemotaxonomic markers for the genus of Piper.     

Flavonoids in the leaves of Hillebrandia and Begonia species (Begoniaceae)

The fresh leaves of Hillebrandia sandwicensis and 126 Begonia taxa were chemotaxonomically surveyed for flavonoids. Of their taxa, H. sandwicensis and 119 species, one variety and three hybrids were analyzed for flavonoids for the first time. Ten flavonols and eleven C-glycosylflavones were isolated and characterized as quercetin 3-O-rutinoside (1), kaempferol 3-O-rutinoside (2), isorhamnetin 3-O-rutinoside (3), quercetin 3-O-glucoside (4), quercetin 3-methyl ether 7-O-rhamnosylglucoside (5), quercetin 3,3'-dimethyl ether 7-O-rhamnosylglucoside (6), quercetin glycoside (13), quercetin glycoside (acylated) (14), kaempferol glycoside (17) and quercetin 3-O-rhamnoside (18) as flavonols, and isovitexin (7), vitexin (8), isoorientin (9), orientin (10), luteolin 6-C-pentoside (11), luteolin 8-C-pentoside (12), schaftoside (15), isoschaftoside (16), chrysoeriol 6,8-di-C-pentoside (19), apigenin 6,8-di-C-arabinoside (20) and isovitexin 2''-O-glucoside (21) as C-glycosylflavones. Quercetin 3-O-rutinoside (1) alone was isolated from H. sandwicensis endemic to Hawaii. Major flavonoids of almost Begonia species was also 1. Begonia species were divided into two chemotypes, i.e. flavonol containing type and C-glycosylflavone containing type. Of 14 section of the Begonia, almost species of many section, i.e. sect. Augustia, Coelocentrum, Doratometra, Leprosae, Loasibegonia, Monopteron and Ruizoperonia, were flavonol types. On the other hand, C-glycosyflavone type was comparatively most in sect. Platycentrum.     

Chevalierinoside B and C: Two new isoflavonoid glycosides from the stem bark of Antidesma laciniatum Muell. Arg (syn. Antidesma chevalieri Beille)

Chevalierinosides B (1) and C (2), two new isoflavonoid glycosides, characterized as biochanin A 7-O-[β-d-apiofuranosyl-(1→2)-β-d-glucopyranoside] and genistein 7-O-[β-d-apiofuranosyl-(1→2)-β-d-glucopyranoside], together with the known isoflavonoids, chevalierinoside A (3) and genistein 7-O-β-d-glucopyranoside (4), kaempferol 3-O-β-d-glucopyranoside (5) and triterpenes, friedelin (6), betulinic acid (7), 30-oxobetulinic acid (8), 30-hydroxybetulinic acid (9), were isolated from the stem bark of Antidesma laciniatum Muell. Arg. (syn. Antidesma chevalieri Beille). Their structures were established by direct interpretation of their spectral data, mainly HR-TOFESIMS, 1D-NMR (¹H, ¹³C and DEPT) and 2D-NMR (COSY, NOESY, TOCSY, HSQC and HMBC), and by comparison with the literature.     

Phytochemical and chemotaxonomic study on Saussurea medusa Maxim. (Compositae)

A phytochemical investigation of Saussurea medusa Maxim. led to the isolation of eleven compounds, including neoechinulin A (1), 8-hydroxypinoresinol (2), caruilignan D (3), 7(S)-hydroxyarctigenin (4), pinoresinol (5), arctigenin (6), arctii (7), epipinoresinol (8), loliolide (9), apigenin (10), and luteolin (11). Their structures were elucidated by spectroscopic methods and comparison with previously reported spectral data. Among them, compounds 1 and 2 were firstly obtained from this species, compounds 3 and 4 were isolated from the genus Saussurea for the first time. Furthermore, the chemotaxonomic significance of these compounds was discussed in details.     

Occurrence of bergenin phenylpropanoates in Vatica bantamensis

We isolated five bergenin phenylpropanoates, i.e., 11-O-(E)-sinapate (1), 11-O-(E)-ferulate (2), 11-O-(Z)-ferulate (3), 11-O-(E)-coumalate (4), and 11-O-(Z)-coumalate (5), and three bergenin hydroxybenzoates, i.e., 11-O-syringate (6), 11-O-vanillate (7), and 11-O-p-hydroxybenzoate (8), along with bergenin (9), from the leaves of Vatica bantamensis. Moreover, we identified the geometrical isomerization between 2 and 3. These structures were characterized by nuclear magnetic resonance (NMR). This is the first report that shows the occurrence of bergenin phenolic acid esters in dipterocarpaceaeous plants.     

New flavonoids from the fruits of Cornus mas,Cornaceae

One new β-hydroxychalcone, 4-acetoxy-5,2′,4′,6′,β-pentahydroxy-3-methoxychalcone (1), one new flavanone, 7,3′-dihydroxy-5,4′-dimethoxyflavanone (2) and seven known compounds, 2R, 3R-trans-aromadendrin (3), naringenin-7-O-methylether (4), myricetin (5), quercetin-3-O-rutinoside (6), ursolic acid (7), gallic acid (8) and d-glucose (9) were isolated from the methanolic fruit extract of Cornus mas L. (=Cornus mascula L.), Cornaceae. The structures of the new compounds were elucidated on the basis of extensive spectroscopic methods, including 2D NMR experiments and of known compounds by comparison of physical and spectral data with literature.     

Isoflavonoids and norneolignan from Caragana changduensis

Two new isoflavonoids, named 6,7,2′-trihydroxy-4′-methoxyisoflavone (1), 7,3′-dimethoxy-5′-hydroxyisoflavone (2), one new norneolignan, named (8S)-2,4-dihydroxy-8-hydroxymethyl-4′-methoxydeoxybenzoin (3); together with six known compounds, methyl 4-hydroxylbenzoate (4), ethyl 4-hydroxybenzoate (5), piceatannol (6), cararosin A (7), 2,4-dihydroxybenzoate (8), and 6,7,4′-trihydroxyisoflavone (9) were isolated from the red heartwood in the rhizomes of Caragana changduensis by using chromatographic methods Their structures were determined by extensive spectroscopic analysis and comparison of their spectral data with previous reported data.     

Chemical constituents from the roots of Cichorium glandulosum Boiss. et Huet (Asteraceae)

A phytochemical investigation of the roots extract of Cichorium glandulosum led to the isolation and characterization of fourteen compounds, including five sesquiterpene lactones (1–5), five flavonoids (6–10), and four lignans (11–14). Their structures were determined by spectroscopic data analysis and comparison with the literatures. This is the first report of the crystal data of lactucopicrin (1). This is the first time to report the isolation of 6,8,11-epi-desacetylmatricarin (2), desacetylmatricarin (3), ixerisoslde C (4), magnodelavin (5), 2ʹ,4-dihydroxy-4ʹ-methoxy-6ʹ-O-β-glucopyranoside dihydrochalcone (6), (−)-evofolin B (7), isoquercitrin (8), myricetin 7-methyl-ether-3-O-glucoside (9), (+)-medioresinol (12), 4-O-methylcedrusin [2-(3ʹ,4ʹ-dimethoxyphenyl)-3-hydroxymethyl-2,3-dihydro-7-hydroxybenzofuran-5-propan-1-ol] (13), and (2R,3S)-samwirin A (14) from C. glandulosum. Among them, compounds 5, 9, 13, and 14 were obtained from Asteraceae family for the first time. The chemotaxonomic significance of all the isolates 1–14 was discussed.     

Cytotoxic biotransformed products from andrographolide by Rhizopus stolonifer ATCC 12939

Biotransformation of andrographolide (1) by Rhizopus stolonifer ATCC 12939 was investigated. Ten bioconversion products were isolated and identified. Their structures were elucidated by high resolution mass spectroscopy (HR-MS), extensive NMR techniques, including ¹H NMR, ¹³C NMR, DEPT, ¹H–¹H correlation spectroscopy (COSY), two dimensional nuclear Overhauser effect correlation spectroscopy (NOESY), heteronuclear multiple quantum coherence (HMQC) and heteronuclear multiple bond coherence (HMBC). Their structures were identified to be 12(R),13(R)-12-hydroxyandrographolide (2), 12(S),13(S)-12-hydroxyandrographolide (3), isoandrographolide (4), 3-dehydro-isoandrographolide (5), 14-deoxy-11,12-didehydroandrographolide (6), 3-oxo-14-deoxy-11,12-didehydroandrographolide (7), 3-dehydroandrographolide (8), 14-deoxyandrographolide (9), 3-dehydro-14-deoxyandrographolide (10) and 3-dehydro-14-deoxyandrographolide-19-oic acid (11). Among them, compounds 5 and 11 are novel compounds. The biosynthetic pathways of andrographolide by R. stolonifer were proposed. Most of the products showed potential antiproliferative activities against human breast cancer (MCF-7), human colon cancer (HCT-116) and human leukemia (HL-60) cell lines, and their structure–activity relationships (SAR) were discussed in detail.