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Sample records for 17-hydroxygeranyllinalool diterpene glycosides

  1. Jasmonate and ppHsystemin regulate key Malonylation steps in the biosynthesis of 17-Hydroxygeranyllinalool Diterpene Glycosides, an abundant and effective direct defense against herbivores in Nicotiana attenuata.

    PubMed

    Heiling, Sven; Schuman, Meredith C; Schoettner, Matthias; Mukerjee, Purba; Berger, Beatrice; Schneider, Bernd; Jassbi, Amir R; Baldwin, Ian T

    2010-01-01

    We identified 11 17-hydroxygeranyllinalool diterpene glycosides (HGL-DTGs) that occur in concentrations equivalent to starch (mg/g fresh mass) in aboveground tissues of coyote tobacco (Nicotiana attenuata) and differ in their sugar moieties and malonyl sugar esters (0-2). Concentrations of HGL-DTGs, particularly malonylated compounds, are highest in young and reproductive tissues. Within a tissue, herbivore elicitation changes concentrations and biosynthetic kinetics of individual compounds. Using stably transformed N. attenuata plants silenced in jasmonate production and perception, or production of N. attenuata Hyp-rich glycopeptide systemin precursor by RNA interference, we identified malonylation as the key biosynthetic step regulated by herbivory and jasmonate signaling. We stably silenced N. attenuata geranylgeranyl diphosphate synthase (ggpps) to reduce precursors for the HGL-DTG skeleton, resulting in reduced total HGL-DTGs and greater vulnerability to native herbivores in the field. Larvae of the specialist tobacco hornworm (Manduca sexta) grew up to 10 times as large on ggpps silenced plants, and silenced plants suffered significantly more damage from herbivores in N. attenuata's native habitat than did wild-type plants. We propose that high concentrations of HGL-DTGs effectively defend valuable tissues against herbivores and that malonylation may play an important role in regulating the distribution and storage of HGL-DTGs in plants.

  2. Using the knowns to discover the unknowns: MS-based dereplication uncovers structural diversity in 17-hydroxygeranyllinalool diterpene glycoside production in the Solanaceae.

    PubMed

    Heiling, Sven; Khanal, Santosh; Barsch, Aiko; Zurek, Gabriela; Baldwin, Ian T; Gaquerel, Emmanuel

    2016-02-01

    Exploring the diversity of plant secondary metabolism requires efficient methods to obtain sufficient structural insights to discriminate previously known from unknown metabolites. De novo structure elucidation and confirmation of known metabolites (dereplication) remain a major bottleneck for mass spectrometry-based metabolomic workflows, and few systematic dereplication strategies have been developed for the analysis of entire compound classes across plant families, partly due to the complexity of plant metabolic profiles that complicates cross-species comparisons. 17-hydroxygeranyllinalool diterpene glycosides (HGL-DTGs) are abundant defensive secondary metabolites whose malonyl and glycosyl decorations are induced by jasmonate signaling in the ecological model plant Nicotiana attenuata. The multiple labile glycosidic bonds of HGL-DTGs result in extensive in-source fragmentation (IS-CID) during ionization. To reconstruct these IS-CID clusters from profiling data and identify precursor ions, we applied a deconvolution algorithm and created an MS/MS library from positive-ion spectra of purified HGL-DTGs. From this library, 251 non-redundant fragments were annotated, and a workflow to characterize leaf, flower and fruit extracts of 35 solanaceous species was established. These analyses predicted 105 novel HGL-DTGs that were restricted to Nicotiana, Capsicum and Lycium species. Interestingly, malonylation is a highly conserved step in HGL-DTG metabolism, but is differentially affected by jasmonate signaling among Nicotiana species. This MS-based workflow is readily applicable for cross-species re-identification/annotation of other compound classes with sufficient fragmentation knowledge, and therefore has the potential to support hypotheses regarding secondary metabolism diversification.

  3. Jasmonate and ppHsystemin Regulate Key Malonylation Steps in the Biosynthesis of 17-Hydroxygeranyllinalool Diterpene Glycosides, an Abundant and Effective Direct Defense against Herbivores in Nicotiana attenuata[W

    PubMed Central

    Heiling, Sven; Schuman, Meredith C.; Schoettner, Matthias; Mukerjee, Purba; Berger, Beatrice; Schneider, Bernd; Jassbi, Amir R.; Baldwin, Ian T.

    2010-01-01

    We identified 11 17-hydroxygeranyllinalool diterpene glycosides (HGL-DTGs) that occur in concentrations equivalent to starch (mg/g fresh mass) in aboveground tissues of coyote tobacco (Nicotiana attenuata) and differ in their sugar moieties and malonyl sugar esters (0-2). Concentrations of HGL-DTGs, particularly malonylated compounds, are highest in young and reproductive tissues. Within a tissue, herbivore elicitation changes concentrations and biosynthetic kinetics of individual compounds. Using stably transformed N. attenuata plants silenced in jasmonate production and perception, or production of N. attenuata Hyp-rich glycopeptide systemin precursor by RNA interference, we identified malonylation as the key biosynthetic step regulated by herbivory and jasmonate signaling. We stably silenced N. attenuata geranylgeranyl diphosphate synthase (ggpps) to reduce precursors for the HGL-DTG skeleton, resulting in reduced total HGL-DTGs and greater vulnerability to native herbivores in the field. Larvae of the specialist tobacco hornworm (Manduca sexta) grew up to 10 times as large on ggpps silenced plants, and silenced plants suffered significantly more damage from herbivores in N. attenuata's native habitat than did wild-type plants. We propose that high concentrations of HGL-DTGs effectively defend valuable tissues against herbivores and that malonylation may play an important role in regulating the distribution and storage of HGL-DTGs in plants. PMID:20081114

  4. Synthesis and sensory evaluation of ent-kaurane diterpene glycosides.

    PubMed

    Prakash, Indra; Campbell, Mary; San Miguel, Rafael Ignacio; Chaturvedula, Venkata Sai Prakash

    2012-07-26

    Catalytic hydrogenation of the three ent-kaurane diterpene glycosides isolated from Stevia rebaudiana, namely rubusoside, stevioside, and rebaudioside-A has been carried out using Pd(OH)₂ and their corresponding dihydro derivatives have been isolated as the products. Synthesis of reduced steviol glycosides was performed using straightforward chemistry and their structures were characterized on the basis of 1D and 2D NMR spectral data and chemical studies. Also, we report herewith the sensory evaluation of all the reduced compounds against their corresponding original steviol glycosides and sucrose for the sweetness property of these molecules.

  5. Diterpene glycosides from Stevia phlebophylla A. Gray.

    PubMed

    Ceunen, Stijn; Wim, De Borggraeve; Compernolle, Frans; Mai, Anh Hung; Geuns, Jan M C

    2013-09-20

    The rare Mexican species Stevia phlebophylla A. Gray was long considered to be the only known Stevia species, beside the well-known S. rebaudiana, containing the highly sweet diterpenoid steviol glycosides. We report a re-evaluation of this claim after phytochemically screening leaves obtained from two herbarium specimens of S. phlebophylla for the presence of steviol glycosides. Despite extensive MS analyses, no steviol glycosides could be unambiguously verified. Instead, the main chromatographic peak eluting at retention times similar to those of steviol glycosides was identified as a new compound, namely 16β-hydroxy-17-acetoxy-ent-kauran-19-oic acid-(6-O-β-D-xylopyranosyl-β-D-glucopyranosyl) ester (1) on the basis of extensive NMR and MS data as well as the characterization of its acid hydrolysate. Seven more compounds were detected by ESIMS which are possibly structurally related to 1. It can therefore be concluded that S. phlebophylla is unlikely to contain significant amounts of steviol glycosides, if any.

  6. Minor diterpene glycosides from the leaves of Stevia rebaudiana.

    PubMed

    Ibrahim, Mohamed A; Rodenburg, Douglas L; Alves, Kamilla; Fronczek, Frank R; McChesney, James D; Wu, Chongming; Nettles, Brian J; Venkataraman, Sylesh K; Jaksch, Frank

    2014-05-23

    Two new diterpene glycosides in addition to five known glycosides have been isolated from a commercial extract of the leaves of Stevia rebaudiana. Compound 1 (rebaudioside KA) was shown to be 13-[(O-β-d-glucopyranosyl)oxy]ent-kaur-16-en-19-oic acid 2-O-β-d-glucopyranosyl-β-d-glucopyranosyl ester and compound 2, 12-α-[(2-O-β-d-glucopyranosyl-β-d-glucopyranosyl)oxy]ent-kaur-16-en-19-oic acid β-d-glucopyranosyl ester. Five additional known compounds were identified, rebaudioside E, rebaudioside M, rebaudioside N, rebaudioside O, and stevioside, respectively. Enzymatic hydrolysis of stevioside afforded the known ent-kaurane aglycone 13-hydroxy-ent-kaur-16-en-19-oic acid (steviol) (3). The isolated metabolite 1 possesses the ent-kaurane aglycone steviol (3), while compound 2 represents the first example of the isomeric diterpene 12-α-hydroxy-ent-kaur-16-en-19-oic acid existing as a glycoside in S. rebaudiana. The structures of the isolated metabolites 1 and 2 were determined based on comprehensive 1D- and 2D-NMR (COSY, HSQC, and HMBC) studies. A high-quality crystal of compound 3 has formed, which allowed the acquisition of X-ray diffraction data that confirmed its structure. The structural similarities between the new metabolites and the commercially available stevioside sweeteners suggest the newly isolated metabolites should be examined for their organoleptic properties. Accordingly rebaudiosides E, M, N, O, and KA have been isolated in greater than gram quantities.

  7. Additional minor diterpene glycosides from Stevia rebaudiana Bertoni.

    PubMed

    Prakash, Indra; Chaturvedula, Venkata Sai Prakash

    2013-10-31

    Two additional novel minor diterpene glycosides were isolated from the commercial extract of the leaves of Stevia rebaudiana Bertoni. The structures of the new compounds were identified as 13-{β-D-glucopyranosyl-(1 → 2)-O-[β-D-glucopyranosyl-(1 → 3)-β-D-glucopyranosyl-oxy} ent-kaur-16-en-19-oic acid {β-D-xylopyranosyl-(1 → 2)-O-[β-D-glucopyranosyl-(1 → 3)]-O-β-D-glucupyranosyl-ester} (1), and 13-{β-D-6-deoxy-glucopyranosyl-(1 → 2)-O-[β-D-glucopyranosyl-(1 → 3)-β-D-glucopyranosyl-oxy} ent-kaur-16-en-19-oic acid {β-D-glucopyranosyl-(1 → 2)-O-[β-D-glucopyranosyl-(1 → 3)-β-D-gluco-pyranosyl-ester} (2), on the basis of extensive 1D (1H- and 13C-) 2D NMR (COSY, HSQC and HMBC) and MS spectroscopic data as well as chemical studies.

  8. Clerodane and Ent-kaurane Diterpene Glycosyl and Glycoside Derivatives from the Leaves of Casearia sylvestris

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Five new clerodane diterpene glycosides caseariasides A-E (1-4) and three new ent-kaurane diterpene glucosides sylvestrisides C-E (6-8) were isolated from the leaves of Casearia sylvestris. Their structures were determined on the basis of chemical and spectroscopic analyses....

  9. A New Diterpene Glycoside: 15α-Hydroxy-Rebaudioside M Isolated from Stevia rebaudiana.

    PubMed

    Prakash, Indra; Ma, Gil; Bunders, Cynthia; Devkota, Krishna P; Charan, Romila D; Ramirez, Catherine; Snyder, Tara M; Priedemann, Christopher

    2015-07-01

    In a continued search for novel diterpenoid glycosides, we recently isolated and characterized a Rebaudioside M derivative with a hydroxyl group at position 15 in the central diterpene core from an extract of Stevia rebaudiana Bertoni. Here we report the complete structure elucidation of 15α-hydroxy-Rebaudioside M (2) on the basis of NMR (1H, 13C, COSY, HSQC-DEPT, HMBC, 1D TOCSY, NOESY) and mass spectral data. Steviol glycoside with a hydroxyl group at C-15 in the central diterpene core has not been previously reported.

  10. Structures of some novel α-glucosyl diterpene glycosides from the glycosylation of steviol glycosides.

    PubMed

    Prakash, Indra; Chaturvedula, Venkata Sai Prakash

    2014-12-04

    Four new minor diterpene glycosides with a rare α-glucosyl linkage were isolated from a cyclodextrin glycosyltransferase glucosylated stevia extract containing more than 98% steviol glycosides. The new compounds were identified as 13-[(2-O-β-D-glucopyranosyl-3-O-(4-O-α-D-glucopyranosyl)-β-D-glucopyranosyl-β-D-glucopyranosyl)oxy] ent-kaur-16-en-19-oic acid-[(4-O-α-D-glucopyranosyl-β-D-glucopyranosyl) ester] (1), 13-[(2-O-β-D-glucopyranosyl-β-D-glucopyranosyl)oxy] ent-kaur-16-en-19-oic acid-[(4-O-(4-O-(4-O-α-D-glucopyranosyl)-α-D-glucopyranosyl)-α-D-glucopyranosyl)-β-D-glucopyranosyl ester] (2), 13-[(2-O-β-D-glucopyranosyl-3-O-(4-O-(4-O-(4-O-α-D-glucopyranosyl)-α-D-glucopyranosyl)-α-D-glucopyranosyl)-β-D-glucopyranosyl-β-D-glucopyranosyl)oxy] ent-kaur-16-en-19-oic acid β-D-glucopyranosyl ester (3), and 13-[(2-O-β-D-glucopyranosyl-3-O-(4-O-(4-O-(4-O-α-D-glucopyranosyl)-α-D-glucopyranosyl)-α-D-glucopyranosyl)-β-D-glucopyranosyl- β-D-glucopyranosyl)oxy] ent-kaur-16-en-19-oic acid-[(4-O-α-D-glucopyranosyl-β-D-glucopyranosyl) ester] (4) on the basis of extensive NMR and mass spectral (MS) data as well as hydrolysis studies.

  11. A Novel Diterpene Glycoside with Nine Glucose Units from Stevia rebaudiana Bertoni.

    PubMed

    Prakash, Indra; Ma, Gil; Bunders, Cynthia; Charan, Romila D; Ramirez, Catherine; Devkota, Krishna P; Snyder, Tara M

    2017-01-31

    Following our interest in new diterpene glycosides with better taste profiles than that of Rebaudioside M, we have recently isolated and characterized Rebaudioside IX-a novel steviol glycoside-from a commercially-supplied extract of Stevia rebaudiana Bertoni. This molecule contains a hexasaccharide group attached at C-13 of the central diterpene core, and contains three additional glucose units when compared with Rebaudioside M. Here we report the complete structure elucidation-based on extensive Nuclear Magnetic Resonance (NMR) analysis (1H, 13C, Correlation Spectroscopy (COSY), Heteronuclear Single Quantum Coherence-Distortionless Enhancement Polarization Transfer (HSQC-DEPT), Heteronuclear Multiple Bond Correlation (HMBC), 1D Total Correlation Spectroscopy (TOCSY), Nuclear Overhauser Effect Spectroscopy (NOESY)) and mass spectral data-of this novel diterpene glycoside with nine sugar moieties and containing a relatively rare 16 α-linked glycoside. A steviol glycoside bearing nine glucose units is unprecedented in the literature, and could have an impact on the natural sweetener catalog.

  12. Two new ent-kaurane-type diterpene glycosides from zucchini (Cucurbita pepo L.) seeds.

    PubMed

    Kikuchi, Takashi; Ando, Hiromi; Maekawa, Ken-Ichiro; Arie, Hiroki; Yamada, Takeshi; Tanaka, Reiko

    2015-12-01

    Two new ent-kaurane diterpene glycosides; 12α-(β-d-glucopyranosyloxy)-7β-hydroxykaurenolide (1) and 7β-(β-d-glucopyranosyloxy)-12α-hydroxykaurenolide (2), a new steroid; (24S)-stigmasta-7,22E,25-trien-3-one (12), and known compounds (3-11, 13-14) were isolated from zucchini (Cucurbita pepo L.) seeds. The absolute structures of 1 and 2 were determined by acid hydrolysis and application of a modified Moscher's method. Furthermore, isolated compounds (1-14), and a derivative, 1a, were evaluated for their inhibitory effects on macrophage activation by an inhibitory assay of nitric oxide (NO) production.

  13. New Ent-Kaurane-Type Diterpene Glycosides and Benzophenone from Ranunculus muricatus Linn.

    PubMed

    Wu, Bi-Ling; Zou, Hui-Liang; Qin, Fang-Min; Li, Hong-Yu; Zhou, Guang-Xiong

    2015-12-15

    Two new ent-kaurane diterpene glycosides, ranunculosides A (1) and B (2), and a new benzophenone, ranunculone C (3), were isolated from the aerial part of Ranunculus muricatus Linn. The chemical structures of compounds 1-3 were established to be (2S)-ent-kauran-2β-ol-15-en-14-O-β-d-glucopyranoside, (2S,4S)-ent-kauran-2β,18-diol-15-en-14-O-β-d-glucopyranoside, and (R)-3-[2-(3,4-dihydroxybenzoyl)-4,5-dihydroxy-phenyl]-2-hydroxylpropanoic acid, respectively, by spectroscopic data and chemical methods. The absolute configuration of 1 was determined by the combinational application of RP-HPLC analysis and Mosher's method.

  14. Isolation and structural characterization of a new minor diterpene glycoside from Stevia rebaudiana.

    PubMed

    Chaturvedula, Venkata Sai Prakash; Zamora, Julian

    2014-12-01

    From the commercial extract of the leaves of the sweet plant Stevia rebaudiana Bertoni obtained from Sinochem Qingdao Co. Ltd., a new diterpene glycoside having three β-D-glucopyranosyl units of which two of them were connected in a relatively rare linkage of 3-β-D-glucobiosyl substitution at C-19 position of the aglycone steviol. The structure of the new compound has been characterized as 13-β-D-glucopyranosyloxy ent-kaur-16-en-19-oic acid-[(3-O-β-D- glucopyranosyl-β-D-glucopyranosyl) ester (1) on the basis of extensive 1D (1H and 13C) and 2D NMR (TOCSY, HMQC, and HMBC), and High Resolution mass spectroscopic data as well as hydrolysis studies.

  15. The Calyculaglycosides: Dilophol-Type Diterpene Glycosides Exhibiting Antiinflammatory Activity from the Caribbean Gorgonian Eunicea sp.(1)(,)(2).

    PubMed

    Cóbar, Oscar M.; Rodríguez, Abimael D.; Padilla, Omayra L.; Sánchez, Juan A.

    1997-10-17

    Three new diterpenoid hexose-glycosides, calyculaglycosides A-C (1-3) were isolated from the Caribbean gorgonian Eunicea sp. Calyculaglycosides A-C are rare diterpene glycosides possessing dilophol (4) aglycones related in biosynthetic origin to the elemene-type glycoside class of potent antiinflammatory agents known as fuscosides. The structures of the new compounds, which were assigned on the basis of spectral studies, were further corroborated by molecular modeling studies. Calyculaglycoside B (2) is an effective topical antiinflammatory agent stronger in potency than the industrial standard indomethacin. Calyculaglycoside B inhibits the synthesis of both prostaglandin PGE(2) and leukotriene LTB(4), suggesting it is a nonselective inhibitor of the 5-lipoxygenase and cyclooxygenase pathways. At concentrations of 10(-4)-10(-5)M, calyculaglycoside B produced LC(50)-level differential responses against a majority of the NCI ovarian cancer lines and several of the renal, prostate, and colon tumor lines.

  16. Stevia rebaudiana ethanolic extract exerts better antioxidant properties and antiproliferative effects in tumour cells than its diterpene glycoside stevioside.

    PubMed

    López, Víctor; Pérez, Sergio; Vinuesa, Arturo; Zorzetto, Christian; Abian, Olga

    2016-04-01

    Steviol glycosides are currently being used as natural sweeteners by the food industry and Stevia rebaudiana has long been used as a sweet plant in South America for patients suffering from diabetes. In this study, a Stevia rebaudiana ethanolic extract (SREE) was prepared, analysed and tested for antioxidant activity in terms of free radical scavenging properties and antiproliferative effects in cervix (HeLa), pancreatic (MiaPaCa-2) and colonic (HCT116) cancer cells. The antiproliferative mechanism was confirmed by testing the effects on cyclin D1-CDK4. Bioassays were also performed for the diterpene glycoside stevioside. Our results demonstrate that the extract acts as an antioxidant being able to scavenge free radicals, but this activity was not due to stevioside. The extract also induced cell death in the three cell lines, being more active against cervix cancer cells (HeLa); however, the concentration of stevioside needed to produce antiproliferative effects was higher than the amount of steviol glycosides found in a lower dose of extract inducing cell death. In addition, the extract clearly inhibited CDK4 whereas stevioside did not, concluding that the antiproliferative activity of stevia may be due to inhibition of cyclin-dependent kinases performed by other compounds of the extract.

  17. Hydrogenation of the exocyclic olefinic bond at C-16/C-17 position of ent-kaurane diterpene glycosides of Stevia rebaudiana using various catalysts.

    PubMed

    Chaturvedula, Venkata Sai Prakash; Prakash, Indra

    2013-07-26

    Catalytic hydrogenation of the exocyclic double bond present between C16 and C17 carbons of the four ent-kaurane diterpene glycosides namely rebaudioside A, rebaudioside B, rebaudioside C, and rebaudioside D isolated from Stevia rebaudiana has been carried out using Pt/C, Pd(OH)2, Rh/C, Raney Ni, PtO2, and 5% Pd/BaCO3 to their corresponding dihydro derivatives with 17α and 17β methyl group isomers. Reactions were performed using the above-mentioned catalysts with the solvents methanol, water, and ethanol/water (8:2) under various conditions. Synthesis of reduced steviol glycosides was performed using straightforward chemistry and their structures were characterized on the basis of 1D and 2D NMR spectral data, including a comparison with reported spectral data.

  18. Hydrogenation of the Exocyclic Olefinic Bond at C-16/C-17 Position of ent-Kaurane Diterpene Glycosides of Stevia rebaudiana Using Various Catalysts

    PubMed Central

    Chaturvedula, Venkata Sai Prakash; Prakash, Indra

    2013-01-01

    Catalytic hydrogenation of the exocyclic double bond present between C16 and C17 carbons of the four ent-kaurane diterpene glycosides namely rebaudioside A, rebaudioside B, rebaudioside C, and rebaudioside D isolated from Stevia rebaudiana has been carried out using Pt/C, Pd(OH)2, Rh/C, Raney Ni, PtO2, and 5% Pd/BaCO3 to their corresponding dihydro derivatives with 17α and 17β methyl group isomers. Reactions were performed using the above-mentioned catalysts with the solvents methanol, water, and ethanol/water (8:2) under various conditions. Synthesis of reduced steviol glycosides was performed using straightforward chemistry and their structures were characterized on the basis of 1D and 2D NMR spectral data, including a comparison with reported spectral data. PMID:23896597

  19. Acyclic diterpene glycosides, capsianosides VIII, IX, X, XIII, XV and XVI from the fruits of Paprika Capsicum annuum L. var. grossum BAILEY and Jalapeño Capsicum annuum L. var. annuum.

    PubMed

    Lee, Jong-Hyun; Kiyota, Naoko; Ikeda, Tsuyoshi; Nohara, Toshihiro

    2006-10-01

    Paprika and Jalapeño are used as vegetables and spices. We have obtained six new acyclic diterpene glycosides, called capsianosides XIII (2), XV (3), IX (4), XVI (5), X (6) and VIII (7) together with known capsianoside II (1) from the fruits of the Paprika and Jalapeño. The structures of these compounds have been elucidated by the (1)H- and (13)C-NMR spectra and two-dimensional NMR methods.

  20. Three new labdane-type diterpene glycosides from fruits of Rubus chingii and their cytotoxic activities against five humor cell lines.

    PubMed

    Zhong, Ruijian; Guo, Qing; Zhou, Guoping; Fu, Huizheng; Wan, Kaihua

    2015-04-01

    Three new labdane-type diterpene glycosides, 15,18-di-O-β-d-glucopyranosyl-13(E)-ent-labda-7(8),13(14)-diene-3β,15,18-triol (1), 15,18-di-O-β-d-glucopyranosyl-13(E)-ent-labda-8(9),13(14)-diene-3β,15,18-triol (2), and 15-O-β-d-apiofuranosyl-(1→2)-β-d-glucopyranosyl-18-O-β-d-glucopyranosyl-13(E)-ent-labda-8(9),13(14)-diene-3β,15,18-triol (3), were isolated from the fruits of Rubus chingii. Their structures were elucidated on the basis of spectroscopic data and chemical methods. The cytotoxic activities of compounds 1-3 were evaluated against five human tumor cell lines (HCT-8, BGC-823, A549, and A2780). Compounds 3 showed cytotoxic activity against A549 with an IC50 value of 2.32μM.

  1. Isolation, NMR Spectral Analysis and Hydrolysis Studies of a Hepta Pyranosyl Diterpene Glycoside from Stevia rebaudiana Bertoni.

    PubMed

    Chaturvedula, Venkata Sai Prakash; Chen, Steven; Yu, Oliver; Mao, Guohong

    2013-09-30

    From the commercial extract of the leaves of Stevia rebaudiana Bertoni, a minor steviol glycoside, 13-[(2-O-β-D-glucopyranosyl-3-O-β-D-glucopyranosyl-β-D-glucopyranosyl)oxy] ent-kaur-16-en-19-oic acid-[(2-O-(3-O-β-D-glucopyranosyl-α-L-rhamnopyranosyl)-3-O-β-D-glucopyranosyl-β-D-glucopyranosyl) ester] (1); also known as rebaudioside O having seven sugar units has been isolated. Its structural characterization has been achieved by the extensive 1D (1H and 13C), and 2D NMR (COSY, HMQC, HMBC) as well as mass spectral data. Further, hydrolysis studies were performed on rebaudioside O using acid and enzymatic methods to identify aglycone and sugar residues in its structure as well as their configurations.

  2. Isolation, NMR Spectral Analysis and Hydrolysis Studies of a Hepta Pyranosyl Diterpene Glycoside from Stevia rebaudiana Bertoni

    PubMed Central

    Chaturvedula, Venkata Sai Prakash; Chen, Steven; Yu, Oliver; Mao, Guohong

    2013-01-01

    From the commercial extract of the leaves of Stevia rebaudiana Bertoni, a minor steviol glycoside, 13-[(2-O-β-d-glucopyranosyl-3-O-β-d-glucopyranosyl-β-d-glucopyranosyl)oxy] ent-kaur-16-en-19-oic acid-[(2-O-(3-O-β-d-glucopyranosyl-α-l-rhamnopyranosyl)-3-O-β-d-glucopyranosyl-β-d-glucopyranosyl) ester] (1); also known as rebaudioside O having seven sugar units has been isolated. Its structural characterization has been achieved by the extensive 1D (1H and 13C), and 2D NMR (COSY, HMQC, HMBC) as well as mass spectral data. Further, hydrolysis studies were performed on rebaudioside O using acid and enzymatic methods to identify aglycone and sugar residues in its structure as well as their configurations. PMID:24970189

  3. Effect of harvest timing on leaf production and yield of diterpene glycosides in Stevia rebaudiana Bert: a specialty perennial crop for Mississippi

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Stevia rebaundiana (Bertoni), a perennial shrub of the Asteraceae, is one of the most important sources of non-caloric natural sweeteners. Stevia’s plant extracts and glycosides have been used for several years in Paraguay and Brazil. Several studies suggest that Stevia and its glycosides exert ben...

  4. Diterpenes and phenolic compounds from Sideritis pullulans.

    PubMed

    Faiella, Laura; Piaz, Fabrizio Dal; Bader, Ammar; Braca, Alessandra

    2014-10-01

    Phytochemical investigation of Sideritis pullulans aerial part and root extracts allowed to isolate six ent-kaurane diterpenes, two phenylpropanoids, and one coumarin, identified as 1α,3α,7β,18-tetrahydroxy-ent-kaur-16-ene (sideripullol A) (1), 3α,11α,18-trihydroxy-ent-kaur-16-ene (sideripullol B) (2), 3α,7β,18-trihydroxy-17-nor-ent-kauran-16-one (sideritone A) (3), 3α,7β-dihydroxy-18-acetyloxy-17-nor-ent-kauran-16-one (sideritone B) (4), 3α,7β,16α,17-tetrahydroxy-18-acetyloxy-ent-kaurane (sideripullol C) (5), 7β,16α,17,18-tetrahydroxy-ent-kaurane (sideripullol D) (6), β-(3-methoxy-4-hydroxyphenyl)-ethyl-O-α-l-arabinopiranosyl-(1→2)-α-l-rhamnopyranosyl-(1→3)-6-O-t-feruloyl-β-d-glucopyranoside (sideritiside A) (7), β-(3,4-dihydroxyphenyl)-ethyl-O-α-l-arabinopiranosyl-(1→2)-α-l-rhamnopyranosyl-(1→3)-6-O-t-feruloyl-β-d-glucopyranoside (sideritiside B) (8), and 7-demethyl-8-methoxycoumarsabin (9), respectively. Twenty known compounds, including phenolics, flavonol glycosides, iridoids, diterpenes, sesquiterpenes, lignans, coumarins, and phenylpropanoids were also isolated and characterized. All diterpenes were evaluated for their cytotoxic activity.

  5. Geranyllinalool Synthases in Solanaceae and Other Angiosperms Constitute an Ancient Branch of Diterpene Synthases Involved in the Synthesis of Defensive Compounds1[C][W][OPEN

    PubMed Central

    Falara, Vasiliki; Alba, Juan M.; Kant, Merijn R.; Schuurink, Robert C.; Pichersky, Eran

    2014-01-01

    Many angiosperm plants, including basal dicots, eudicots, and monocots, emit (E,E)-4,8,12-trimethyltrideca-1,3,7,11-tetraene, which is derived from geranyllinalool, in response to biotic challenge. An Arabidopsis (Arabidopsis thaliana) geranyllinalool synthase (GLS) belonging to the e/f clade of the terpene synthase (TPS) family and two Fabaceae GLSs that belong to the TPS-g clade have been reported, making it unclear which is the main route to geranyllinalool in plants. We characterized a tomato (Solanum lycopersicum) TPS-e/f gene, TPS46, encoding GLS (SlGLS) and its homolog (NaGLS) from Nicotiana attenuata. The Km value of SlGLS for geranylgeranyl diphosphate was 18.7 µm, with a turnover rate value of 6.85 s–1. In leaves and flowers of N. attenuata, which constitutively synthesize 17-hydroxygeranyllinalool glycosides, NaGLS is expressed constitutively, but the gene can be induced in leaves with methyl jasmonate. In tomato, SlGLS is not expressed in any tissue under normal growth but is induced in leaves by alamethicin and methyl jasmonate treatments. SlGLS, NaGLS, AtGLSs, and several other GLSs characterized only in vitro come from four different eudicot families and constitute a separate branch of the TPS-e/f clade that diverged from kaurene synthases, also in the TPS-e/f clade, before the gymnosperm-angiosperm split. The early divergence of this branch and the GLS activity of genes in this branch in diverse eudicot families suggest that GLS activity encoded by these genes predates the angiosperm-gymnosperm split. However, although a TPS sequence belonging to this GLS lineage was recently reported from a basal dicot, no representative sequences have yet been found in monocot or nonangiospermous plants. PMID:25052853

  6. Steviol glycosides: chemical diversity, metabolism, and function.

    PubMed

    Ceunen, Stijn; Geuns, Jan M C

    2013-06-28

    Steviol glycosides are a group of highly sweet diterpene glycosides discovered in only a few plant species, most notably the Paraguayan shrub Stevia rebaudiana. During the past few decades, the nutritional and pharmacological benefits of these secondary metabolites have become increasingly apparent. While these properties are now widely recognized, many aspects related to their in vivo biochemistry and metabolism and their relationship to the overall plant physiology of S. rebaudiana are not yet understood. Furthermore, the large size of the steviol glycoside pool commonly found within S. rebaudiana leaves implies a significant metabolic investment and poses questions regarding the benefits S. rebaudiana might gain from their accumulation. The current review intends to thoroughly discuss the available knowledge on these issues.

  7. Isolation, characterization and sensory evaluation of a Hexa beta-D-glucopyranosyl diterpene from Stevia rebaudiana.

    PubMed

    Prakash, Indra; Chaturvedula, Venkata Sai Prakash; Markosyan, Avetik

    2013-11-01

    From the extract of the leaves of Stevia rebaudiana Bertoni, a diterpene glycoside was isolated which was identified as 13-[(2-O-beta-D-glucopyranosyl-3-O-beta-D-glucopyranosyl-beta-D-glucopyranosyl)oxy] ent-kaur-16-en-19-oic acid-(2-O-beta-D-glucopyranosyl-3-O-beta-D-glucopyranosyl-D-glucopyranosyl) ester (1). The complete 1H and 13C NMR assignment of 1 is reported for the first time, from extensive NMR (1H and 13C, COSY, HSQC, and HMBC) and mass spectral data. Also, we report the sensory evaluation of 1 against sucrose for the sweetness property of this molecule.

  8. Seasonal Variation of Cistus ladanifer L. Diterpenes.

    PubMed

    Alías, Juan Carlos; Sosa, Teresa; Valares, Cristina; Escudero, José Carlos; Chaves, Natividad

    2012-07-26

    The exudate of Cistus ladanifer L. consists mainly of two families of secondary metabolites: flavonoids and diterpenes. The amount of flavonoids present in the leaves has a marked seasonal variation, being maximum in summer and minimum in winter. In the present study, we demonstrate that the amount of diterpenes varies seasonally, but with a different pattern: maximum concentration in winter and minimum in spring-summer. The experiments under controlled conditions have shown that temperature influences diterpene production, and in particular, low temperatures. Given this pattern, the functions that these compounds perform in C. ladanifer are probably different.

  9. Seasonal Variation of Cistus ladanifer L. Diterpenes

    PubMed Central

    Alías, Juan Carlos; Sosa, Teresa; Valares, Cristina; Escudero, José Carlos; Chaves, Natividad

    2012-01-01

    The exudate of Cistus ladanifer L. consists mainly of two families of secondary metabolites: flavonoids and diterpenes. The amount of flavonoids present in the leaves has a marked seasonal variation, being maximum in summer and minimum in winter. In the present study, we demonstrate that the amount of diterpenes varies seasonally, but with a different pattern: maximum concentration in winter and minimum in spring-summer. The experiments under controlled conditions have shown that temperature influences diterpene production, and in particular, low temperatures. Given this pattern, the functions that these compounds perform in C. ladanifer are probably different. PMID:27137636

  10. Anxiolytic Activity of Diterpene Alkaloid Songorine.

    PubMed

    Nesterova, Yu V; Povet'eva, T N; Suslov, N I; Shults, E E; Ziuz'kov, G N; Aksinenko, S G; Afanas'eva, O G; Krapivin, A V; Kharina, T G

    2015-09-01

    Antianxiety action of diterpene alkaloid songorine was studied using Vogel conflict test. Songorine in a dose of 0.25 mg/kg demonstrated high anxiolytic activity comparable to that of phenazepam and produced no sedative effect.

  11. Cardiac glycoside overdose

    MedlinePlus

    ... found in the leaves of the digitalis (foxglove) plant. This plant is the original source of this medicine. People ... Digitoxin (Crystodigin) Digoxin (Lanoxicaps, Lanoxin) Besides the foxglove plant, cardiac glycosides also occur naturally in plants such ...

  12. New diterpenes from the heartwood of Chamaecyparis obtusa var. formosana.

    PubMed

    Kuo, Y H; Chen, C H; Huang, S L

    1998-06-26

    An abietane diterpene, 11,14-dihydroxy-8,11,13-abietatrien-7-one (1); a seco-abietane diterpene, obtuanhydride (2); and an isopimarane diterpene, 18,19-O-isopropylidene-18, 19-dihydroxyisopimara-8(14),15-diene (3) were isolated from the heartwood of Chamaecyparis obtusa var. formosana. The structures of these new compounds were elucidated by spectroscopic methods.

  13. Iridoid glycosides from Globularia trichosantha.

    PubMed

    Caliş, I; Kirmizibekmez, H; Sticher, O

    2001-01-01

    A new iridoid glycoside, deacetylalpinoside (2), was isolated from the aerial parts of Globularia trichosantha together with nine known iridoid glycosides: catalpol, 10-O-benzoyl-catalpol, aucubin, asperuloside, deacetylasperuloside, asperulosidic acid, scandoside, geniposidic acid, and alpinoside (1). From the underground parts of the same plant, two new bisiridoid glycosides, globulosides A (3) and B (4); a known iridoid glycoside, globularidin; a lignan glycoside, liriodendrin; and seven phenylethanoid glycosides, arenarioside, verbascoside (= acteoside), isoacteoside, crenatoside, isocrenatoside, and trichosanthosides A and B, were isolated. Compounds 2-4 are new iridoids containing an 8,9 double bond representing a rare carbon skeleton. Their structures were established by spectroscopic methods.

  14. Steviol glycoside biosynthesis.

    PubMed

    Brandle, J E; Telmer, P G

    2007-07-01

    Steviol glycosides are found in high concentrations in the leaves of the Paraguayan perennial herb Stevia rebaudiana and their intense sweetness, as well as high concentration in Stevia leaf tissue, has made them the subject of research interest for over 100 years. Steviol glycosides are diterpenoids whose biosynthetic pathways share four steps in common with gibberellic acid formation. The convergence of genomics and plant biochemistry has led to the rapid elucidation of the genes coding for the various enzymes in the biosynthetic pathway. Functional characterization of the enzymes coded for by those genes is on-going. The first committed step in the pathway is the synthesis of the aglycone steviol and the various glycosides found in the leaf tissue result from the elaboration of steviol by a number of glucosyltransferases.

  15. A new lignan glycoside from Juniperus rigida.

    PubMed

    Woo, Kyeong Wan; Choi, Sang Un; Park, Jong Cheol; Lee, Kang Ro

    2011-12-01

    A new lignan glycoside, named juniperigiside (1) was isolated from the CHCl(3) soluble fraction of the MeOH extract of stems and leaves of Juniperus rigida S.et Z. Compound 1 was identified by 1D- and 2D-NMR spectroscopy as well as CD analysis as (2R,3S)-2,3-dihydro-7-methoxy-2-(4'-hydroxy-3'-methoxyphenyl)-3-hydroxymethyl-5-benzofuranpropanol 4'-O-(3-O-methyl)-α-L-rhamnopyranoside. Five known lignans, icariside E4 (2), desoxypodophyllotoxin (3), savinin (4), thujastandin (5), and (-)-nortrachelogenin (6) in addition to five known labdane diterpenes including trans-communic acid (7), 13-epi-torulosal (8), 13-epi-cupressic acid (9), imbricatoric acid (10), and isocupressic acid (11) were also isolated and their structures were characterized by comparing their spectroscopic data with those in the literature. All compounds were isolated for the first time from this plant, and 5 and 6 were first reported from the genus Juniperus. The isolated compounds were tested for cytotoxicity against four human tumor cell lines in vitro using a Sulforhodamin B bioassay. Compounds 3, 4, 7, and 8 showed considerable cytotoxicity against four human cancer cell lines in vitro.

  16. Identification of a Dolabellane Type Diterpene Synthase and other Root-Expressed Diterpene Synthases in Arabidopsis

    PubMed Central

    Wang, Qiang; Jia, Meirong; Huh, Jung-Hyun; Muchlinski, Andrew; Peters, Reuben J.; Tholl, Dorothea

    2016-01-01

    Arabidopsis thaliana maintains a complex metabolism for the production of secondary or specialized metabolites. Such metabolites include volatile and semivolatile terpenes, which have been associated with direct and indirect defensive activities in flowers and leaves. In comparison, the structural diversity and function of terpenes in Arabidopsis roots has remained largely unexplored despite a substantial number of root-expressed genes in the Arabidopsis terpene synthase (TPS) gene family. We show that five root-expressed TPSs of an expanded subfamily-a type clade in the Arabidopsis TPS family function as class I diterpene synthases that predominantly convert geranylgeranyl diphosphate (GGPP) to different semi-volatile diterpene products, which are in part detectable at low levels in the ecotypes Columbia (Col) and Cape Verde Island (Cvi). The enzyme TPS20 produces a macrocyclic dolabellane diterpene alcohol and a dolabellane-related diterpene olefin named dolathaliatriene with a so far unknown C6-C11 bicyclic scaffold besides several minor olefin products. The TPS20 compounds occur in all tissues of Cvi but are absent in the Col ecotype because of deletion and substitution mutations in the Col TPS20 sequence. The primary TPS20 diterpene products retard the growth of the root rot pathogen Pythium irregulare but only at concentrations exceeding those in planta. Together, our results demonstrate that divergence and pseudogenization in the Arabidopsis TPS gene family allow for structural plasticity in diterpene profiles of above- and belowground tissues. PMID:27933080

  17. Antifungal diterpenes from Hypoestes serpens (Acanthaceae).

    PubMed

    Rasoamiaranjanahary, Lalao; Marston, Andrew; Guilet, David; Schenk, Kurt; Randimbivololona, Fanantenanirainy; Hostettmann, Kurt

    2003-02-01

    Two new diterpenes, fusicoserpenol A and dolabeserpenoic acid A, with antifungal activity, were isolated from leaves of Hypoestes serpens (Acanthaceae). Their structures were elucidated by means of spectrometric methods including 1D and 2D NMR experiments and MS analysis. X-ray crystallographic analysis confirmed the structure of fusicoserpenol A and established the relative configuration.

  18. Methylerythritol and mevalonate pathway contributions to biosynthesis of mono-, sesqui-, and diterpenes in glandular trichomes and leaves of Stevia rebaudiana Bertoni.

    PubMed

    Wölwer-Rieck, Ursula; May, Bianca; Lankes, Christa; Wüst, Matthias

    2014-03-19

    The biosynthesis of the diterpenoid steviol glycosides rebaudioside A and stevioside in nonrooted cuttings of Stevia rebaudiana was investigated by feeding experiments using the labeled key precursors [5,5-(2)H2]-mevalonic acid lactone (d2-MVL) and [5,5-(2)H2]-1-deoxy-d-xylulose (d2-DOX). Labeled glycosides were extracted from the leaves and stems and were directly analyzed by LC-(-ESI)-MS/MS and by GC-MS after hydrolysis and derivatization of the resulting isosteviol to the corresponding TMS-ester. Additionally, the incorporation of the proffered d2-MVL and d2-DOX into volatile monoterpenes, sesquiterpenes, and diterpenes in glandular trichomes on leaves and stems was investigated by headspace-solid phase microextraction-GC-MS (HS-SPME-GC-MS). Incorporation of the labeled precursors indicated that diterpenes in leaves and monoterpenes and diterpenes in glandular trichomes are predominately biosynthesized via the methylerythritol phosphate (MEP) pathway, whereas both the MEP and mevalonate (MVA) pathways contribute to the biosynthesis of sesquiterpenes at equal rates in glandular trichomes. These findings give evidence for a transport of MEP pathway derived farnesyl diphosphate precursors from plastids to the cytosol. Contrarily, the transport of MVA pathway derived geranyl diphosphate and geranylgeranyl diphosphate precursors from the cytosol to the plastid is limited.

  19. Spatial organisation of four enzymes from Stevia rebaudiana that are involved in steviol glycoside synthesis.

    PubMed

    Humphrey, Tania V; Richman, Alex S; Menassa, Rima; Brandle, Jim E

    2006-05-01

    The sweet steviol glycosides found in the leaves of Stevia rebaudiana Bert. are derived from the diterpene steviol which is produced from a branch of the gibberellic acid (GA) biosynthetic pathway. An understanding of the spatial organisation of the two pathways including subcellular compartmentation provides important insight for the metabolic engineering of steviol glycosides as well as other secondary metabolites in plants. The final step of GA biosynthesis, before the branch point for steviol production, is the formation of (-)-kaurenoic acid from (-)-kaurene, catalysed by kaurene oxidase (KO). Downstream of this, the first committed step in steviol glycoside synthesis is the hydroxylation of kaurenoic acid to form steviol which is then sequentially glucosylated by a series of UDP-glucosyltransferases (UGTs) to produce the variety of steviol glycosides. The subcellular location of KO and three of the UGTs involved in steviol glycoside biosynthesis was investigated by expression of GFP fusions and cell fractionation which revealed KO to be associated with the endoplasmic reticulum and the UGTs in the cytoplasm. It has also been shown by expressing the Stevia UGTs in Arabidopsis that the pathway can be partially reconstituted by recruitment of a native Arabidopsis glucosyltransferase.

  20. Variants of glycoside hydrolases

    DOEpatents

    Teter, Sarah; Ward, Connie; Cherry, Joel; Jones, Aubrey; Harris, Paul; Yi, Jung

    2013-02-26

    The present invention relates to variants of a parent glycoside hydrolase, comprising a substitution at one or more positions corresponding to positions 21, 94, 157, 205, 206, 247, 337, 350, 373, 383, 438, 455, 467, and 486 of amino acids 1 to 513 of SEQ ID NO: 2, and optionally further comprising a substitution at one or more positions corresponding to positions 8, 22, 41, 49, 57, 113, 193, 196, 226, 227, 246, 251, 255, 259, 301, 356, 371, 411, and 462 of amino acids 1 to 513 of SEQ ID NO: 2 a substitution at one or more positions corresponding to positions 8, 22, 41, 49, 57, 113, 193, 196, 226, 227, 246, 251, 255, 259, 301, 356, 371, 411, and 462 of amino acids 1 to 513 of SEQ ID NO: 2, wherein the variants have glycoside hydrolase activity. The present invention also relates to nucleotide sequences encoding the variant glycoside hydrolases and to nucleic acid constructs, vectors, and host cells comprising the nucleotide sequences.

  1. Variants of glycoside hydrolases

    DOEpatents

    Teter, Sarah; Ward, Connie; Cherry, Joel; Jones, Aubrey; Harris, Paul; Yi, Jung

    2011-04-26

    The present invention relates to variants of a parent glycoside hydrolase, comprising a substitution at one or more positions corresponding to positions 21, 94, 157, 205, 206, 247, 337, 350, 373, 383, 438, 455, 467, and 486 of amino acids 1 to 513 of SEQ ID NO: 2, and optionally further comprising a substitution at one or more positions corresponding to positions 8, 22, 41, 49, 57, 113, 193, 196, 226, 227, 246, 251, 255, 259, 301, 356, 371, 411, and 462 of amino acids 1 to 513 of SEQ ID NO: 2 a substitution at one or more positions corresponding to positions 8, 22, 41, 49, 57, 113, 193, 196, 226, 227, 246, 251, 255, 259, 301, 356, 371, 411, and 462 of amino acids 1 to 513 of SEQ ID NO: 2, wherein the variants have glycoside hydrolase activity. The present invention also relates to nucleotide sequences encoding the variant glycoside hydrolases and to nucleic acid constructs, vectors, and host cells comprising the nucleotide sequences.

  2. Quinoid glycosides from Forsythia suspensa.

    PubMed

    Li, Chang; Dai, Yi; Zhang, Shu-Xiang; Duan, Ying-Hui; Liu, Ming-Li; Chen, Liu-Yuan; Yao, Xin-Sheng

    2014-08-01

    Phytochemical investigation on Forsythia suspensa (Thunb.) Vahl afforded 10 compounds, including quinoid glycosides, lignan glycosides, phenylethanoid glycoside and allylbenzene glycoside together with 13 known ones. Their structures were established based on extensive spectroscopic data analyses, including IR, UV, HRESIMS, 1D NMR and 2D NMR. Absolute configurations were determined by ECD calculation method and chemical degradation. In addition, all compounds were evaluated for their antiviral activity against influenza A (H1N1) virus and several were further evaluated against respiratory syncytial virus (RSV) in vitro. Among them, two previously known compounds showed significant activities against RSV with EC50 values of 3.43 and 6.72 μM.

  3. Glycoside vs. Aglycon: The Role of Glycosidic Residue in Biological Activity

    NASA Astrophysics Data System (ADS)

    Křen, Vladimír

    A large number of biologically active compounds are glycosides. Sometimes the glycosidic residue is crucial for their activity, in other cases glycosylation only improves pharmacokinetic parameters. Recent developments in molecular glycobiology brought better understanding of aglycon vs. glycoside activities, and made possible the development of new, more active or more effective glycodrugs based on these findings - a very illustrative recent example is vancomycin. The new enzymatic methodology "glycorandomization" enabled preparation of glycoside libraries and opened up paths to the preparation of optimized or entirely novel glycoside antibiotics. This chapter deals with an array of glycosidic compounds currently used in medicine but also covers the biological activity of some glycosidic metabolites of known drugs. The chapter discusses glycosides of vitamins, polyphenolic glycosides (flavonoids), alkaloid glycosides, glycosides of antibiotics, glycopeptides, cardiac glycosides, steroid and terpenoid glycosides etc. The physiological role of the glycosyl moiety and structure-activity relations (SAR) in the glycosidic moiety (-ies) are also discussed.

  4. Cytotoxicity of pregnane glycosides of Cynanchum otophyllum.

    PubMed

    Zhang, Mi; Li, Xiang; Xiang, Cheng; Qin, Yi; He, Jing; Li, Bao-Cai; Li, Peng

    2015-12-01

    Fourteen new pregnane glycosides, including nine caudatin glycosides (1-9), three qinyangshengenin glycosides (10-12), one kidjoranin glycosides (13) and one gagaminin glycosides (14), along with twelve known analogs (15-26) were isolated from roots of Cynanchum otophyllum Schneid. Their structures were deduced by detailed analysis of 1D and 2D NMR spectra, as well as HRESIMS. In this study, all pregnane glycosides obtained (1-26) were evaluated for their cytotoxic activities using three cancer cell lines (HepG2, Hela, U251). As results, except 6 and 10, other twenty-four pregnane glycosides showed cytotoxicities at different degrees against three cell lines.

  5. Plant diterpene synthases: exploring modularity and metabolic diversity for bioengineering.

    PubMed

    Zerbe, Philipp; Bohlmann, Jörg

    2015-07-01

    Plants produce thousands of diterpenoid natural products; some of which are of significant industrial value as biobased pharmaceuticals (taxol), fragrances (sclareol), food additives (steviosides), and commodity chemicals (diterpene resin acids). In nature, diterpene synthase (diTPS) enzymes are essential for generating diverse diterpene hydrocarbon scaffolds. While some diTPSs also form oxygenated compounds, more commonly, oxygenation is achieved by cytochrome P450-dependent mono-oxygenases. Recent genome-, transcriptome-, and metabolome-guided gene discovery and enzyme characterization identified novel diTPS functions that form the core of complex modular pathway systems. Insights into diterpene metabolism may translate into the development of new bioengineered microbial and plant-based production systems.

  6. Neo-clerodane diterpenes from the hallucinogenic sage Salvia divinorum.

    PubMed

    Shirota, Osamu; Nagamatsu, Kumi; Sekita, Setsuko

    2006-12-01

    Seven new neo-clerodane diterpenes, salvidivins A (2), B, (3), C (4), and D (5), salvinorins H (6) and I (7), and divinatorin [corrected] F (8), along with eight known neo-clerodane diterpenes, salvinorins A (1)-F, divinatorins A and B, and seven other constituents, were isolated from the hallucinogenic sage Salvia divinorum. The structures of 1-7 were elucidated on the basis of 2D NMR spectroscopic studies.

  7. NaJAZh Regulates a Subset of Defense Responses against Herbivores and Spontaneous Leaf Necrosis in Nicotiana attenuata Plants[C][W][OA

    PubMed Central

    Oh, Youngjoo; Baldwin, Ian T.; Gális, Ivan

    2012-01-01

    The JASMONATE ZIM DOMAIN (JAZ) proteins function as negative regulators of jasmonic acid signaling in plants. We cloned 12 JAZ genes from native tobacco (Nicotiana attenuata), including nine novel JAZs in tobacco, and examined their expression in plants that had leaves elicited by wounding or simulated herbivory. Most JAZ genes showed strong expression in the elicited leaves, but NaJAZg was mainly expressed in roots. Another novel herbivory-elicited gene, NaJAZh, was analyzed in detail. RNA interference suppression of this gene in inverted-repeat (ir)JAZh plants deregulated a specific branch of jasmonic acid-dependent direct and indirect defenses: irJAZh plants showed greater trypsin protease inhibitor activity, 17-hydroxygeranyllinalool diterpene glycosides accumulation, and emission of volatile organic compounds from leaves. Silencing of NaJAZh also revealed a novel cross talk in JAZ-regulated secondary metabolism, as irJAZh plants had significantly reduced nicotine levels. In addition, irJAZh spontaneously developed leaf necrosis during the transition to flowering. Because the lesions closely correlated with the elevated expression of programmed cell death genes and the accumulations of salicylic acid and hydrogen peroxide in the leaves, we propose a novel role of the NaJAZh protein as a repressor of necrosis and/or programmed cell death during plant development. PMID:22496510

  8. NaJAZh regulates a subset of defense responses against herbivores and spontaneous leaf necrosis in Nicotiana attenuata plants.

    PubMed

    Oh, Youngjoo; Baldwin, Ian T; Gális, Ivan

    2012-06-01

    The JASMONATE ZIM DOMAIN (JAZ) proteins function as negative regulators of jasmonic acid signaling in plants. We cloned 12 JAZ genes from native tobacco (Nicotiana attenuata), including nine novel JAZs in tobacco, and examined their expression in plants that had leaves elicited by wounding or simulated herbivory. Most JAZ genes showed strong expression in the elicited leaves, but NaJAZg was mainly expressed in roots. Another novel herbivory-elicited gene, NaJAZh, was analyzed in detail. RNA interference suppression of this gene in inverted-repeat (ir)JAZh plants deregulated a specific branch of jasmonic acid-dependent direct and indirect defenses: irJAZh plants showed greater trypsin protease inhibitor activity, 17-hydroxygeranyllinalool diterpene glycosides accumulation, and emission of volatile organic compounds from leaves. Silencing of NaJAZh also revealed a novel cross talk in JAZ-regulated secondary metabolism, as irJAZh plants had significantly reduced nicotine levels. In addition, irJAZh spontaneously developed leaf necrosis during the transition to flowering. Because the lesions closely correlated with the elevated expression of programmed cell death genes and the accumulations of salicylic acid and hydrogen peroxide in the leaves, we propose a novel role of the NaJAZh protein as a repressor of necrosis and/or programmed cell death during plant development.

  9. Detoxification of hostplant's chemical defence rather than its anti-predator co-option drives β-glucosidase-mediated lepidopteran counteradaptation

    PubMed Central

    Poreddy, Spoorthi; Mitra, Sirsha; Schöttner, Matthias; Chandran, Jima; Schneider, Bernd; Baldwin, Ian T.; Kumar, Pavan; Pandit, Sagar S.

    2015-01-01

    The evolutionary plant–herbivore arms race sometimes gives rise to remarkably unique adaptation strategies. Here we report one such strategy in the lepidopteran herbivore Manduca sexta against its hostplant Nicotiana attenuata's major phytotoxins, 17-hydroxygeranyllinalool diterpene glycoside, lyciumoside IV and its malonylated forms. We show that alkalinity of larval regurgitant non-enzymatically demalonylates the malonylated forms to lyciumoside IV. Lyciumoside IV is then detoxified in the midgut by β-glucosidase 1-catalysed deglycosylation, which is unusual, as typically the deglycosylation of glycosylated phytochemicals by insects results in the opposite: toxin activation. Suppression of deglucosylation by silencing larval β-glucosidase 1 by plant-mediated RNAi causes moulting impairments and mortality. In the native habitat of N. attenuata, β-glucosidase 1 silencing also increases larval unpalatability to native predatory spiders, suggesting that the defensive co-option of lyciumoside IV may be ecologically advantageous. We infer that M. sexta detoxifies this allelochemical to avoid its deleterious effects, rather than co-opting it against predators. PMID:26443324

  10. Mono and diterpene production in Escherichia coli.

    PubMed

    Reiling, K Kinkead; Yoshikuni, Yasuo; Martin, Vincent J J; Newman, Jack; Bohlmann, Jörg; Keasling, Jay D

    2004-07-20

    Mono- and diterpenoids are of great industrial and medical value as specialty chemicals and pharmaceuticals. Production of these compounds in microbial hosts, such as Escherichia coli, can be limited by intracellular levels of the polyprenyl diphosphate precursors, geranyl diphosphate (GPP), and geranylgeranyl diphosphate (GGPP). To alleviate this limitation, we constructed synthetic operons that express three key enzymes for biosynthesis of these precursors: (1). DXS,1-deoxy-d-xylulose-5-phosphate synthase; (2). IPPHp, IPP isomerase from Haematococcus pluvialis; and (3). one of two variants of IspA, FPP synthase that produces either GPP or GGPP. The reporter plasmids pAC-LYC and pACYC-IB, which encode enzymes that convert either FPP or GGPP, respectively, to the pigment lycopene, were used to demonstrate that at full induction, the operon encoding the wild-type FPP synthase and mutant GGPP synthase produced similar levels of lycopene. To synthesize di- or monoterpenes in E. coli using the GGPP and GPP encoding operons either a diterpene cyclase [casbene cyclase (Ricinus communis L) and ent-kaurene cyclase (Phaeosphaeria sp. L487)] or a monoterpene cyclase [3-carene cyclase (Picea abies)] was coexpressed with their respective precursor production operon. Analysis of culture extracts or headspace by gas chromatography-mass spectrometry confirmed the in vivo production of the diterpenes casbene, kaur-15-ene, and kaur-16-ene and the monoterpenes alpha-pinene, myrcene, sabinene, 3-carene, alpha-terpinene, limonene, beta-phellandrene, alpha-terpinene, and terpinolene. Construction and functional expression of GGPP and GPP operons provides an in vivo precursor platform host for the future engineering of di- and monoterpene cyclases and the overproduction of terpenes in bacteria.

  11. Flavonol Glycosides from Gaura Biennis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Phytochemical investigation of the native American plant Gaura biennis led to the isolation of three new flavonol glycosides (1-3), along with eight known ones. Their structures were established primarily by spectroscopic data as quercetin 3-O-(2"-O-a-L-rhamnopyranosyl-6"-O-E-p-coumaroyl)-ß-D- gluco...

  12. Interaction of coffee compounds with serum albumins. Part II: Diterpenes.

    PubMed

    Guercia, Elena; Forzato, Cristina; Navarini, Luciano; Berti, Federico

    2016-05-15

    Cafestol and 16-O-methylcafestol are diterpenes present in coffee, but whilst cafestol is found in both Coffea canephora and Coffea arabica, 16-O-methylcafestol (16-OMC) was reported to be specific of only C. canephora. The interactions of such compounds, with serum albumins, have been studied. Three albumins have been considered, namely human serum albumin (HSA), fatty acid free HSA (ffHSA) and bovine serum albumin (BSA). The proteins interact with the diterpenes at the interface between Sudlow site I and the fatty acid binding site 6 in a very peculiar way, leading to a significant change in the secondary structure. The diterpenes do not displace reference binding drugs of site 2, but rather they enhance the affinity of the site for the drugs. They, therefore, may alter the pharmacokinetic profile of albumin - bound drugs.

  13. Trihydroxylated linear diterpenes from the brown alga Bifurcaria bifurcata.

    PubMed

    Culioli, Gérald; Ortalo-Magné, Annick; Daoudi, Mohammed; Thomas-Guyon, Hélène; Valls, Robert; Piovetti, Louis

    2004-07-01

    Two novel polar diterpenes were isolated from the brown alga Bifurcaria bifurcata collected off the Atlantic coast of Morocco, and their structures established by spectral methods. Both compounds are trihydroxylated acyclic diterpenes derived from 12-hydroxygeranylgeraniol. They were tested in vitro for their cytotoxicity and proved to be active against the NSCLC-N6 cell line. Their absolute configuration at the C-12 position has been determined with a modified Mosher's method [J. Am. Chem. Soc. 113 (1991) 4092] and that of the 12-hydroxygeranylgeraniol (bifurcadiol) has been revised.

  14. Novel diterpenes from the heartwood of Chamaecyparis obtusa var. formosana.

    PubMed

    Kuo, Yueh-Hsiung; Chen, Chia-Hsien; Chien, Shih-Chang; Lin, Hsiu-Chuan

    2004-06-01

    Two novel diterpenes, obtusanal B (1) and obtusadione (2), along with obtusanal A (3), obtunone (4), 12-hydroxy-6,7-secoabieta-8,11,13-triene-6,7-dial, 8,12-dihydroxydielmentha-5,9-diene-7,11-dione and myrcene, isolated from the heartwood of Chamaecyparis obtusa var. formosana, were characterized by spectroscopic means, including 2D-NMR techniques. Compounds 1 and 2 are 7(6-->2)abeoabietane and 14(8-->9)abeoabietane type diterpenes, respectively. Their biosyntheses were proposed.

  15. Phytotoxic clerodane diterpenes from Salvia miniata Fernald (Lamiaceae).

    PubMed

    Bisio, Angela; Damonte, Gianluca; Fraternale, Daniele; Giacomelli, Emanuela; Salis, Annalisa; Romussi, Giovanni; Cafaggi, Sergio; Ricci, Donata; De Tommasi, Nunziatina

    2011-02-01

    Our ongoing research to identify natural growth inhibitors with diterpene and triterpene skeletons exuding from the surface of the aerial parts of Salvia species led us to study Salvia miniata Fernald. Ten clerodane diterpenoids were found, along with three known diterpenes. Most of the isolated compounds from S. miniata inhibited the germination of Papaver rhoeas L. and Avena sativa L. in Petri dish experiments. Parallel results have been obtained in experiments carried out to evaluate the subsequent growth of the seedlings of the target species in the presence of the tested compounds.

  16. Pimarane diterpenes from the Arctic fungus Eutypella sp. D-1.

    PubMed

    Lu, Xiao-Ling; Liu, Jing-Tang; Liu, Xiao-Yu; Gao, Yun; Zhang, Jianpeng; Jiao, Bing-Hua; Zheng, Heng

    2014-02-01

    Two new diterpenes, libertellenone G(1) and libertellenone H(2) were isolated from the fungus Eutypella sp. D-1 isolated from the soil of high latitude of Arctic, together with two known pimarane diterpenes (3-4). The structures of 1 and 2 were elucidated from spectroscopic data (nuclear magnetic resonance, mass spectrometry and infrared). These compounds were evaluated for cytotoxic activity against seven human tumor cell lines. Compound 2 showed a range of cytotoxicity between 3.31 and 44.1 μM. Compound 1 exhibited antibacterial activity against Escherichia coli, Bacillus subtilis and Staphylococcus aureus.

  17. Steroidal glycosides from Reineckia carnea.

    PubMed

    Song, Xiaomei; Zhang, Dongdong; He, Hao; Li, Yuze; Yang, Xinjie; Deng, Chong; Tang, Zhishu; Cui, Jiucheng; Yue, Zhenggang

    2015-09-01

    Three new steroidal glycosides (1-3) and a novel natural product 4 firstly obtained from a plant source, together with two known steroidal glycosides (5-6) have been isolated from the whole plant of Reineckia carnea. Their structures were determined by physicochemical properties and spectroscopic methods, and their cytotoxic activities against human 1299 tumor cells were evaluated by the MTT method. Compounds 4, 5 and 6 exhibited cytotoxicity with IC50 values of 50.3 μmol·L(-1), 67.2 μmol·L(-1) and 61.8 μmol·L(-1), while compounds 1, 2, and 3 showed no cytotoxicity with the cells.

  18. Microbial hydrolysis of steviol glycosides.

    PubMed

    Renwick, A G; Tarka, S M

    2008-07-01

    A review of the role of gut microbiota in the metabolism of the steviol glycosides, stevioside and rebaudioside A, indicates that they are not absorbed intact but undergo hydrolysis by the intestinal microflora to steviol. Steviol is not metabolized by the intestinal flora and is absorbed from the intestine. The rate of hydrolysis for stevioside is greater than for rebaudioside A. Recent studies using mass spectrometry have shown that steviol-16,17-epoxide is not a microbial metabolite of steviol glycosides. Bacteroides species are primarily responsible for hydrolysis via their beta-glucosidase activity. Fecal incubation studies with both human and animal mixed flora provide similar results, and this indicates that the rat is an appropriate model for studies on steviol glycosides. Given the similarity in the microbial metabolism of stevioside and rebaudioside A with the formation of steviol as the single hydrolysis product that is absorbed from the intestinal tract, the toxicological data on stevioside are relevant to the risk assessment of rebaudioside A.

  19. Bioactive clerodane diterpenes from roots of Carex distachya.

    PubMed

    Fiorentino, Antonio; D'Abrosca, Brigida; Pacifico, Severina; Izzo, Angelina; D'Angelo, Grazia; Monaco, Pietro

    2010-10-01

    Two new clerodane diterpenes were isolated from roots of Carex distachya Desf., a perennial plant widely distributed in the coastal area of the Mediterranean basin. Chemical characterization of the metabolites was carried out mainly by 1D and 2D NMR spectroscopy. The isolated compounds influenced either positively or negatively the plant growth (root and shoot elongation) of three coexisting herbaceous species.

  20. Methyl carnosate, an antibacterial diterpene isolated from Salvia officinalis leaves.

    PubMed

    Climati, Elisa; Mastrogiovanni, Fabio; Valeri, Maria; Salvini, Laura; Bonechi, Claudia; Mamadalieva, Nilufar Zokirzhonovna; Egamberdieva, Dilfuza; Taddei, Anna Rita; Tiezzi, Antonio

    2013-04-01

    Ethanolic extracts of Salvia officinalis leaves demonstrated antibacterial activity against Bacillus cereus. Fractionation of the extracts led to the isolation of the most active antibacterial compound, which, from spectroscopic and LC-MS evidence, was proved to be the diterpene, methyl carnosate.

  1. The chemical synthesis of aryltetralin glycosides.

    PubMed

    Sun, Jian-Song; Liu, Hui; Guo, Xiao-Hong; Liao, Jin-Xi

    2016-01-28

    Led by etoposide and teniposide, the synthesis of aryltetralin glycosides has been experiencing flourishing development in the past five decades. Herein, a review focusing on the total synthesis of aryltetralin glycosides is provided. The main body of this review is composed of two parts, one is the enantioselective synthesis of aryltetralin derivatives and the other one is the construction of key glycosidic linkages. In each part the contents are organised based on the different strategies or protocols applied in the original documents. The total synthesis of aryltetralin glycosides represents the developing direction of this field, and sooner or later will replace the currently applied semi-total synthesis method, using the aglycon residue acquired directly from natural sources. This account provides a comprehensive and deep insight into the field of aryltetralin glycoside synthesis for chemists who have the intention of committing themselves to the development of aryltetralin glycoside medicine.

  2. Aroma Glycosides in Grapes and Wine.

    PubMed

    Liu, Jibin; Zhu, Xiao-Lin; Ullah, Niamat; Tao, Yong-Sheng

    2017-02-01

    The major aroma components in grapes and wine include free volatile compounds and glycosidic nonvolatile compounds. The latter group of compounds is more than 10 times abundant of the former, and constitutes a big aroma reserve in grapes and wine. This review summarizes the research results obtained recently for the identification of aroma glycosides in grapes and wine, including grape glycoside structures, differences in aroma glycosides among grape varieties, hydrolysis mechanisms, and the factors that influence them. It also presents the analytical techniques used to identify the glycosidic aroma precursors. The operational strategies, challenges, and improvements of each step encountered in the analysis of glycosidic aroma precursors are described. This review intends to provide a convenient reference for researchers interested in the methods used for the determination of the aroma glucosides composition and the recognition of their chemical structures.

  3. Facile synthesis of aminooxy glycosides by gold(III)-catalyzed glycosidation.

    PubMed

    Thadke, Shivaji A; Neralkar, Mahesh; Hotha, Srinivas

    2016-07-22

    The O-glycosidation of hydroxysuccinimides and hydroxyphthalimides with a variety of aldose derived propargyl 1,2-orthoesters under the gold(III)-catalyzed glycosidation conditions is reported. A wide range of hydroxysuccinimidyl and hydroxyphthalimidyl glycosides were synthesized from corresponding glycosyl orthoesters including glucosyl, mannosyl, galactosyl, ribofuranosyl, arabinofuranosyl, lyxofuranosyl and xylofuranosyl using gold catalysis repertoire. The protocol is identified to be compatible for the synthesis of aminooxy glycosides of higher oligosaccharides as well.

  4. New lignan glycosides from Justicia procumbens.

    PubMed

    Jin, Hong; Yang, Shu; Dong, Jun-Xing

    2017-01-01

    Four new lignan glycosides (1-4), named procumbenosides I, K, L, and M, together with cleistanthin B (5) reported for the first time in the genus Justicia, and 5 other known arylnaphthalene lignan glycosides (6-10) were isolated from the whole plant of Justicia procumbens. The structures of the new compounds were elucidated by extensive one-dimensional (1D) and two-dimensional (2D) NMR experiments and mass spectrometry. Procumbenoside M (4) was a rare sesquilignan glycoside never previously reported in the species of Justicia. The paper also provided insight into the conformational equilibria existing in the lignan glycosides of the plant.

  5. Bioconversion of steroid glycosides by Nocardia restricta.

    PubMed

    Belic, I; Kastelic-Suhadolc, T; Kralj, B

    1985-09-01

    The bioconversion of steroid alkaloid tomatine by Nocardia restricta yields the conjugate with lactic acid. We studied the bioconversion of some steroid glycosides without a nitrogen atom in the molecule to determine the effect of the nitrogen atom. The glycosides were of three different types: sterol glycosides, bufadienolide rhamnoside and steroid saponine. The results of bioconversions showed that Nocardia restricta converts steroid glycosides differently according to the sugar bound to the steroid aglycone. It can be concluded that in the absence of a nitrogen atom in the steroid molecule no conjugation with lactic acid by Nocardia restricta occurs.

  6. Lipoxygenase-inhibiting phenolic glycosides and monoterpene glycosides from Paeonia lactiflora.

    PubMed

    Zou, Liang; Hu, Lin-Feng; Guo, Yi-Dong; Song, Yu; Fu, Qiang

    2015-01-01

    The EtOH extract of the roots of Paeonia lactiflora afforded a new phenolic glycoside paenoside A (1) and a new monoterpene glycoside paeonin D (2), and five known monoterpene glycosides. Their structures were elucidated on the basis of spectroscopic means and hydrolysis products. All compounds displayed inhibitory potential against enzyme lipoxygenase.

  7. Gene Discovery of Modular Diterpene Metabolism in Nonmodel Systems1[W][OA

    PubMed Central

    Zerbe, Philipp; Hamberger, Björn; Yuen, Macaire M.S.; Chiang, Angela; Sandhu, Harpreet K.; Madilao, Lina L.; Nguyen, Anh; Hamberger, Britta; Bach, Søren Spanner; Bohlmann, Jörg

    2013-01-01

    Plants produce over 10,000 different diterpenes of specialized (secondary) metabolism, and fewer diterpenes of general (primary) metabolism. Specialized diterpenes may have functions in ecological interactions of plants with other organisms and also benefit humanity as pharmaceuticals, fragrances, resins, and other industrial bioproducts. Examples of high-value diterpenes are taxol and forskolin pharmaceuticals or ambroxide fragrances. Yields and purity of diterpenes obtained from natural sources or by chemical synthesis are often insufficient for large-volume or high-end applications. Improvement of agricultural or biotechnological diterpene production requires knowledge of biosynthetic genes and enzymes. However, specialized diterpene pathways are extremely diverse across the plant kingdom, and most specialized diterpenes are taxonomically restricted to a few plant species, genera, or families. Consequently, there is no single reference system to guide gene discovery and rapid annotation of specialized diterpene pathways. Functional diversification of genes and plasticity of enzyme functions of these pathways further complicate correct annotation. To address this challenge, we used a set of 10 different plant species to develop a general strategy for diterpene gene discovery in nonmodel systems. The approach combines metabolite-guided transcriptome resources, custom diterpene synthase (diTPS) and cytochrome P450 reference gene databases, phylogenies, and, as shown for select diTPSs, single and coupled enzyme assays using microbial and plant expression systems. In the 10 species, we identified 46 new diTPS candidates and over 400 putatively terpenoid-related P450s in a resource of nearly 1 million predicted transcripts of diterpene-accumulating tissues. Phylogenetic patterns of lineage-specific blooms of genes guided functional characterization. PMID:23613273

  8. Two New Triterpene Glycosides from Centella asiatica

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Phytochemical investigation of the leaves of Centella asiatica resulted in the isolation and characterization of one new ursane type triterpene glycoside; asiaticoside G along with nine known compounds, that were characterized as ursane type triterpenes and /or their glycoside; asiatic acid (2), mad...

  9. Synthesis of Neoclerodane Diterpenes and Their Pharmacological Effects

    NASA Astrophysics Data System (ADS)

    Lovell, Kimberly M.; Prevatt-Smith, Katherine M.; Lozama, Anthony; Prisinzano, Thomas E.

    Salvinorin A is a neoclerodane diterpene that has been shown to be an agonist at kappa opioid receptors. Its unique structure makes it an attractive target for synthetic organic chemists due to its seven chiral centers and diterpene scaffold. This molecule is also interesting to pharmacologists because it is a non-serotonergic hallucinogen, and the first opioid ligand discovered that lacks a basic nitrogen. There have been several total synthesis approaches to salvinorin A, and these will be detailed within this chapter. Additionally, research efforts have concentrated on structure modification of the salvinorin A scaffold through semi-synthetic methods. Most modifications have focused on the manipulation of the acetate at C-2 and the furan ring. However, chemistry has also been developed to generate analogs at the C-1 ketone, the C-4 methyl ester, and the C-17 lactone. The synthetic methodologies developed for the salvinorin A scaffold will be described, as well as specific analogs with interesting biological activities.

  10. Salvinicins A and B, new neoclerodane diterpenes from Salvia divinorum.

    PubMed

    Harding, Wayne W; Tidgewell, Kevin; Schmidt, Matthew; Shah, Kushal; Dersch, Christina M; Snyder, John; Parrish, Damon; Deschamps, Jeffrey R; Rothman, Richard B; Prisinzano, Thomas E

    2005-07-07

    [reaction: see text] Two new neoclerodane diterpenes, salvinicins A (4) and B (5), were isolated from the dried leaves of Salvia divinorum. The structures of these compounds were elucidated by spectroscopic techniques, including (1)H and (13)C NMR, NOESY, HMQC, and HMBC. The absolute stereochemistry of these compounds was assigned on the basis of single-crystal X-ray crystallographic analysis of salvinicin A (4) and a 3,4-dichlorobenzoate derivative of salvinorin B.

  11. Salvinicins A and B, New Neoclerodane Diterpenes from Salvia divinorum

    PubMed Central

    Harding, Wayne W.; Tidgewell, Kevin; Schmidt, Matthew; Shah, Kushal; Dersch, Christina M.; Snyder, John; Parrish, Damon; Deschamps, Jeffrey R.; Rothman, Richard B.

    2008-01-01

    Two new neoclerodane diterpenes, salvinicins A (4) and B (5), were isolated from the dried leaves of Salvia divinorum. The structures of these compounds were elucidated by spectroscopic techniques, including 1H and 13C NMR, NOESY, HMQC, and HMBC. The absolute stereochemistry of these compounds was assigned on the basis of single crystal X-ray crystallographic analysis of salvinicin A (4) and a 3,4-dichlorobenzoate derivative of salvinorin B. PMID:15987194

  12. Dactylomelane diterpenes from the sea hare Aplysia depilans.

    PubMed

    Petraki, Anastasia; Ioannou, Efstathia; Papazafiri, Panagiota; Roussis, Vassilios

    2015-03-27

    A chemical investigation of the organic extract of the sea hare Aplysia depilans, collected off Skyros Island, Greece, yielded eight new brominated diterpenes (1-8), featuring the rare dactylomelane skeleton, together with the previously reported luzodiol (9). The structure elucidation and the assignment of the relative configurations of the new natural products were based on extensive NMR spectroscopic and MS spectrometric analyses. Compounds 1-9 were evaluated for their cytotoxic activities against five human tumor cell lines, but were proven inactive.

  13. Structure elucidation of casbane diterpenes from Croton argyrophyllus.

    PubMed

    e Silva-Filho, Francisco Artur; Braz-Filho, Raimundo; Silveira, Edilberto Rocha; Lima, Mary Anne Sousa

    2011-06-01

    Two novel casbane diterpenes 1-hydroxy-(2E,6Z,12E)-casba-2,6,12-triene-4,5-dione (1) and 6E,12E-casba-1,3,6,12-tetraen-1,4-epoxy-5-one (2) were isolated from the ethanol extract of the stems of Croton argyrophyllus. Structural characterization including the relative stereochemistry of all compounds was established on the basis of spectroscopic methods, mainly 1D and 2D NMR, and HRESIMS.

  14. Antileishmanial activity of diterpene acids in copaiba oil

    PubMed Central

    dos Santos, Adriana Oliveira; Izumi, Erika; Ueda-Nakamura, Tânia; Dias-Filho, Benedito Prado; da Veiga-Júnior, Valdir Florêncio; Nakamura, Celso Vataru

    2013-01-01

    Leishmaniasis is a neglected tropical disease. According to the World Health Organization, there are approximately 1.5-two million new cases of cutaneous leishmaniasis each year worldwide. Chemotherapy against leishmaniasis is based on pentavalent antimonials, which were developed more than a century ago. The goals of this study were to investigate the antileishmanial activity of diterpene acids in copaiba oil, as well as some possible targets of their action against Leishmania amazonensis. Methyl copalate and agathic, hydroxycopalic, kaurenoic, pinifolic and polyaltic acids isolated from Copaifera officinales oleoresins were utilised. Ultrastructural changes and the specific organelle targets of diterpenes were investigated with electron microscopy and flow cytometry, respectively. All compounds had some level of activity against L. amazonensis. Hydroxycopalic acid and methyl copalate demonstrated the most activity against promastigotes and had 50% inhibitory concentration (IC50) values of 2.5 and 6.0 µg/mL, respectively. However, pinifolic and kaurenoic acid demonstrated the most activity against axenic amastigote and had IC50 values of 3.5 and 4.0 µg/mL, respectively. Agathic, kaurenoic and pinifolic acid caused significant increases in plasma membrane permeability and mitochondrial membrane depolarisation of the protozoan. In conclusion, copaiba oil and its diterpene acids should be explored for the development of new antileishmanial drugs. PMID:23440116

  15. Volatile diterpene emission from dominant conifers in Japan

    NASA Astrophysics Data System (ADS)

    Matsunaga, S. N.; Chatani, S.; Nakatsuka, S.; Kusumoto, D.; Kubota, K.; Utsumi, Y.; Enoki, T.; Tani, A.; Hiura, T.

    2011-07-01

    Reactive volatile organic compounds (VOCs) are known to affect atmospheric chemistry, especially biogenic VOCs (BVOCs) which have a significant impact on regional air quality due to their large emission rates and high reactivities. Diterpenes (Kaur-16-ene and a diterpene likely to be Hibaene) were detected in all of the 205 enclosure air samples collected over multiple seasons at two different sites from Cryptomeria japonica and Chamaecyparis obtusa trees, the dominant coniferous trees in Japan. The emission rate of Kaur-16-ene, was determined to be from 0.01 to 7.1 μg dwg-1 h-1 (average: 0.61 μg dwg-1 h-1) by branch enclosure measurements and solid phase - liquid extraction techniques. The emission rate was an order of magnitude higher than that of monoterpenes which are known to comprise a major portion of total BVOC emissions. In addition, total emission of Kaur-16-ene at 30 °C was estimated to be comparable to that of total anthropogenic VOC emissions. To our knowledge, this is the first report of volatile diterpene emissions from trees.

  16. Triterpenoidal glycosides from Justicia betonica.

    PubMed

    Kanchanapoom, Tripetch; Noiarsa, Pawadee; Ruchirawat, Somsak; Kasai, Ryoji; Otsuka, Hideaki

    2004-09-01

    dFrom the aerial portion of Justicia betonica L., four triterpenoidal glycosides (justiciosides A-D) were isolated. Their structures were established through chemical and NMR spectroscopic analyses as olean-12-ene-1beta,3beta,11alpha,28-tetraol 28-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranoside, olean-12-ene-1beta,3beta,11alpha,28-tetraol 28-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranoside, 11alpha-methoxy-olean-12-ene-1beta,3beta,28-triol 28-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranoside, 11alpha-methoxy-olean-12-ene-1beta,3beta,28-triol 28-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranoside, respectively.

  17. Glycosides from the root of Iodes cirrhosa.

    PubMed

    Gan, Maoluo; Zhang, Yanling; Lin, Sheng; Liu, Mingtao; Song, Weixia; Zi, Jiachen; Yang, Yongchun; Fan, Xiaona; Shi, Jiangong; Hu, Jinfeng; Sun, Jiandong; Chen, Naihong

    2008-04-01

    Seven new neolignan glycosides ( 1- 7), two arylglycerol glycosides ( 8, 9), and 18 known glycosides have been isolated from an ethanolic extract of the root of Iodes cirrhosa. Their structures including absolute configurations were determined by spectroscopic and chemical methods. Based on analysis of the NMR data of threo and erythro 8-4'-oxyneolignans and arylglycerols in different solvents, the validity of J 7,8 and Deltadelta C8-C7 values to distinguish threo and erythro derivatives was discussed. In the in vitro assays, compound 4 and liriodendrin ( 17) both showed activity against glutamate-induced PC12 cell damage at 10 (-5) M.

  18. Four new phenolic glycosides from Baoyuan decoction.

    PubMed

    Ma, Xiaoli; Guo, Xiaoyu; Zhao, Mingbo; Tu, Pengfei; Jiang, Yong

    2017-03-01

    Four new phenolic glycosides, including two flavonoid glycosides (1 and 2) and two lignan glycosides (3 and 4), were isolated from the traditional Chinese medicine formula, Baoyuan decoction. Their structures were established by detailed analysis of the NMR and HR-ESI-MS spectroscopic data and their absolute configurations were determined by the experimental electronic circular dichroism data as well as chemical methods. Furthermore, the sources of the four new compounds were determined by the UPLC-Qtrap-MS method, which proved that 1 and 2 are originated from Glycyrrhiza uralensis, and 3 and 4 are from Cinnamomum cassia.

  19. Cloning of Casbene Synthases from Euphorbiaceae Plants and Implications for Diterpene Biosynthesis in This Family

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A large number of diterpenes have been isolated from Euphorbiaceae plants, many of which are of interest due to toxicity or potential therapeutic activity. Specific Euphorbiaceae diterpenes of medical interest include the latent HIV-1 activator prostratin (and related 12-deoxyphorbol esters), the an...

  20. Recent developments in β-C-glycosides: synthesis and applications.

    PubMed

    Lalitha, Krishnamoorthy; Muthusamy, Kumarasamy; Prasad, Y Siva; Vemula, Praveen Kumar; Nagarajan, Subbiah

    2015-01-30

    In the last few years, considerable progress has been made in the synthesis of C-glycosides. Despite its challenging chemistry, due to its versatility, C-glycosides play a pivotal role in developing novel materials, surfactants and bioactive molecules. In this review, we present snapshots of various synthetic methodologies developed for C-glycosides in the recent years and the potential application of C-glycosides derived from β-C-glycosidic ketones.

  1. Discovery and Characterization of a New Family of Diterpene Cyclases in Bacteria and Fungi.

    PubMed

    Yang, Yan-Long; Zhang, Shasha; Ma, Ke; Xu, Yuxing; Tao, Qiaoqiao; Chen, Yihua; Chen, Juan; Guo, Shunxing; Ren, Jinwei; Wang, Wenzhao; Tao, Yong; Yin, Wen-Bing; Liu, Hongwei

    2017-04-18

    Diterpene cyclases from bacteria and basidiomycete fungi are seldom studied. Here, we presented the identification and verification of EriG, a member of the UbiA superfamily, as the enzyme responsible for the cyclization of the cyathane skeleton in the mushroom Hericium erinaceum. Genome mining using the EriG protein sequence as a probe led to the discovery of a new family of ubiquitous UbiA-related diterpene cyclases in bacteria and fungi. We successfully characterized seven new diterpene cyclases from bacteria or basidiomycete fungi with the help of an engineered Escherichia coli strain and determined the structures of their corresponding products. A new diterpene with an unusual skeleton was generated during this process. The discovery of this new family of diterpene cyclases provides new insight into the UbiA superfamily.

  2. Stereoselective Synthesis of β-manno-Glycosides

    NASA Astrophysics Data System (ADS)

    Ishiwata, Akihiro; Ito, Yukishige

    Among the various types of O-glycosides with biological relevance, the β-glycoside of D-mannose (β-manno-glycoside) has been considered as one of the most challenging targets from a synthetic point of view. The majority of synthetic approaches to β-manno-glycoside can be put into two categories (the direct glycosylation and the glycosylation-inversion approaches). Additionally, a variety of intriguing approaches have been investigated with substantial success (alkylative glycosylation of 1,2-stannylene acetal, reductive manipulation of orthoester, intramolecular aglycon delivery, and enzymatic glycosylation). In this chapter, progress in the conceptually demanding β-mannosylation technology will be discussed, including current state of the art, with particular focus upon applications related to the synthesis of glycoprotein-related oligosaccharides.

  3. Two new coumarin glycosides from Peucedanum praeruptorum.

    PubMed

    Chang, Hai-Tao; Okada, Yoshihito; Ma, Ting-Jun; Okuyama, Toru; Tu, Peng-Fei

    2008-01-01

    Two new coumarin glycosides, praerosides VI (1) and VII (2), were isolated from the roots of Peucedanum praeruptorum Dunn. Their structures were elucidated by chemical reaction and NMR spectroscopic methods.

  4. Three new glycosides from Hylocereus undatus.

    PubMed

    Wu, Xin; Wang, Ying; Huang, Xiao-Jun; Fan, Chun-Lin; Wang, Guo-Cai; Zhang, Xiao-Qi; Zhang, Qin-Wen; Ye, Wen-Cai

    2011-08-01

    Three new glycosides, undatusides A-C (1-3), and 11 known compounds (4-14) were isolated from the flowers of Hylocereus undatus. Their structures were elucidated on the basis of spectroscopic data and chemical method.

  5. Triterpenoid glycosides from Ladenbergia hexandra Klotzsch.

    PubMed

    Furukawa, Megumi; Kamo, Satoshi; Makino, Mitsuko; Kurita, Masahiro; Tabata, Keiichi; Matsuzaki, Keiichi; Suzuki, Takashi; Uchiyama, Taketo

    2017-04-01

    From the bark of Ladenbergia hexandra Klotzsch, ten triterpenoid glycosides were isolated along with five known compounds, and their structures were determined based on extensive NMR and mass spectroscopic, GC and HPLC analyses. Some triterpenoid glycosides contained 6-deoxy-D-allose or D-allose as a sugar moiety. The absolute stereochemical assignment of the sugars was determined by comparison with synthetic samples, as well as by GC and HPLC analysis.

  6. Pregnane glycosides from Caralluma adscendens var. fimbriata.

    PubMed

    Kunert, Olaf; Rao, Vijayalakshmi Gurunath; Babu, Gummadi Sridhar; Sujatha, Palatheeya; Sivagamy, Malayalam; Anuradha, Sandala; Rao, Belvotagi Venkatrao Adavi; Kumar, Bobbala Ravi; Alex, Robert Michael; Schühly, Wolfgang; Kühnelt, Doris; Rao, Ghanakota Venkateshwara; Rao, Achanta Venkata Narasimha Appa

    2008-02-01

    Eleven novel pregnane glycosides, 2-7 and 9-13, of which four, i.e., 10-13, comprised a new pregnane-type genin exhibiting a hydroxymethylene instead of a Me group at C(19), and the known pregnane glycoside stalagmoside V (8) were isolated from whole plants of Caralluma adscendens var. fimbriata, a native Indian succulent plant. Their structures were elucidated by extensive 2D-NMR spectroscopic studies.

  7. New pregnane glycosides from Caralluma dalzielii.

    PubMed

    De Leo, Marinella; De Tommasi, Nunziatina; Sanogo, Rokia; Autore, Giuseppina; Marzocco, Stefania; Pizza, Cosimo; Morelli, Ivano; Braca, Alessandra

    2005-08-01

    Twenty-seven new pregnane glycosides were isolated from the whole plant of Caralluma dalzielii, and their structures elucidated from extensive 2D NMR analysis as well as ESI-MS experiments. All isolated compounds were tested for their antiproliferative activity on J774.A1, HEK-293, and WEHI-164 cell lines. Moderate to high potency of cytotoxicities were found in almost all tested compounds, confirming the significant cytotoxic activity of pregnane glycosides.

  8. Structural Characterization of the Degradation Products of a Minor Natural Sweet Diterpene Glycoside Rebaudioside M under Acidic Conditions

    PubMed Central

    Prakash, Indra; Chaturvedula, Venkata Sai Prakash; Markosyan, Avetik

    2014-01-01

    Degradation of rebaudioside M, a minor sweet component of Stevia rebaudiana Bertoni, under conditions that simulated extreme pH and temperature conditions has been studied. Thus, rebaudioside M was treated with 0.1 M phosphoric acid solution (pH 2.0) and 80 °C temperature for 24 h. Experimental results indicated that rebaudioside M under low pH and higher temperature yielded three minor degradation compounds, whose structural characterization was performed on the basis of 1D (1H-, 13C-) & 2D (COSY, HSQC, HMBC) NMR, HRMS, MS/MS spectral data as well as enzymatic and acid hydrolysis studies. PMID:24424316

  9. Structural characterization of the degradation products of a minor natural sweet diterpene glycoside Rebaudioside M under acidic conditions.

    PubMed

    Prakash, Indra; Chaturvedula, Venkata Sai Prakash; Markosyan, Avetik

    2014-01-14

    Degradation of rebaudioside M, a minor sweet component of Stevia rebaudiana Bertoni, under conditions that simulated extreme pH and temperature conditions has been studied. Thus, rebaudioside M was treated with 0.1 M phosphoric acid solution (pH 2.0) and 80 °C temperature for 24 h. Experimental results indicated that rebaudioside M under low pH and higher temperature yielded three minor degradation compounds, whose structural characterization was performed on the basis of 1D (1H-, 13C-) & 2D (COSY, HSQC, HMBC) NMR, HRMS, MS/MS spectral data as well as enzymatic and acid hydrolysis studies.

  10. A labdane diterpene glucoside from the rhizomes of Curcuma mangga.

    PubMed

    Abas, Faridah; Lajis, Nordin H; Shaari, Khozirah; Israf, Daud Ahmad; Stanslas, Johnson; Yusuf, Umi Kalsom; Raof, Salahuddin Mohd

    2005-07-01

    A new labdane diterpene glucoside, curcumanggoside (1), together with nine known compounds, including labda-8(17),12-diene-15,16-dial (2), calcaratarin A (3), zerumin B (4), scopoletin, demethoxycurcumin, bisdemethoxycurcumin, 1,7-bis(4-hydroxyphenyl)-1,4,6-heptatrien-3-one, curcumin, and p-hydroxycinnamic acid, have been isolated from the rhizomes of Curcuma mangga. Their structures were determined using a combination of 1D (1H NMR, 13C NMR, DEPT) and 2D (COSY, HSQC, HMBC) NMR techniques. All diarylheptanoids and scopoletin showed significant antioxidant activity. Zerumin B, demethoxycurcumin, bisdemethoxycurcumin, and curcumin also exhibited cytotoxic activity against a panel of five human tumor cell lines.

  11. Steroidal glycosides from the leaves of Cestrum nocturnum.

    PubMed

    Mimaki, Yoshihiro; Watanabe, Kazuki; Sakagami, Hiroshi; Sashida, Yutaka

    2002-12-01

    Further phytochemical analysis aimed at the steroidal glycoside constituents of the leaves of Cestrum nocturnum has resulted in the isolation of eight new steroidal glycosides (1-8), which were classified into a spirostanol saponin (1), a furostanol saponin (2), a pseudo-furostanol saponin (3), two pregnane glycosides (4, 5), two cholestane glycosides (6, 7), and pregnane-carboxylic acid gamma-lactone glycoside (8), and of two known spirostanol glycosides (9, 10). The structures of the new compounds were elucidated on the basis of chemical and spectroscopic evidence.

  12. Expanding the Landscape of Diterpene Structural Diversity through Stereochemically Controlled Combinatorial Biosynthesis

    PubMed Central

    Andersen‐Ranberg, Johan; Kongstad, Kenneth Thermann; Nielsen, Morten Thrane; Jensen, Niels Bjerg; Pateraki, Irini; Bach, Søren Spanner; Hamberger, Britta; Zerbe, Philipp; Staerk, Dan; Bohlmann, Jörg; Møller, Birger Lindberg

    2016-01-01

    Abstract Plant‐derived diterpenoids serve as important pharmaceuticals, food additives, and fragrances, yet their low natural abundance and high structural complexity limits their broader industrial utilization. By mimicking the modularity of diterpene biosynthesis in plants, we constructed 51 functional combinations of class I and II diterpene synthases, 41 of which are “new‐to‐nature”. Stereoselective biosynthesis of over 50 diterpene skeletons was demonstrated, including natural variants and novel enantiomeric or diastereomeric counterparts. Scalable biotechnological production for four industrially relevant targets was accomplished in engineered strains of Saccharomyces cerevisiae. PMID:26749264

  13. Alternative oxidase in resistance to biotic stresses: Nicotiana attenuata AOX contributes to resistance to a pathogen and a piercing-sucking insect but not Manduca sexta larvae.

    PubMed

    Zhang, Lu; Oh, Youngjoo; Li, Hongyu; Baldwin, Ian T; Galis, Ivan

    2012-11-01

    The role of the alternative respiratory pathway in the protection of plants against biotic stress was examined in transgenic tobacco (Nicotiana attenuata) plants (irAOX) silenced in the expression of ALTERNATIVE OXIDASE (AOX) gene. Wild-type and irAOX plants were independently challenged with (1) chewing herbivores (Manduca sexta), (2) piercing-sucking insects (Empoasca spp.), and (3) bacterial pathogens (Pseudomonas syringae pv tomato DC3000), showing that all these treatments can strongly elicit accumulation of AOX gene transcripts in wild-type plants. When N. attenuata chemical defenses and resistance were examined, irAOX plants showed wild-type levels of defense-related phytohormones, secondary metabolites, and resistance to M. sexta. In contrast, piercing-sucking leafhoppers (Empoasca spp.) caused more leaf damage and induced significantly higher salicylic acid levels in irAOX compared with wild-type plants in the field and/or glasshouse. Subsequently, irAOX plants accumulated lower levels of defense metabolites, 17-hydroxygeranyllinalool diterpene glycosides, caffeoylputrescine, and nicotine compared with wild-type plants under prolonged attack of Empoasca spp. in the glasshouse. Finally, an accelerated cell death phenotype was observed in irAOX plants infected with P. syringae, which correlated with higher levels of salicylic acid and hydrogen peroxide levels in pathogen-infected irAOX compared with wild-type leaves. Overall, the AOX-associated changes in phytohormone and/or redox levels appear to support the resistance of N. attenuata plants against cell piercing-sucking insects and modulate the progression of cell death in pathogen-infected tissues but are not effective against rapidly feeding specialist herbivore M. sexta.

  14. Alternative Oxidase in Resistance to Biotic Stresses: Nicotiana attenuata AOX Contributes to Resistance to a Pathogen and a Piercing-Sucking Insect But Not Manduca sexta Larvae1[W][OA

    PubMed Central

    Zhang, Lu; Oh, Youngjoo; Li, Hongyu; Baldwin, Ian T.; Galis, Ivan

    2012-01-01

    The role of the alternative respiratory pathway in the protection of plants against biotic stress was examined in transgenic tobacco (Nicotiana attenuata) plants (irAOX) silenced in the expression of ALTERNATIVE OXIDASE (AOX) gene. Wild-type and irAOX plants were independently challenged with (1) chewing herbivores (Manduca sexta), (2) piercing-sucking insects (Empoasca spp.), and (3) bacterial pathogens (Pseudomonas syringae pv tomato DC3000), showing that all these treatments can strongly elicit accumulation of AOX gene transcripts in wild-type plants. When N. attenuata chemical defenses and resistance were examined, irAOX plants showed wild-type levels of defense-related phytohormones, secondary metabolites, and resistance to M. sexta. In contrast, piercing-sucking leafhoppers (Empoasca spp.) caused more leaf damage and induced significantly higher salicylic acid levels in irAOX compared with wild-type plants in the field and/or glasshouse. Subsequently, irAOX plants accumulated lower levels of defense metabolites, 17-hydroxygeranyllinalool diterpene glycosides, caffeoylputrescine, and nicotine compared with wild-type plants under prolonged attack of Empoasca spp. in the glasshouse. Finally, an accelerated cell death phenotype was observed in irAOX plants infected with P. syringae, which correlated with higher levels of salicylic acid and hydrogen peroxide levels in pathogen-infected irAOX compared with wild-type leaves. Overall, the AOX-associated changes in phytohormone and/or redox levels appear to support the resistance of N. attenuata plants against cell piercing-sucking insects and modulate the progression of cell death in pathogen-infected tissues but are not effective against rapidly feeding specialist herbivore M. sexta. PMID:22961128

  15. New triterpenoid glycosides from the roots of Ilex asprella.

    PubMed

    Wang, Lei; Cai, Yan; Zhang, Xiao-Qi; Fan, Chun-Lin; Zhang, Qing-Wen; Lai, Xiao-Ping; Ye, Wen-Cai

    2012-02-15

    Eight new triterpenoid glycosides, named ilexasosides A-H, were isolated from the roots of Ilex asprella. Their structures were elucidated by spectroscopic and chemical analyses. Ilexasosides B and D are rare sulfated derivatives of ursane-type triterpenoid glycosides.

  16. Iridoid and megastigmane glycosides from Phlomis aurea.

    PubMed

    Kamel, M S; Mohamed, K M; Hassanean, H A; Ohtani, K; Kasai, R; Yamasaki, K

    2000-10-01

    From the leaves of Phlomis aurea, two new iridoids of unique structures named 3-epiphlomurin (1) and phlomurin (2), a new megastigmane glucoside phlomuroside (3) and a new benzyl alcohol glycoside having the structure benzyl alcohol-O-beta-xylopyranosyl-(1-->2)-beta-glucopyranoside (4) have been isolated together with four known iridoids auroside, lamiide, 8-epiloganin and ipolamiide, two known phenolic glycosides acteoside (verbascoside) and syringin, one known phenylethanoid glycoside 2-phenylethyl-O-beta-xylopyranosyl-(1-->2)-beta-glucopyranoside, one known lignan liriodendrin and three known flavonoids chrysoeriol-7-O-beta-glucopyranoside, acacetin-7-O-beta-glucopyranoside and luteolin-7-O-beta-glucopyranoside. The structures of the isolated compounds were verified by means of mass spectrometry (MS) and nuclear magnetic resonance (NMR) spectral analyses.

  17. Bioactive spirostane glycosides from Tacca plantaginea.

    PubMed

    Liu, Zhen-Hua; Yan, Huan; Si, Yong-Ai; Ni, Wei; Chen, Yu; He, Li; Liu, Hai-Yang

    2016-02-01

    Eight new spirostane glycosides, taccaosides E-L (2-7, 11, and 14), along with 7 known spirostane glycosides were isolated from the extract of the whole plants of Tacca plantaginea (Hance) Drenth. Their structures were established on the basis of physical data, spectroscopic analysis (MS, 1D and 2D NMR), and chemical methods. The cytotoxicities of the isolates were evaluated in vitro against two human cancer cell lines (HEK293 and HepG2). The results showed that compound 1 had the strongest cytotoxic activity with IC50 values of 1.7 μM and 1.2 μM against the two cancer cell lines, respectively. Furthermore, the spirostane glycosides with 17α-hydroxyl group at their aglycones (10, 12, and 15) were tested for the induced platelet aggregation activity.

  18. New kaurene diterpenoid glycosides from fenugreek seeds.

    PubMed

    Pang, Xu; Kang, Li-Ping; Yu, He-Shui; Zhao, Yang; Xiong, Cheng-Qi; Zhang, Jie; Ma, Bai-Ping

    2013-01-01

    Two new kaurene diterpenoid glycosides, named Graecumoside A (1) and B (2), were isolated from fenugreek seeds, along with three known flavonoid-C-glycosides, isoorientin (3), isovitexin (4) and vitexin (5). By combined analyses of 1D- and 2D-NMR, and MS spectroscopy, the structures of two new compounds were elucidated as 3-O-β- D-glucopyranosyl kaur-5, 16-dien-3β, 6, 13β-trihydroxy-7-oxo-18-oic acid methyl ester and 3-O-β-neohesperidosyl kaur-5, 16-dien-3β, 6, 13β-trihydroxy-7-oxo-18-oic acid methyl ester, respectively. The kaurene diterpenoid glycosides were first isolated and identified from fenugreek seeds.

  19. Cytotoxic phenylpropanoid glycosides from Cirsium japonicum.

    PubMed

    Shang, Dong-Li; Ma, Qin-Ge; Wei, Rong-Rui

    2016-12-01

    Three new phenylpropanoid glycosides 1-3, along with nine known phenylpropanoid glycosides 4-12, were isolated from the aerial parts of Cirsium japonicum. The structures of isolated compounds were elucidated by chemical and spectroscopic methods. Compounds 1, 3, 6, 8, and 11 showed moderate cytotoxicities against MCF-7, U87, HCT116, and A549 cell lines with IC50 values in the range of 1.35-11.32 μM. The known compounds 4-12 were obtained from this plant for the first time.

  20. Polyoxypregnane glycosides from Caralluma retrospiciens.

    PubMed

    Halaweish, Fathi T; Huntimer, Eric; Khalil, Ashaf T

    2004-01-01

    Six related polyoxypregnane glycosides were isolated and characterised from Caralluma retrospiciens leaves. The compounds were identified as 12beta-benzoyloxy-8beta,14beta-dihydroxypregn-20-one-3-O-[3-O-methyl-6-deoxy-beta-D-allopyranosyl-(1 --> 4)-beta-D-cymaropyranosyl-(1 --> 4)-]-beta-D-cymaropyranoside], 12beta-benzoyloxy-8beta,14beta-dihydroxypregn-20-one-3-O-[beta-D-glucopyranosyl-(1 --> 4)-3-O-methyl-6-deoxy-beta-D-allopyranosyl-(1 --> 4)-beta-D-cymaropyranosyl-(1 --> 4)-beta-D-cymaropyranoside], 12beta-benzoyloxy-8beta,14beta-dihydroxypregn-20-one-3-O-[beta-D-glucopyranosyl-(1 --> 4)-3-O-methyl-6-deoxy-beta-D-galactopyranosyl-(1 --> 4)-3-O-methyl-6-deoxy-beta-D-galactopyranoside], 12beta-benzoyloxy-8beta,14beta-dihydroxypregn-20-one-3-O-[beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranosyl-(1 --> 4)-3-O-methyl-6-deoxy-beta-D-galactopyranosyl-(1 --> 4)-3-O-methyl-6-deoxy-beta-D-galactopyranoside], 12beta-benzoyloxy-11alpha-isovaleroyloxy-8beta,14beta-dihydroxypregn-20-one-3-O-[beta-D-glucopyranosyl-(1 --> 4)-3-O-methyl-6-deoxy-beta-D-galactopyranosyl-(1 --> 4)-3-O-methyl-6-deoxy-beta-D-galactopyranoside], and 12beta-benzoyloxy-11alpha-isovaleroyloxy-8beta,14beta-dihydroxypregn-20-one-3-O-[beta-D-glucopyranosyl (1 --> 4)-3-O-methyl-6-deoxy-beta-D-allopyranosyl-(1 --> 4)-beta-D-cymaropyranosyl-(1 --> 4)-beta-D-cymaropyranoside]. The structures were determined by detailed analysis of one- and two-dimensional NMR spectra as well as by chemical means. The compounds showed cytotoxic activities towards brine shrimp having IC50 values of 1.19 x 10(-4), 8.83 x 10(-5), 2.64 x 10(-4), 2.26 x 10(-4), 2.39 x 10(-4) and 1.70 x 10(-4) M, respectively. This is the first report of the isolation of these compounds from a natural source.

  1. A new secotrinervitane diterpene isolated from soldiers of the Madagascan termite species, Nasutitermes canaliculatus.

    PubMed

    Rabemanantsoa, A; Ranarivelo, Y; Andriantsiferana, M; Tillequin, F; Silverton, J V; Garraffo, H M; Spande, T F; Yeh, H J; Daly, J W

    1996-09-01

    Reported herein is the X-ray crystallographic structure of a novel 10-oxygenated secotrinervitane diterpene, 3 alpha, 10 alpha-diacetoxy-7,16-secotrinervita-7,11,15(17)-triene (4), from soldiers of the endemic Madagascan termite Nasutitermes canaliculatus, which was compared with an energy-minimized structure obtained by computer molecular modeling. We also report 1H- and 13C-NMR and MS data for this new diterpene.

  2. Diterpene alkaloids with an aza-ent-kaurane skeleton from Isodon rubescens.

    PubMed

    Liu, Xu; Yang, Jing; Wang, Wei-Guang; Li, Yan; Wu, Ji-Zhou; Pu, Jian-Xin; Sun, Han-Dong

    2015-02-27

    Two compounds belonging to a new group of diterpene alkaloids, kaurines A and B (1 and 2), and an alkaloid bearing a succinimide moiety (3) were obtained from Isodon rubescens. Their structures and absolute configurations were determined by spectroscopy and quantum-chemical computational (13)C NMR and ECD data analysis. These alkaloids differ from known diterpene alkaloids and diterpenoids and are presumably biosynthesized from ent-kaurane diterpenoids.

  3. Synthetic studies of neoclerodane diterpenes from Salvia divinorum: preparation and opioid receptor activity of salvinicin analogues.

    PubMed

    Simpson, Denise S; Katavic, Peter L; Lozama, Anthony; Harding, Wayne W; Parrish, Damon; Deschamps, Jeffrey R; Dersch, Christina M; Partilla, John S; Rothman, Richard B; Navarro, Hernan; Prisinzano, Thomas E

    2007-07-26

    Further modification of salvinorin A (1a), the major active component of Salvia divinorum, has resulted in the synthesis of novel neoclerodane diterpenes with opioid receptor affinity and activity. We report in this study that oxadiazole 11a and salvidivin A (12a), a photooxygenation product of 1a, have been identified as the first neoclerodane diterpenes with kappa antagonist activity. This indicates that additional structural modifications of 1a may lead to analogues with higher potency and utility as drug abuse medications.

  4. Labdane-type diterpenes active against acne from pine cones (Pinus densiflora).

    PubMed

    Sultan, Md Zakir; Jeon, Young-Min; Moon, Surk-Sik

    2008-03-01

    Bioassay-guided extraction and fractionation of the aqueous methanolic extract of the cones of Pinus densiflora (Pinaceae) afforded one new labdane-type diterpene aldehyde, 15-nor-14-oxolabda-8(17),12 E-diene-18-oic acid, along with eight known diterpenes. Their structures were elucidated using spectroscopic methods as well as by comparison with previously reported data. The isolates showed antibacterial (Propionibacterium acnes) and antifungal activities.

  5. Variability of some diterpene esters in coffee beverages as influenced by brewing procedures.

    PubMed

    Moeenfard, Marzieh; Erny, Guillaume L; Alves, Arminda

    2016-11-01

    Several coffee brews, including classical and commercial beverages, were analyzed for their diterpene esters content (cafestol and kahweol linoleate, oleate, palmitate and stearate) by high performance liquid chromatography with diode array detector (HPLC-DAD) combined with spectral deconvolution. Due to the coelution of cafestol and kahweol esters at 225 nm, HPLC-DAD did not give accurate quantification of cafestol esters. Accordingly, spectral deconvolution was used to deconvolve the co-migrating profiles. Total cafestol and kahweol esters content of classical coffee brews ranged from 5-232 to 2-1016 mg/L, respectively. Commercial blends contained 1-54 mg/L of total cafestol esters and 2-403 mg/L of total kahweol esters. Boiled coffee had the highest diterpene esters content, while filtered and instant brews showed the lowest concentrations. However, individual diterpene esters content was not affected by brewing procedure as in terms of kahweol esters, kahweol palmitate was the main compound in all samples, followed by kahweol linoleate, oleate and stearate. Higher amounts of cafestol palmitate and stearate were also observed compared to cafestol linoleate and cafestol oleate. The ratio of diterpene esters esterified with unsaturated fatty acids to total diterpene esters was considered as measure of their unsaturation in analyzed samples which varied from 47 to 52%. Providing new information regarding the diterpene esters content and their distribution in coffee brews will allow a better use of coffee as a functional beverage.

  6. Molecular Signaling Pathways Behind the Biological Effects of Salvia Species Diterpenes in Neuropharmacology and Cardiology.

    PubMed

    Akaberi, M; Iranshahi, M; Mehri, S

    2016-06-01

    The genus Salvia, from the Lamiaceae family, has diverse biological properties that are primarily attributable to their diterpene contents. There is no comprehensive review on the molecular signaling pathways of these active components. In this review, we investigated the molecular targets of bioactive Salvia diterpenes responsible for the treatment of nervous and cardiovascular diseases. The effects on different pathways, including apoptosis signaling, oxidative stress phenomena, the accumulation of amyloid beta plaques, and tau phosphorylation, have all been considered to be mechanisms of the anti-Alzheimer properties of Salvia diterpenes. Additionally, effects on the benzodiazepine and kappa opioid receptors and neuroprotective effects are noted as neuropharmacological properties of Salvia diterpenes, including tanshinone IIA, salvinorin A, cryptotanshinone, and miltirone. Tanshinone IIA, as the primary diterpene of Salvia miltiorrhiza, has beneficial activities in heart diseases because of its ability to scavenge free radicals and its effects on transcription factors, such as nuclear transcription factor-kappa B (NF-κB) and the mitogen-activated protein kinases (MAPKs). Additionally, tanshinone IIA has also been proposed to have cardioprotective properties including antiarrhythmic activities and effects on myocardial infarction. With respect to the potential therapeutic effects of Salvia diterpenes, comprehensive clinical trials are warranted to evaluate these valuable molecules as lead compounds. Copyright © 2016 John Wiley & Sons, Ltd.

  7. Chemosystematic investigations of irregular diterpenes in Anisotome and related New Zealand Apiaceae.

    PubMed

    Zidorn, Christian; Sturm, Sonja; Dawson, John W; van Klink, John W; Stuppner, Hermann; Perry, Nigel B

    2002-02-01

    A chemosystematic HPLC-UV and HPLC-MS investigation of New Zealand members of the Apiaceae was performed. Diterpenes were identified and quantified in methanolic extracts from subaerial parts of 28 taxa and 54 samples of Aciphylla, Anisotome, Apium, Gingidia, Lignocarpa, Oreomyrrhis, and Scandia. Six diterpenes (1-2, 4-7) and four polyacetylenes (8-11) were identified. The known compounds were the diterpenes anisotomenoic acid 1, anisotomene-1-ol 2, 16-acetoxyanisotomenoic acid 4 and anisotomene-1,12-diol 5; and the polyacetylenes falcarinol 8, falcarindiol 9, (+)-9(Z),17-octadecadiene-12,14-diyne-1,11,16-triol 10, and (+)-9(Z),17-octadecadiene-12,14-diyne-1,11,16-triol 1-acetate 11. New irregular diterpenes 13,14-dihydroanisotom-12E-ene-1,14-diol 6 and 14-methoxy-13,14-dihydroanisotom-12E-ene-1-ol 7 were isolated from A. haastii. Isomers of the new semi-synthetic diterpene 16-hydroxyanisotomenoic acid 3 were detected in extracts of Anisitone flexuosa. Structure elucidation was performed by HR mass spectrometry and 1D and 2D NMR spectroscopy. In crude extracts, compounds were identified by their HPLC retention times and their on-line HPLC-UV and MS spectra. Anisotomene diterpenes occurred in eight out of 16 species of the genus Anisotome, but were not detected in any of the other genera. In contrast, polyacetylenes were present in all the genera investigated.

  8. Twisting of glycosidic bonds by hydrolases

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Patterns of scissile bond twisting have been found in crystal structures of glycoside hydrolases (GHs) that are complexed with substrates and inhibitors. To estimate the increased potential energy in the substrates that results from this twisting, we have plotted torsion angles for the scissile bond...

  9. Anticancer activity of sea cucumber triterpene glycosides.

    PubMed

    Aminin, Dmitry L; Menchinskaya, Ekaterina S; Pisliagin, Evgeny A; Silchenko, Alexandra S; Avilov, Sergey A; Kalinin, Vladimir I

    2015-03-06

    Triterpene glycosides are characteristic secondary metabolites of sea cucumbers (Holothurioidea, Echinodermata). They have hemolytic, cytotoxic, antifungal, and other biological activities caused by membranotropic action. These natural products suppress the proliferation of various human tumor cell lines in vitro and, more importantly, intraperitoneal administration in rodents of solutions of some sea cucumber triterpene glycosides significantly reduces both tumor burden and metastasis. The anticancer molecular mechanisms include the induction of tumor cell apoptosis through the activation of intracellular caspase cell death pathways, arrest of the cell cycle at S or G2/M phases, influence on nuclear factors, NF-κB, and up-down regulation of certain cellular receptors and enzymes participating in cancerogenesis, such as EGFR (epidermal growth factor receptor), Akt (protein kinase B), ERK (extracellular signal-regulated kinases), FAK (focal adhesion kinase), MMP-9 (matrix metalloproteinase-9) and others. Administration of some glycosides leads to a reduction of cancer cell adhesion, suppression of cell migration and tube formation in those cells, suppression of angiogenesis, inhibition of cell proliferation, colony formation and tumor invasion. As a result, marked growth inhibition of tumors occurs in vitro and in vivo. Some holothurian triterpene glycosides have the potential to be used as P-gp mediated MDR reversal agents in combined therapy with standard cytostatics.

  10. Anticancer Activity of Sea Cucumber Triterpene Glycosides

    PubMed Central

    Aminin, Dmitry L.; Menchinskaya, Ekaterina S.; Pisliagin, Evgeny A.; Silchenko, Alexandra S.; Avilov, Sergey A.; Kalinin, Vladimir I.

    2015-01-01

    Triterpene glycosides are characteristic secondary metabolites of sea cucumbers (Holothurioidea, Echinodermata). They have hemolytic, cytotoxic, antifungal, and other biological activities caused by membranotropic action. These natural products suppress the proliferation of various human tumor cell lines in vitro and, more importantly, intraperitoneal administration in rodents of solutions of some sea cucumber triterpene glycosides significantly reduces both tumor burden and metastasis. The anticancer molecular mechanisms include the induction of tumor cell apoptosis through the activation of intracellular caspase cell death pathways, arrest of the cell cycle at S or G2/M phases, influence on nuclear factors, NF-κB, and up-down regulation of certain cellular receptors and enzymes participating in cancerogenesis, such as EGFR (epidermal growth factor receptor), Akt (protein kinase B), ERK (extracellular signal-regulated kinases), FAK (focal adhesion kinase), MMP-9 (matrix metalloproteinase-9) and others. Administration of some glycosides leads to a reduction of cancer cell adhesion, suppression of cell migration and tube formation in those cells, suppression of angiogenesis, inhibition of cell proliferation, colony formation and tumor invasion. As a result, marked growth inhibition of tumors occurs in vitro and in vivo. Some holothurian triterpene glycosides have the potential to be used as P-gp mediated MDR reversal agents in combined therapy with standard cytostatics. PMID:25756523

  11. Antiproliferative steroidal glycosides from Digitalis ciliata.

    PubMed

    Perrone, Angela; Capasso, Anna; Festa, Michela; Kemertelidze, Ether; Pizza, Cosimo; Skhirtladze, Alexandre; Piacente, Sonia

    2012-04-01

    Two new compounds, a furostanol glycoside (1) and a pregnane glycoside (4), along with eight known compounds, belonging to the classes of spirostane (2,3), pregnane (5-7) and cardenolide (8-10) glycosides, were isolated from the seeds of Digitalis ciliata. Their structures were elucidated by 1D and 2D-NMR experiments as well as ESI-MS analysis. For the first time pregnane glycosides of the diginigenin series have been isolated from D. ciliata. The cytotoxic effects of compounds 1-10 on cell viability of several cancer cell lines, namely human breast cancer (MCF-7), human glioblastoma (T98G), human lung adenocarcinoma (A549), human colon carcinoma (HT-29), and human prostate cancer (PC-3) cell lines were evaluated. Compounds 1, 4, 7 and 8 showed antiproliferative effects against MCF-7, HT-29 and A549 cancer cells with IC₅₀ values ranging from 8.3 to 20 μM. The effects of compounds 1-10 on cell proliferation were evaluated on these three cancer cell lines by cell cycle analysis of DNA content using flow cytometry. Compounds 7, 8 and 10 induced significant changes in G₂/M cell cycle phase of all analyzed cells. The obtained results indicate that compounds 7, 8 and 10 are cytostatic compounds effective in reducing cell proliferation by inducing accumulation of the cells in the G₂/M phase of the cell cycle.

  12. Glycosides of the Magydaris pastinacea L.

    PubMed

    Cerri, R; Dessì, G; Manconi, P M; Serra, D; Pau, A

    1988-12-01

    From the alcoholic extract of fresh rhizomes from Magydaris pastinacea the glycosidic fraction was separated: it appears to be made up of seven different constituents one of which, 7-0-beta-D-glucopyranosil-8(2',3'-dihydroxy-3'methyl)-butylcoum arin isolated and identified by us, is relatively more abundant.

  13. A new isoflavone glycoside from Pueraria alopecuroides.

    PubMed

    Yang, Junlin; Fan, Qingfei; Zhang, Huanli; Song, Qishi

    2016-01-01

    A new isoflavone glycoside, (-)-tuberosin-3-O-β-D-glucopyranoside (1), along with 10 known compounds 1a-10, was isolated from Pueraria alopecuroides. Their structures were determined on the basis of spectral data including 1D and 2D NMR and HREIMS. These compounds were isolated from this plant for the first time.

  14. Acylated pregnane glycosides from Caralluma russeliana.

    PubMed

    Abdel-Sattar, Essam; Ahmed, Ahmed A; Hegazy, Mohamed-Elamir F; Farag, Mohamed A; Al-Yahya, Mohammad Abdul-Aziz

    2007-05-01

    The chloroform extract of the aerial parts of Caralluma russeliana yielded four acylated pregnane glycosides, namely russeliosides E-H, three were found now. The structures of the compounds were elucidated using MS, 1H NMR, 13C NMR, 1H-1H COSY, HMQC, NOESY and HMBC experiments.

  15. New oxypregnane glycosides from Caralluma penicillata.

    PubMed

    Abdel-Sattar, Essam; Meselhy, Meselhy R; Al-Yahya, Mohammed Abdul-Aziz

    2002-05-01

    The ether fraction of the defatted ethanol extract of the aerial parts of Caralluma penicillata (defl) M. E. Br. (Asclepiadaceae) yielded four new oxypregnane glycosides, penicillosides D-G. The structures of the isolated compounds were established by different spectroscopic methods.

  16. Triterpene glycosides of sea cucumbers (Holothuroidea, Echinodermata) as taxonomic markers.

    PubMed

    Kalinin, Vladimir I; Avilov, Sergey A; Silchenko, Alexandra S; Stonik, Valentin A

    2015-01-01

    Triterpene glycosides are characteristic metabolites of sea cucumbers (Holothurioidea, Echinodermata). The majority of the glycosides belong to the holostane type {lanostane derivatives with an 18(20)-lactone}. Carbohydrate chains of these glycosides contain xylose, glucose, quinovose, 3-O-methylglucose, and, rarely, 3-O-methylxylose, 3-O-methylglucuronic acid, 3-O-methylquinovose, and 6-O-acetyl-glucose. The glycosides are specific for genera, groups of genera and even for species. The advantages and problems in the use of triterpene glycosides as taxonomic markers in the systematics of sea cucumbers are discussed.

  17. Enzymatic Processing of Bioactive Glycosides from Natural Sources

    NASA Astrophysics Data System (ADS)

    Weignerová, Lenka; Křen, Vladimír

    A number of biologically active natural products are glycosides. Often, the glycosidic residue is crucial for their activity. In other cases, glycosylation only improves their pharmacokinetic parameters. Enzymatic modification of these glycosides - both extension of the glycoside moiety and its selective trimming - is advantageous due to their selectivity and mildness of the reaction conditions in the presence of reactive and sensitive complex aglycones. Enzymatic reactions enable the resulting products to be used as "natural products", e.g., in nutraceuticals. This chapter concentrates on naturally occurring glycosides used in medicine but also in the food and flavor industry (e.g., sweeteners). Both "classical" and modern methods will be discussed.

  18. Cembranoid diterpenes from the Caribbean sea whip Eunicea knighti.

    PubMed

    Tello, Edisson; Castellanos, Leonardo; Arevalo-Ferro, Catalina; Duque, Carmenza

    2009-09-01

    Three new cembranoid diterpenes, knightol (1), knightol acetate (2), and knightal (3), along with the known asperdiol (4) and asperdiol acetate (5), were isolated as major compounds from the sea whip Eunicea knighti collected from the Colombian Caribbean. The structures and absolute configurations of 1-5 were determined on the basis of spectroscopic analyses and by a combination of chemical and NMR methods, multiple correlations observed in a ROESY experiment, and using the modified Mosher method. Additionally, five semisynthetic compounds, 6-10, obtained during the chemical transformations of the natural compounds are here reported for the first time. All compounds were tested for antimicrobial activity against marine bacteria associated with heavily fouled surfaces and were also screened for antiquorum sensing (QS) activity. Compounds 1, 3, and 8 showed significant antimicrobial activity against bacterial isolates, and 1, 3, 7, and 8 showed excellent anti-QS inhibition activity measured by means of bioluminescence inhibition with biosensor model systems.

  19. Vibrational spectra and DFT calculations of sonderianin diterpene

    NASA Astrophysics Data System (ADS)

    Oliveira, I. M. M.; Santos, H. S.; Sena, D. M.; Cruz, B. G.; Teixeira, A. M. R.; Freire, P. T. C.; Braz-Filho, R.; Sousa, J. W.; Albuquerque, M. R. J. R.; Bandeira, P. N.; Bernardino, A. C. S. S.; Gusmão, G. O. M.; Bento, R. R. F.

    2015-11-01

    In the present study, the natural product sonderianin diterpene (C21H26O4), a diterpenoid isolated from Croton blanchetianus, with potential application in the drug industry, was characterized by nuclear magnetic resonance, infrared and Raman spectroscopy. Vibrational spectra were supported by Density Functional Theory calculations. Infrared and Raman spectra of sonderianin were recorded at ambient temperature in the regions from 400 cm-1 to 3600 cm-1 and from 40 cm-1 to 3500 cm-1, respectively. DFT calculations with the hybrid functional B3LYP and the basis set 6-31 G(d,p) were performed with the purpose of obtaining information on the structural and vibrational properties of this organic compound. A comparison with experimental spectra allowed us to assign all of the normal modes of the crystal. The assignment of the normal modes was carried out by means of potential energy distribution.

  20. Advance on the Flavonoid C-glycosides and Health Benefits.

    PubMed

    Xiao, Jianbo; Capanoglu, Esra; Jassbi, Amir Reza; Miron, Anca

    2016-07-29

    The dietary flavonoids, especially their glycosides, are the most vital phytochemicals in diets and are of great general interest due to their diverse bioactivity. Almost all natural flavonoids exist as their O-glycoside or C-glycoside forms in plants. The dietary flavonoid C-glycosides have received less attention than their corresponding O-glycosides. This review summarizes current knowledge regarding flavonoid C-glycosides and their influence on human health. Among the flavonoid C-glycosides, flavone C-glycosides, especially vitexin, isoorientin, orientin, isovitexin and their multiglycosides are more frequently mentioned than others. Flavonoid C-monoglycosides are poorly absorbed in human beings with very few metabolites in urine and blood and are deglycosylated and degraded by human intestinal bacteria in colon. However, flavonoid C-multiglycosides are absorbed unchanged in the intestine and distributed to other tissues. Flavonoid C-glycosides showed significant antioxidant activity, anticancer and antitumor activity, hepatoprotective activity, anti-inflammatory activity, anti-diabetes activity, antiviral activity, antibacterial and antifungal activity, and other biological effects. It looks like that the C-glycosylflavonoids in most cases showed higher antioxidant and anti-diabetes potential than their corresponding O-glycosylflavonoids and aglycones. However, there is a lack of in vivo data on the biological benefits of flavonoid C-glycosides. It is necessary to investigate more on how flavonoid C-glycosides prevent and handle the diseases.

  1. A novel glycoside from Acanthus hirsutus (Acanthaceae).

    PubMed

    Capanlar, Seval; Böke, Nazli; Yaşa, Ihsan; Kirmizigül, Süheyla

    2010-04-01

    A novel glycoside, hirsutusoide (1), characterized as 2-(o-hydroxyphenyl)-2-hydroxyethenyl-O-beta-glucopyranoside, was isolated from the endemic Acanthus hirsutus Boiss. In addition to compound 1, three known glycosides, luteolin-7-O-beta-D-glucuronide (2), beta-sitosterol-3-O-beta-D-glucopyranoside (3) and (2R)-2-O-beta-D-glucopyranosyl-2H-1,4-benzoxazin-3(4H)-one (4), were also isolated. Compound 2 was the first report from this genus. Antimicrobial and antioxidant activity of the extracts and the novel compound were investigated by determining MIC (microg/mL) and IC50 (microg/mL) values, respectively.

  2. Phenolic glycosides from berries of Pimenta dioica.

    PubMed

    Kikuzaki, Hiroe; Miyajima, Yoshiko; Nakatani, Nobuji

    2008-05-01

    Four new phenolic glycosides, (2-hydroxy-3-methoxy-5-allyl)phenyl beta- d-(6-O-E-sinapoyl)glucopyranoside (1), (1' R,5' R)-5-(5-carboxymethyl-2-oxocyclopentyl)-3 Z-pentenyl beta-D-(6-O-galloyl)glucopyranoside (2), (S)-alpha-terpinyl [alpha-L-(2-O-galloyl)arabinofuranosyl]-(1-->6)-beta-D-glucopyranoside (3), and (R)-alpha-terpinyl [alpha-L-(2-O-galloyl)arabinofuranosyl]-(1-->6)-beta-D-glucopyranoside (4), were isolated from the berries of Pimenta dioica together with eight known flavonoids. The structures of 1-4 were elucidated on the basis of MS and NMR data and enzymatic hydrolysis. All four glycosides showed radical-scavenging activity against 1,1-diphenyl-2-picrylhydrazyl (DPPH) radicals.

  3. New pregnane glycosides from Gymnema sylvestre.

    PubMed

    Xu, Rui; Yang, Yu; Zhang, Yang; Ren, Fengxia; Xu, Jinlong; Yu, Nengjiang; Zhao, Yimin

    2015-02-12

    Four new pregnane glycosides 1-4 were isolated from the ethanol extract of the stem of Gymnema sylvestre and named gymsylvestrosides A-D. Hydrolysis of compound 1 under the catalysis of Aspergilus niger β-glucosidase afforded compound 5 (gymsylvestroside E). Their structures were determined by spectroscopic methods such as HRESIMS, 1D and 2D NMR, as well as HMQC-TOCSY experiment. Compounds 1-4 were screened for Saccharomyces cerevisiae α-glucosidase inhibitory activity.

  4. A new phenol glycoside from Physalis angulata.

    PubMed

    Sun, Cheng-Peng; Nie, Xiu-Fang; Kang, Ning; Zhao, Feng; Chen, Li-Xia; Qiu, Feng

    2017-05-01

    A new phenol glycoside, physanguloside A (1), was isolated from Physalis angulata together with four known compounds. We report herein, for the first time, the presence of compounds 2-5 in the genus Physalis. The structures of all the compounds were established by NMR, IR, UV and HRESIMS spectroscopic analyses, and comparison with the literature data. All isolated compounds were assayed for inhibitory activity on nitric oxide production by LPS-induced in RAW 264.7 macrophages.

  5. Triterpenoid glycosides from bark of Meliosma lanceolata.

    PubMed

    Abe, F; Yamauchi, T; Shibuya, H; Kitagawa, I

    1996-06-01

    From the bark of Meliosma lanceolate, nine triterpenoid glycosides including the 28-O-beta-D-glucopyranosyl ester of bayogenin-3-O-beta-D-glucuronopyranoside, its 4'-O-beta-D-galactopyranoside and 4'-O-alpha-L-arabinopyranoside were isolated and the structures characterized along with that of 28-O-beta-D-glucopyranosyl-bayogenin-3-O-beta-D-4'-anhydro-4', 5'-didehydroglucuronopyranoside. Bisdesmosidic triosides of hederagenin were obtained as minor components.

  6. Four Pentasaccharide Resin Glycosides from Argyreia acuta.

    PubMed

    Yu, Bang-Wei; Sun, Jing-Jing; Pan, Jie-Tao; Wu, Xiu-Hong; Yin, Yong-Qin; Yan, You-Shao; Hu, Jia-Yan

    2017-03-11

    Four pentasaccharide resin glycosides, acutacoside F-I (1-4), were isolated from the aerial parts of Argyreia acuta. These compounds were characterized as a group of macrolactones of operculinic acid A, and their lactonization site of 11S-hydroxyhexadecanoic acid was esterified at the second saccharide moiety (Rhamnose) at C-2. The absolute configuration of the aglycone was S. Their structures were elucidated by established spectroscopic and chemical methods.

  7. ent-Kaurene Glycosides from Ageratina cylindrica.

    PubMed

    Bustos-Brito, Celia; Sánchez-Castellanos, Mariano; Esquivel, Baldomero; Calderón, José S; Calzada, Fernando; Yépez-Mulia, Lilian; Joseph-Nathan, Pedro; Cuevas, Gabriel; Quijano, Leovigildo

    2015-11-25

    The aqueous extract of the leaves of Ageratina cylindrica afforded six new ent-kaurenoic acid glycosides together with the known diterpenoid paniculoside V, the flavonoid astragalin, chlorogenic acid, and L-chiro-inositol. The structures were elucidated mainly by NMR and MS methods, and the absolute configuration was established by vibrational circular dichroism spectroscopy. The new compounds showed moderate antiprotozoal activity against Entamoeba histolytica and Giardia lamblia trophozoites.

  8. A new lignan glycoside from Eleutherococcus senticosus.

    PubMed

    Li, X C; Barnes, D L; Khan, I A

    2001-11-01

    A new lignan glycoside, named eleutheroside E(2) (1), has been isolated from the roots of Eleutherococcus senticosus (known as "Siberian ginseng"), along with isomaltol 3-O-alpha-D-glucopyranoside (2), eleutherosides B, E and E(1), and thymidine. The structure of 1 was established by spectral interpretations as episyringaresinol 4"-O-beta-D-glucopyranoside. Compound 2 is described here for the first time as a naturally occurring compound.

  9. Labdane diterpenes protect against anoxia/reperfusion injury in cardiomyocytes: involvement of AKT activation

    PubMed Central

    Cuadrado, I; Fernández-Velasco, M; Boscá, L; de las Heras, B

    2011-01-01

    Several labdane diterpenes exert anti-inflammatory and cytoprotective actions; therefore, we have investigated whether these molecules protect cardiomyocytes in an anoxia/reperfusion (A/R) model, establishing the molecular mechanisms involved in the process. The cardioprotective activity of three diterpenes (T1, T2 and T3) was studied in the H9c2 cell line and in isolated rat cardiomyocyte subjected to A/R injury. In both cases, treatment with diterpenes T1 and T2 protected from A/R-induced apoptosis, as deduced by a decrease in the percentage of apoptotic and caspase-3 active positive cells, a decrease in the Bcl-2/Bax ratio and an increase in the expression of antiapoptotic proteins. Analysis of cell survival signaling pathways showed that diterpenes T1 and T2 added after A/R increased phospho-AKT and phospho-ERK 1/2 levels. These cardioprotective effects were lost when AKT activity was pharmacologically inhibited. Moreover, the labdane-induced cardioprotection involves activation of AMPK, suggesting a role for energy homeostasis in their mechanism of action. Labdane diterpenes (T1 and T2) also exerted cardioprotective effects against A/R-induced injury in isolated cardiomyocytes and the mechanisms involved activation of specific survival signals (PI3K/AKT pathways, ERK1/2 and AMPK) and inhibition of apoptosis. PMID:22071634

  10. Oleandrin: A cardiac glycosides with potent cytotoxicity

    PubMed Central

    Kumar, Arvind; De, Tanmoy; Mishra, Amrita; Mishra, Arun K.

    2013-01-01

    Cardiac glycosides are used in the treatment of congestive heart failure and arrhythmia. Current trend shows use of some cardiac glycosides in the treatment of proliferative diseases, which includes cancer. Nerium oleander L. is an important Chinese folk medicine having well proven cardio protective and cytotoxic effect. Oleandrin (a toxic cardiac glycoside of N. oleander L.) inhibits the activity of nuclear factor kappa-light-chain-enhancer of activated B chain (NF-κB) in various cultured cell lines (U937, CaOV3, human epithelial cells and T cells) as well as it induces programmed cell death in PC3 cell line culture. The mechanism of action includes improved cellular export of fibroblast growth factor-2, induction of apoptosis through Fas gene expression in tumor cells, formation of superoxide radicals that cause tumor cell injury through mitochondrial disruption, inhibition of interleukin-8 that mediates tumorigenesis and induction of tumor cell autophagy. The present review focuses the applicability of oleandrin in cancer treatment and concerned future perspective in the area. PMID:24347921

  11. Appetite suppressing pregnane glycosides from the roots of Cynanchum auriculatum.

    PubMed

    Liu, Shuangzhu; Chen, Zhenhua; Wu, Jian; Wang, Luoyi; Wang, Hongmin; Zhao, Weimin

    2013-09-01

    In the search for plant alternatives to Hoodia gordonii containing P57, a pregnane glycoside with potential appetite suppressant effect, the roots of Cynanchum auriculatum were investigated. As a result, 15 pregnane glycosides including nine never previously reported were isolated. Their structures were elucidated on the basis of extensive spectroscopic analyses and chemical methods. Appetite suppressant effect and body weight loss were observed when tested with the most abundant pregnane glycoside, wilfoside K1N, in an in vivo test with rats.

  12. New oxypregnane glycosides from appetite suppressant herbal supplement Hoodia gordonii.

    PubMed

    Pawar, Rahul S; Shukla, Yatin J; Khan, Shabana I; Avula, Bharathi; Khan, Ikhlas A

    2007-06-01

    Hoodigosides A-K (1-11), eleven new oxypregnane glycosides and a previously reported oxypregnane glycoside P57AS3 were isolated from the aerial parts of Hoodia gordonii. The structures of these 12-O-beta-tigloyl isoramanone glycosides were determined on the basis of chemical evidence and extensive spectroscopic methods that include one-dimensional and two-dimensional NMR. Cytotoxicity and antioxidant activities of these compounds were tested in cell based assays where they were found to be inactive.

  13. The Identification of Perillyl Alcohol Glycosides with Improved Antiproliferative Activity

    PubMed Central

    2015-01-01

    A facile route to perillyl alcohol (POH) differential glycosylation and the corresponding synthesis of a set of 34 POH glycosides is reported. Subsequent in vitro studies revealed a sugar dependent antiproliferative activity and the inhibition of S6 ribosomal protein phosphorylation as a putative mechanism of representative POH glycosides. The most active glycoside from this cumulative study (4′-azido-d-glucoside, PG9) represents one of the most cytotoxic POH analogues reported to date. PMID:25121720

  14. Cardiac glycosides from Yellow Oleander (Thevetia peruviana) seeds.

    PubMed

    Kohls, Sarah; Scholz-Böttcher, Barbara M; Teske, Jörg; Zark, Patrick; Rullkötter, Jürgen

    2012-03-01

    Thevetia cardiac glycosides can lead to intoxication, thus they are important indicators for forensic and pharmacologic surveys. Six thevetia cardiac glycosides, including two with unknown structures, were isolated from the seeds of the Yellow Oleander (Thevetia peruviana (Pers.) K. Shum., Apocynaceae). LC-ESI⁺-MS(/MS) analysis under high-resolution conditions used as a qualitative survey of the primary glycosides did not lead to fragmentation of the aglycones. Acid hydrolysis of the polar and non-volatile thevetia glycosides under severe conditions yielded the aglycones of the thevetia glycosides and made them amenable to GC-MS analysis. Comparison of mass spectral fragmentation patterns of the aglycones, as well as high-resolution mass spectrometric and NMR data of four of the primary thevetia glycosides including the two unknowns, revealed the structures of the complete set of six thevetia glycosides. The identified compounds are termed thevetin C and acetylthevetin C and differ by an 18,20-oxido-20,22-dihydro functionality from thevetin B and acetylthevetin B, respectively. The absence of an unsaturated lactone ring renders the glycosides cardio-inactive. The procedures developed in this study and the sets of analytical data obtained will be useful for screening and structure assessment of other, particularly polar, cardiac glycosides.

  15. Antifungal active triterpene glycosides from sea cucumber Holothuria scabra.

    PubMed

    Han, Hua; Yi, Yang-Hua; Li, Ling; Liu, Bao-Shu; La, Ming-Ping; Zhang, Hong-Wei

    2009-06-01

    To study the new antifungal active triterpene glycosides of sea cucumber Holothuria scabra. Triterpene glycosides from Holothuria scabra were separated and purified by silica gel chromatography, reversed-phase silica gel chromatography and RP-HPLC. Their structures were elucidated on the basis of spectral data and chemical evidence. Three triterpene glycosides were identified as scabraside A (1), echinoidea A (2) and holothurin A1 (3). Scabraside A (1) is a new triterpene glycoside, and compounds 2 and 3 were isolated from Holothuria scabra for the first time. They showed antifungal activities (1 < or = MIC80 < or = 16 microg mL(-1)).

  16. Characterization of Diterpenes from Euphorbia prolifera and Their Antifungal Activities against Phytopathogenic Fungi.

    PubMed

    Xu, Jing; Kang, Jing; Cao, Xiangrong; Sun, Xiaocong; Yu, Shujing; Zhang, Xiao; Sun, Hongwei; Guo, Yuanqiang

    2015-07-01

    Euphorbia prolifera is a poisonous plant belonging to the Euphorbiaceae family. In this survey on plant secondary metabolites to obtain bioactive substances for the development of new antifungal agents for agriculture, the chemical constituents of the plant E. prolifera were investigated. This procedure led to the isolation of six new and two known diterpenes. Their structures, including absolute configurations, were elucidated on the basis of extensive NMR spectroscopic data analyses and time-dependent density functional theory ECD calculations. Biological screenings revealed that these diterpenes possessed antifungal activities against three phytopathogenic fungi. The results of the phytochemical investigation further revealed the chemical components of the poisonous plant E. prolifera, and biological screenings implied the extract or bioactive diterpenes from this plant may be regarded as candidate agents of antifungal agrochemicals for crop protection products.

  17. Additional diterpenes from Physcomitrella patens synthesized by copalyl diphosphate/kaurene synthase (PpCPS/KS).

    PubMed

    Zhan, Xin; Bach, Søren Spanner; Hansen, Nikolaj Lervad; Lunde, Christina; Simonsen, Henrik Toft

    2015-11-01

    The bifunctional diterpene synthase, copalyl diphosphate/kaurene synthase from the moss Physcomitrella patens (PpCPS/KS), catalyses the formation of at least four diterpenes, including ent-beyerene, ent-sandaracopimaradiene, ent-kaur-16-ene, and 16-hydroxy-ent-kaurene. The enzymatic activity has been confirmed through generation of a targeted PpCPS/KS knock-out mutant in P. patens via homologous recombination, through transient expression of PpCPS/KS in Nicotiana benthamiana, and expression of PpCPS/KS in E. coli. GC-MS analysis of the knock-out mutant shows that it lacks the diterpenoids, supporting that all are products of PpCPS/KS as observed in N. benthamiana and E. coli. These results provide additional knowledge of the mechanism of this bifunctional diterpene synthase, and are in line with proposed reaction mechanisms in kaurene biosynthesis.

  18. Effects of kaurane diterpene derivatives on germination and growth of Lactuca sativa seedlings.

    PubMed

    Vieira, Henriete S; Takahashi, Jacqueline A; Pimenta, Lúcia P S; Boaventura, Maria Amélia D

    2005-01-01

    Kaurenoic and grandiflorenic acid, isolated from Wedelia paludosa (Asteraceae), some derivatives from these acids (alcohols, esters, amides, lactones, oximes) and other naturally occurring kaurane diterpenes were tested for their action on the growth of radical and shoot of Lactuca sativa. Gibberellic acid, GA3, a commercially available phytohormone, belonging to the same class of diterpenes, was also tested. Some of the tested substances showed a remarkable activity either in the inhibition or in stimulation of L. sativa growth. The activity, in some cases, was even higher than that of GA3.

  19. [Effects of ginkgo diterpene lactones meglumine injection's activated carbon adsorption technology on officinal components].

    PubMed

    Zhou, En-li; Wang, Ren-jie; Li, Miao; Wang, Wei; Xu, Dian-hong; Hu, Yang; Wang, Zhen-zhong; Bi, Yu-an; Xiao, Wei

    2015-10-01

    With the diversion rate of ginkgolide A, B, K as comprehensive evaluation indexes, the amount of activated carbon, ad- sorption time, mix rate, and adsorption temperature were selected as factors, orthogonal design which based on the evaluation method of information entropy was used to optimize activated carbon adsorption technology of ginkgo diterpene lactones meglumine injection. Opti- mized adsorption conditions were as follows: adsorbed 30 min with 0.2% activated carbon in 25 °C, 40 r ·min⁻¹, validation test re- sult display. The optimum extraction condition was stable and feasible, it will provide a basis for ginkgo diterpene lactone meglumine injection' activated carbon adsorption process.

  20. Potential anti-allergic ent-kaurene diterpenes from the bark of Suregada multiflora.

    PubMed

    Cheenpracha, Sarot; Yodsaoue, Orapun; Karalai, Chatchanok; Ponglimanont, Chanita; Subhadhirasakul, Sanan; Tewtrakul, Supinya; Kanjana-opas, Akkharawit

    2006-12-01

    Two ent-kaurene diterpenes, ent-16-kaurene-3beta,15beta,18-triol (1) and ent-3-oxo-16-kaurene-15beta,18-diol (2), were isolated from a dichloromethane extract of the bark of Suregada multiflora along with five known diterpenes:ent-16-kaurene-3beta,15beta-diol (3), abbeokutone (4), helioscopinolide A (5), helioscopinolide C (6) and helioscopinolide I (7). Their structures were elucidated on the basis of spectroscopic analysis. Compounds 1-7 possessed appreciable anti-allergic activities in RBL-2H3 cells model with IC50 values ranging from 22.5 to 42.2 microM.

  1. Pseudoirroratin A, a new cytotoxic ent-kaurene diterpene from Isodon pseudo-irrorata.

    PubMed

    Zhang, Hongjie; Fan, Zhuting; Tan, Ghee T; Chai, Hee-Byung; Pezzuto, John M; Sun, Handong; Fong, Harry H S

    2002-02-01

    A new ent-kaurene diterpene, pseudoirroratin A (1), and a known diterpene, pseurata A, were isolated from Isodon pseudo-irrorata. Compound 1 showed significant cytotoxicity against the Lu1, SW626, LNCaP, KB, and HOS cancer cell lines with IC(50) values of 0.26 (0.75), 0.20 (0.57), 0.90 (2.59), 0.90 (2.59), and 0.50 (1.44) microg/mL (microM), respectively. The structure of 1 was elucidated by spectroscopic means including 1D and 2D NMR techniques.

  2. Triterpene glycosides from the deep-water North-Pacific sea cucumber Synallactes nozawai Mitsukuri.

    PubMed

    Silchenko, Alexandra S; Avilov, Sergey A; Antonov, Alexandr A; Kalinin, Vladimir I; Kalinovsky, Anatoly I; Smirnov, Alexey V; Riguera, Ricardo; Jiménez, Carlos

    2002-12-01

    Five non-sulfated triterpene glycosides, synallactosides A(1) (1), A(2) (2), B(1) (3), B(2) (4), and C (5), have been isolated from the sea cucumber Synallactes nozawai. Their structures have been deduced by extensive analysis of NMR and mass spectra. The glycosides 2-5 are new glycosides. Glycosides 2-4 have carbohydrate chains without precedent in the glycosides from sea cucumbers. This is the first time glycosides are found in members of the family Synallactidae.

  3. Phenylethanoid glycosides and phenolic glycosides from stem bark of Magnolia officinalis.

    PubMed

    Xue, Zhenzhen; Yan, Renyi; Yang, Bin

    2016-07-01

    An investigation of the hydrophilic constituents of the stem bark of Magnolia officinalis was performed and which led to isolation and identification of twenty-one previously unreported glycosides. These included eleven phenylethanoid glycosides, magnolosides F-P, and ten phenolic glycosides, magnolosides Q-Z, along with eight known compounds. Their structures were elucidated on the basis of extensive spectroscopic analyses and chemical hydrolysis methods, as well as by comparison with literature data. Most of the phenylethanoid glycosides contained an allopyranose moiety, which is rare in the plant kingdom. Magnolosides I and K as well as 2-(3,4-dihydroxyphenyl) ethanol 1-O-[4-O-caffeoyl-2-O-α-l-rhamnopyranosyl-3-O-α-l-rhamnopyranosyl-6-O-β-d-glucopyranosyl]-β-d-glucopyranoside showed more potent α-glucosidase inhibitory effects (IC50 values of 0.13, 0.27, and 0.29mM, respectively) than the positive control, acarbose (IC50 value of 1.09mM) in vitro. Magnolosides H, E and D also showed moderate cytotoxicity against MGC-803 and HepG2 cells with IC50 values of 13.59-17.16μM and 29.53-32.46μM, respectively.

  4. A new iridoid glycoside from Scrophularia ningpoensis.

    PubMed

    Niu, Zheng-Rui; Wang, Ru-Feng; Shang, Ming-Ying; Cai, Shao-Qing

    2009-01-01

    A new iridoid glycoside, named 6'-O-cinnamoylharpagide (1), has been isolated from the roots of Scrophularia ningpoensis (Scrophulariaceae) together with nine known compounds, harpagide (2), harpagoside (3), 8-O-feruloylharpagide (4), 8-O-(p-coumaroyl)harpagide (5), 6-O-methylcatalpol (6), aucubin (7), buergerinin B (8), teuhircoside (9) and 6-O-cinnamoyl-D-glucopyranose (10). Compound 10 was obtained as an inseparable mixture of 6-O-cinnamoyl-alpha-D-glucopyranose and 6-O-cinnamoyl-beta-D-glucopyranose at a ratio of 1 : 1, which is presumably formed by cleavage of compound 1. Their structures were elucidated on the basis of chemical and spectral analysis.

  5. Acylated flavonol glycoside from Platanus orientalis.

    PubMed

    Tantry, Mudasir A; Akbar, Seema; Dar, Javid A; Irtiza, Syed; Galal, Ahmed; Khuroo, Mohammad A; Ghazanfar, Khalid

    2012-03-01

    The ethylacetate and n-butanol fractions of ethanolic extract of Platanus orientalis leaves led to the isolation of new acylated flavonol glycoside as 3',5,7-trihydroxy-4'-methoxyflavonol 3-[O-2-O-(2,4-Dihydroxy)-E-cinnamoyl-α-L-rhamnopyranosyl-(1→6)-β-D-glucopyranosyl (1→2)]-β-D-glucopyranoside, along with seven known compounds. All the compounds were characterized by NMR including 2D NMR techniques. The isolates were evaluated for NF-κB, nitric oxide (NO), aromatase and QR2 chemoprevention activities and some of them appeared to be modestly active.

  6. Three new triterpene glycosides from Ilex asprella.

    PubMed

    Zhang, Zhen-Xia; Fu, Qiang; Zheng, Ken Yu-Zhong

    2013-01-01

    Three new sulfated triterpene glycosides, asprellanosides C-E (1-3), were isolated from the roots of Ilex asprella. Their structures were elucidated as 3β-[(2-O-sulfo-β-d-xylopyranosyl)oxy]urs-12,19(29)-diene-28-oic acid 28-β-d-glucopyranoside (1), 3β-[(2-O-sulfo-β-d-xylopyranosyl)oxy]urs-12,19-diene-28-oic acid 28-β-d-glucopyranoside (2), and 3β-[(2-O-sulfo-β-d-xylopyranosyl)oxy]urs-12,19-diene-28-oic acid (3) on the basis of the spectral and chemical methods.

  7. In vitro metabolism of the glycosidic sweeteners, stevia mixture and enzymatically modified stevia in human intestinal microflora.

    PubMed

    Koyama, E; Kitazawa, K; Ohori, Y; Izawa, O; Kakegawa, K; Fujino, A; Ui, M

    2003-03-01

    Stevia mixture, sweeteners extracted from the leaves of Stevia rebaudiana Bertoni, consists mainly of stevioside and rebaudioside A (glycosides of the diterpene derivative steviol). The aim of this study was to investigate human intestinal metabolism of stevia mixture and its alpha-glucose derivative (known in Japan as enzymatically modified stevia) by LC/MS/ESI analysis. Degradation was examined by incubating stevia mixture, enzymatically modified stevia, stevioside, rebaudioside A, alpha-monoglucosylstevioside, alpha-monoglucosylrebaudioside A and the aglycone, steviol with pooled human faecal homogenates (obtained from five healthy volunteers) for 0, 8 and 24 h under anaerobic conditions. Stevia mixture, enzymatically modified stevia, stevioside and rebaudioside A (0.2 mg/ml) were completely eliminated within 24 h, whereas no degradation of steviol (0.08 and 0.2 mg/ml) appeared to be found during the incubation period. Stevia mixture, stevioside and rebaudioside A appeared to be hydrolyzed to steviol by human intestinal microflora: this observation is consistent with previous rat metabolism studies. Similarly, enzymatically modified stevia appeared to be metabolized via stevia components and, finally, to steviol. This study suggests that there are apparently no species differences in intestinal metabolism of stevia mixture between rats and humans.

  8. Enzymatic hydrolysis of steryl ferulates and steryl glycosides

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Steryl ferulates and steryl glycosides are phytosterol conjugates found characteristically in cereals. Their properties in enzymatic hydrolysis are, however, not yet well known. Steryl ferulates and steryl glycosides were extracted and purified from rye and wheat bran. Their rates of hydrolysis with...

  9. Phytosteryl glycosides reduce cholesterol absorption: mechanisms in mice

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Phytosteryl glycosides occur in natural foods but little is known about their metabolism and bioactivity. Purified acylated steryl glycosides (ASG) were compared with phytosteryl esters (PSE) in mice. Animals on a phytosterol-free diet received ASG or PSE by gavage in purified soybean oil along with...

  10. Evaluating the Cancer Therapeutic Potential of Cardiac Glycosides

    PubMed Central

    Calderón-Montaño, José Manuel; Burgos-Morón, Estefanía; Orta, Manuel Luis; Maldonado-Navas, Dolores; García-Domínguez, Irene; López-Lázaro, Miguel

    2014-01-01

    Cardiac glycosides, also known as cardiotonic steroids, are a group of natural products that share a steroid-like structure with an unsaturated lactone ring and the ability to induce cardiotonic effects mediated by a selective inhibition of the Na+/K+-ATPase. Cardiac glycosides have been used for many years in the treatment of cardiac congestion and some types of cardiac arrhythmias. Recent data suggest that cardiac glycosides may also be useful in the treatment of cancer. These compounds typically inhibit cancer cell proliferation at nanomolar concentrations, and recent high-throughput screenings of drug libraries have therefore identified cardiac glycosides as potent inhibitors of cancer cell growth. Cardiac glycosides can also block tumor growth in rodent models, which further supports the idea that they have potential for cancer therapy. Evidence also suggests, however, that cardiac glycosides may not inhibit cancer cell proliferation selectively and the potent inhibition of tumor growth induced by cardiac glycosides in mice xenografted with human cancer cells is probably an experimental artifact caused by their ability to selectively kill human cells versus rodent cells. This paper reviews such evidence and discusses experimental approaches that could be used to reveal the cancer therapeutic potential of cardiac glycosides in preclinical studies. PMID:24895612

  11. Enzymatic (13)C labeling and multidimensional NMR analysis of miltiradiene synthesized by bifunctional diterpene cyclase in Selaginella moellendorffii.

    PubMed

    Sugai, Yoshinori; Ueno, Yohei; Hayashi, Ken-ichiro; Oogami, Shingo; Toyomasu, Tomonobu; Matsumoto, Sadamu; Natsume, Masahiro; Nozaki, Hiroshi; Kawaide, Hiroshi

    2011-12-16

    Diterpenes show diverse chemical structures and various physiological roles. The diversity of diterpene is primarily established by diterpene cyclases that catalyze a cyclization reaction to form the carbon skeleton of cyclic diterpene. Diterpene cyclases are divided into two types, monofunctional and bifunctional cyclases. Bifunctional diterpene cyclases (BDTCs) are involved in hormone and defense compound biosyntheses in bryophytes and gymnosperms, respectively. The BDTCs catalyze the successive two-step type-B (protonation-initiated cyclization) and type-A (ionization-initiated cyclization) reactions of geranylgeranyl diphosphate (GGDP). We found that the genome of a lycophyte, Selaginella moellendorffii, contains six BDTC genes with the majority being uncharacterized. The cDNA from S. moellendorffii encoding a BDTC-like enzyme, miltiradiene synthase (SmMDS), was cloned. The recombinant SmMDS converted GGDP to a diterpene hydrocarbon product with a molecular mass of 272 Da. Mutation in the type-B active motif of SmMDS abolished the cyclase activity, whereas (+)-copalyl diphosphate, the reaction intermediate from the conversion of GGDP to the hydrocarbon product, rescued the cyclase activity of the mutant to form a diterpene hydrocarbon. Another mutant lacking type-A activity accumulated copalyl diphosphate as the reaction intermediate. When the diterpene hydrocarbon was enzymatically synthesized from [U-(13)C(6)]mevalonate, all carbons were labeled with (13)C stable isotope (>99%). The fully (13)C-labeled product was subjected to (13)C-(13)C COSY NMR spectroscopic analyses. The direct carbon-carbon connectivities observed in the multidimensional NMR spectra demonstrated that the hydrocarbon product by SmMDS is miltiradiene, a putative biosynthetic precursor of tanshinone identified from the Chinese medicinal herb Salvia miltiorrhiza. Hence, SmMDS functions as a bifunctional miltiradiene synthase in S. moellendorffii. In this study, we demonstrate that one

  12. Hydrolysis of soybean isoflavonoid glycosides by Dalbergia beta-glucosidases.

    PubMed

    Chuankhayan, Phimonphan; Rimlumduan, Thipwarin; Svasti, Jisnuson; Cairns, James R Ketudat

    2007-03-21

    Two beta-glucosidases from the legumes Dalbergia cochinchinensis and Dalbergia nigrescens were compared for their ability to hydrolyze isoflavonoid glycosides from soybean. Both D. nigrescens and D. cochinchinensis beta-glucosidases could hydrolyze conjugated soybean glycosides, but D. nigrescens beta-glucosidase hydrolyzed both conjugated and nonconjugated glycosides in crude soybean extract more rapidly. The kinetic properties Km, kcat, and kcat/Km of the Dalbergia beta-glucosidases toward conjugated isoflavonoid glycosides, determined using high-performance liquid chromatography, confirmed the higher efficiency of the D. nigrescens beta-glucosidase in hydrolyzing these substrates. The D. nigrescens beta-glucosidase could also efficiently hydrolyze isoflavone glycosides in soy flour suspensions, suggesting its application to increase free isoflavones in soy products.

  13. The first structure of a bacterial diterpene cyclase: CotB2.

    PubMed

    Janke, Ronja; Görner, Christian; Hirte, Max; Brück, Thomas; Loll, Bernhard

    2014-06-01

    Sesquiterpenes and diterpenes are a diverse class of secondary metabolites that are predominantly derived from plants and some prokaryotes. The properties of these natural products encompass antitumor, antibiotic and even insecticidal activities. Therefore, they are interesting commercial targets for the chemical and pharmaceutical industries. Owing to their structural complexity, these compounds are more efficiently accessed by metabolic engineering of microbial systems than by chemical synthesis. This work presents the first crystal structure of a bacterial diterpene cyclase, CotB2 from the soil bacterium Streptomyces melanosporofaciens, at 1.64 Å resolution. CotB2 is a diterpene cyclase that catalyzes the cyclization of the linear geranylgeranyl diphosphate to the tricyclic cyclooctat-9-en-7-ol. The subsequent oxidation of cyclooctat-9-en-7-ol by two cytochrome P450 monooxygenases leads to bioactive cyclooctatin. Plasticity residues that decorate the active site of CotB2 have been mutated, resulting in alternative monocyclic, dicyclic and tricyclic compounds that show bioactivity. These new compounds shed new light on diterpene cyclase reaction mechanisms. Furthermore, the product of mutant CotB2(W288G) produced the new antibiotic compound (1R,3E,7E,11S,12S)-3,7,18-dolabellatriene, which acts specifically against multidrug-resistant Staphylococcus aureus. This opens a sustainable route for the industrial-scale production of this bioactive compound.

  14. A study of the diterpene alkaloids of Aconitum napellus ssp. neomontanum during its onthogenetic cycle.

    PubMed

    Colombo, M L; Bravin, M; Tome, F

    1988-12-01

    Qualitative and quantitative variations in the diterpene alkaloids content in the neomontanum subspecies of Aconitum napellus, growing near lake of Como, were studied throughout its complete onthogenetic cycle. Aconitine, N-deethylaconitine and two compounds with m.w. = 688 and m.w. = 629 have been detected in the various organs of plant almost at any time during the vegetative cycle.

  15. Dolabelladienols A-C, new diterpenes isolated from Brazilian brown alga Dictyota pfaffii.

    PubMed

    Pardo-Vargas, Alonso; de Barcelos Oliveira, Ingrid; Stephens, Paulo Roberto Soares; Cirne-Santos, Claudio Cesar; de Palmer Paixão, Izabel Christina Nunes; Ramos, Freddy Alejandro; Jiménez, Carlos; Rodríguez, Jaime; Resende, Jackson Antonio Lamounier Camargos; Teixeira, Valeria Laneuville; Castellanos, Leonardo

    2014-07-23

    The marine brown alga Dictyota pfaffii from Atol das Rocas, in Northeast Brazil is a rich source of dolabellane diterpene, which has the potential to be used in future antiviral drugs by inhibiting reverse transcriptase (RT) of HIV-1. Reexamination of the minor diterpene constituents yielded three new dolabellane diterpenes, (1R*,2E,4R*,7S,10S*,11S*,12R*)10,18-diacetoxy-7-hydroxy-2,8(17)-dolabelladiene (1), (1R*,2E,4R*,7R*,10S*,11S*,12R*)10,18-diacetoxy-7-hydroxy-2,8(17)-dolabelladiene (2), (1R*,2E,4R*,8E,10S*,11S,12R*)10,18-diacetoxy-7-hydroxy-2,8-dolabelladiene (3), termed dolabelladienols A-C (1-3) respectively, in addition to the known dolabellane diterpenes (4-6). The elucidation of the compounds 1-3 was assigned by 1D and 2D NMR, MS, optical rotation and molecular modeling, along with the relative configuration of compound 4 and the absolute configuration of 5 by X-ray diffraction. The potent anti-HIV-1 activities displayed by compounds 1 and 2 (IC50 = 2.9 and 4.1 μM), which were more active than even the known dolabelladienetriol 4, and the low cytotoxic activity against MT-2 lymphocyte tumor cells indicated that these compounds are promising anti-HIV-1 agents.

  16. Synthesis of an Advanced Intermediate of the Jatrophane Diterpene Pl-4: A Dibromide Coupling Approach

    PubMed Central

    2013-01-01

    The preparation of an advanced intermediate toward the synthesis of the jatrophane diterpene Pl-4 is described. The key step is a regioselective chelation-controlled lithiation of the (Z)-configured bromide in the corresponding vinyl dibromide precursor. The method outlined within this Article is suitable for the facile access of sterically hindered internal vinyl halides for further coupling reactions. PMID:23895274

  17. Nepetanal and nepetanoate: a new diterpene aldehyde and a benzene derivative ester from Nepeta juncea.

    PubMed

    Hussain, Javid; Jamila, Nargis; Khan, Farman Ullah; Devkota, Krishna Prasad; Shah, M Raza; Anwar, Saeed

    2009-07-01

    One new tricyclic clerodane type diterpene aldehyde nepetanal (1) and one new benzene derivative nepetanoate (2) have been isolated from a plant Nepeta juncea together with two known compounds oleanolic acid (3) and ursolic acid (4). The structures of the isolated compounds were elucidated by means of modern spectroscopic techniques and comparison with literature data.

  18. Dolabelladienols A–C, New Diterpenes Isolated from Brazilian Brown Alga Dictyota pfaffii

    PubMed Central

    Pardo-Vargas, Alonso; Oliveira, Ingrid de Barcelos; Stephens, Paulo Roberto Soares; Cirne-Santos, Claudio Cesar; Paixão, Izabel Christina Nunes de Palmer; Ramos, Freddy Alejandro; Jiménez, Carlos; Rodríguez, Jaime; Resende, Jackson Antonio Lamounier Camargos; Teixeira, Valeria Laneuville; Castellanos, Leonardo

    2014-01-01

    The marine brown alga Dictyota pfaffii from Atol das Rocas, in Northeast Brazil is a rich source of dolabellane diterpene, which has the potential to be used in future antiviral drugs by inhibiting reverse transcriptase (RT) of HIV-1. Reexamination of the minor diterpene constituents yielded three new dolabellane diterpenes, (1R*,2E,4R*,7S,10S*,11S*,12R*)10,18-diacetoxy-7-hydroxy-2,8(17)-dolabelladiene (1), (1R*,2E,4R*,7R*,10S*,11S*,12R*)10,18-diacetoxy-7-hydroxy-2,8(17)-dolabelladiene (2), (1R*,2E,4R*,8E,10S*,11S,12R*)10,18-diacetoxy-7-hydroxy-2,8-dolabelladiene (3), termed dolabelladienols A–C (1–3) respectively, in addition to the known dolabellane diterpenes (4–6). The elucidation of the compounds 1–3 was assigned by 1D and 2D NMR, MS, optical rotation and molecular modeling, along with the relative configuration of compound 4 and the absolute configuration of 5 by X-ray diffraction. The potent anti-HIV-1 activities displayed by compounds 1 and 2 (IC50 = 2.9 and 4.1 μM), which were more active than even the known dolabelladienetriol 4, and the low cytotoxic activity against MT-2 lymphocyte tumor cells indicated that these compounds are promising anti-HIV-1 agents. PMID:25056631

  19. The effect of the diterpene 5-epi-icetexone on the cell cycle of Trypanosoma cruzi.

    PubMed

    Lozano, Esteban; Barrera, Patricia; Tonn, Carlos; Nieto, Matías; Sartor, Tirso; Sosa, Miguel A

    2012-06-01

    Numerous natural compounds have been used against Trypanosoma cruzi, the causative agent of Chagas' disease. Here, we studied the effect of the diterpene 5-epi-icetexone on growth and morphology of parasites synchronized with hydroxyurea, at different periods of time after removal of the nucleotide. We observed that the diterpene does not affect the growth of the parasites when added within 10 h after removal of hydroxyurea, but the compound was effective on growth when added to the cultures after 12 h. Thymidine incorporation was somewhat inhibited when the diterpene was added at 12 h after removal of hydroxyurea, possibly on the transition S/G2. Using transmission electron microscopy we observed that the diterpene induced a delay in the progression of cell division. We conclude that the compound, at cytostatic dose, affects the cell cycle of T. cruzi, possibly in the transition S/G2 phase and cell division. Further studies will focus to identify the molecular targets for the action of 5-epi-icetexone.

  20. Diterpenes from rosemary (Rosmarinus officinalis): Defining their potential for anti-cancer activity.

    PubMed

    Petiwala, Sakina M; Johnson, Jeremy J

    2015-10-28

    Recently, rosemary extracts standardized to diterpenes (e.g. carnosic acid and carnosol) have been approved by the European Union (EU) and given a GRAS (Generally Recognized as Safe) status in the United States by the Food and Drug Administration (FDA). Incorporation of rosemary into our food system and through dietary selection (e.g. Mediterranean Diet) has increased the likelihood of exposure to diterpenes in rosemary. In consideration of this, a more thorough understanding of rosemary diterpenes is needed to understand its potential for a positive impact on human health. Three agents in particular have received the most attention that includes carnosic acid, carnosol, and rosmanol with promising results of anti-cancer activity. These studies have provided evidence of diterpenes to modulate deregulated signaling pathways in different solid and blood cancers. Rosemary extracts and the phytochemicals therein appear to be well tolerated in different animal models as evidenced by the extensive studies performed for approval by the EU and the FDA as an antioxidant food preservative. This mini-review reports on the pre-clinical studies performed with carnosic acid, carnosol, and rosmanol describing their mechanism of action in different cancers.

  1. Crispene A, B, C and D, Four New Clerodane Type Furanoid Diterpenes from Tinospora crispa (L.)

    PubMed Central

    Hossen, Farhad; Ahasan, Rubaida; Haque, Mohammad Rashedul; Begum, Bilkis; Hasan, Choudhury Mahmood

    2016-01-01

    Background: Tinospora crispa (L.) is used to alleviate the symptoms of diabetes mellitus in folk medicine. It is also used for hypertension and to treat malaria, remedy for diarrhea, and as vermifuge. Materials and Methods: Stems of T. crispa were collected, sun dried for several days followed by oven dried for 24 h at a considerably low temperature and then ground into coarse powder. The powdered stems were soaked in methanol at room temperature for 14 days with occasional shaking. The extract was collected by filtration, and the solvent was evaporated under reduced pressure in a rotary evaporator to obtain a solid residue which was then subjected to fractionation using the modified Kupchan partitioning method into n-hexane, CCl4, CHCl3 and aqueous soluble fractions. The n-hexane soluble fraction was chromatographed over sephadex (LH-20) and the column was eluted with n-hexane: CH2Cl2:MeOH (2:5:1) followed by CH2Cl2:MeOH (9:1) and MeOH (100%) in order to increase the polarities. The column fractions were then concentrated and subjected to thin layer chromatography screening and the fractions with a satisfactory resolution of compounds were rechromatographed over silica gel to isolate the pure compounds. Results: Four new furanoid diterpenes of clerodane types, Crispene A, B, C, and D (1–4), including one known furanoid diterpene glucoside, borapetoside E (5), were isolated from the stems of T. crispa. The structures of these compounds were elucidated by means of extensive spectroscopic analysis and by comparison of their spectral data with closely related compounds. Conclusion: We have reported four new furanoid diterpenes of clerodane types, including one known furanoid diterpene glucoside. This is the first report of any clerodane diterpene having olefinic bond between C-6 and C-7. SUMMARY Crispene A, B, C, and D, four new furanoid diterpenes of clerodane types from Tinospora crispaCrispene C, an unusual furanoid diterpene with olifinic bond between C-6 and C

  2. Effects of tripterygium glycosides on restenosis following endovascular treatment

    PubMed Central

    HAN, BING; GE, CHANG-QING; ZHANG, HONG-GUANG; ZHOU, CHEN-GUANG; JI, GUO-HUI; YANG, ZHENG; ZHANG, LIANG

    2016-01-01

    The mechanism and associated factors of restenosis following intravascular stent implantation remain to be elucidated. The present two-part experimental and clinical study aimed to investigate the effects of tripterygium glycosides on in-stent restenosis subsequent to intra-arterial therapy. Following endovascular stent implantation in rabbit iliac arteries, post-stent outcomes were evaluated in cyclosporine groups, low-dose and high-dose tripterygium glycosides groups and controls. Post-operative angiography indicated that vessel diameters were similar between groups; however, at 28 days after receiving the therapeutic agents, vessels of the cyclosporine and tripterygium glycosides groups were significantly larger than those of the controls. Furthermore, three groups of patients had comparable baseline levels of interleukin (IL)-10, IL-18 and C-reactive protein, and intima-media thickness. However, 1 month after stent implantation, levels of IL-10 and IL-18 were markedly reduced in the high- and low-dose tripterygium glycosides groups compared with controls. At 6 months after surgery, the stent patency rate in patients with bare stents was significantly lower than in patients receiving tripterygium glycosides (P≤0.009). In addition, the ankle-brachial index was also higher than in those without tripterygium glycosides (P<0.001). Results of the experimental and clinical studies suggest that tripterygium glycosides may inhibit and possibly aid in the prevention of in-stent restenosis formation following endovascular treatment of lower-extremity artery disease. PMID:27108914

  3. Steviol glycoside safety: are highly purified steviol glycoside sweeteners food allergens?

    PubMed

    Urban, Jonathan D; Carakostas, Michael C; Taylor, Steve L

    2015-01-01

    Steviol glycoside sweeteners are extracted from the plant Stevia rebaudiana (Bertoni), a member of the Asteraceae (Compositae) family. Many plants from this family can induce hypersensitivity reactions via multiple routes of exposure (e.g., ragweed, goldenrod, chrysanthemum, echinacea, chamomile, lettuce, sunflower and chicory). Based on this common taxonomy, some popular media reports and resources have issued food warnings alleging the potential for stevia allergy. To determine if such allergy warnings are warranted on stevia-based sweeteners, a comprehensive literature search was conducted to identify all available data related to allergic responses following the consumption of stevia extracts or highly purified steviol glycosides. Hypersensitivity reactions to stevia in any form are rare. The few cases documented in the peer-reviewed literature were reported prior to the introduction of high-purity products to the market in 2008 when many global regulatory authorities began to affirm the safety of steviol glycosides. Neither stevia manufacturers nor food allergy networks have reported significant numbers of any adverse events related to ingestion of stevia-based sweeteners, and there have been no reports of stevia-related allergy in the literature since 2008. Therefore, there is little substantiated scientific evidence to support warning statements to consumers about allergy to highly purified stevia extracts.

  4. Glycoside Hydrolases across Environmental Microbial Communities

    PubMed Central

    Berlemont, Renaud

    2016-01-01

    Across many environments microbial glycoside hydrolases support the enzymatic processing of carbohydrates, a critical function in many ecosystems. Little is known about how the microbial composition of a community and the potential for carbohydrate processing relate to each other. Here, using 1,934 metagenomic datasets, we linked changes in community composition to variation of potential for carbohydrate processing across environments. We were able to show that each ecosystem-type displays a specific potential for carbohydrate utilization. Most of this potential was associated with just 77 bacterial genera. The GH content in bacterial genera is best described by their taxonomic affiliation. Across metagenomes, fluctuations of the microbial community structure and GH potential for carbohydrate utilization were correlated. Our analysis reveals that both deterministic and stochastic processes contribute to the assembly of complex microbial communities. PMID:27992426

  5. Cardiac glycosides and pregnanes from Adenium obesum (studies on the constituents of Adenium. I).

    PubMed

    Yamauchi, T; Abe, F

    1990-03-01

    Cardiac glycosides and pregnanes from the roots and the stems of Adenium obesum Roem. et Schult. were investigated. Among 30 cardiac glycosides including 15 known glycosides and 15 new combinations of the known aglycones and sugars, the structures of 11 glycosides were elucidated. Oleandrigenin beta-gentiobiosyl-beta-D-thevetoside was the main glycoside. Neridienone A and 16,17-dihydroneridienone A, common pregnanes in Apocynaceae, were also isolated.

  6. New benzophenone and quercetin galloyl glycosides from Psidium guajava L.

    PubMed Central

    Matsuzaki, Keiichi; Ishii, Rie; Kobiyama, Kaori

    2010-01-01

    New benzophenone and flavonol galloyl glycosides were isolated from an 80% MeOH extract of Psidium guajava L. (Myrtaceae) together with five known quercetin glycosides. The structures of the novel glycosides were elucidated to be 2,4,6-trihydroxybenzophenone 4-O-(6″-O-galloyl)-β-d-glucopyranoside (1, guavinoside A), 2,4,6-trihydroxy-3,5-dimethylbenzophenone 4-O-(6″-O-galloyl)-β-d-glucopyranoside (2, guavinoside B), and quercetin 3-O-(5″-O-galloyl)-α-l-arabinofuranoside (3, guavinoside C) by NMR, MS, UV, and IR spectroscopies. Isolated phenolic glycosides showed significant inhibitory activities against histamine release from rat peritoneal mast cells, and nitric oxide production from a murine macrophage-like cell line, RAW 264.7. PMID:20354804

  7. Chrysophanol glycosides from callus cultures of monocotyledonous Kniphofia spp. (Asphodelaceae).

    PubMed

    Ito, Hideyuki; Nishida, Yasuko; Yamazaki, Mie; Nakahara, Keisuke; Michalska-Hartwich, Malgorzata; Furmanowa, Miroslawa; Leistner, Eckhard; Yoshida, Takashi

    2004-10-01

    We established callus cultures of the monocotyledonous plants Kniphofia foliosa and K. tuckii (Asphodelaceae), which produce the anthraquinone derivatives chrysophanol and its glycosides. The minor product chrysophanol 8-O-beta-gentiobioside was fully characterized by spectroscopic analysis and synthesis.

  8. Differential effects of quercetin glycosides on GABAC receptor channel activity.

    PubMed

    Kim, Hyeon-Joong; Lee, Byung-Hwan; Choi, Sun-Hye; Jung, Seok-Won; Kim, Hyun-Sook; Lee, Joon-Hee; Hwang, Sung-Hee; Pyo, Mi-Kyung; Kim, Hyoung-Chun; Nah, Seung-Yeol

    2015-01-01

    Quercetin, a representative flavonoid, is a compound of low molecular weight found in various colored plants and vegetables. Quercetin shows a wide range of neuropharmacological activities. In fact, quercetin naturally exists as monomer-(quercetin-3-O-rhamnoside) (Rham1), dimer-(Rutin), or trimer-glycosides [quercetin-3-(2(G)-rhamnosylrutinoside)] (Rham2) at carbon-3 in fruits and vegetables. The carbohydrate components are removed after ingestion into gastrointestinal systems. The role of the glycosides attached to quercetin in the regulation of γ-aminobutyric acid class C (GABAC) receptor channel activity has not been determined. In the present study, we examined the effects of quercetin glycosides on GABAC receptor channel activity by expressing human GABAC alone in Xenopus oocytes using a two-electrode voltage clamp technique and also compared the effects of quercetin glycosides with quercetin. We found that GABA-induced inward current (I GABA ) was inhibited by quercetin or quercetin glycosides. The inhibitory effects of quercetin and its glycosides on I GABA were concentration-dependent and reversible in the order of Rutin ≈ quercetin ≈ Rham 1 > Rham 2. The inhibitory effects of quercetin and its glycosides on I GABA were noncompetitive and membrane voltage-insensitive. These results indicate that quercetin and its glycosides regulate GABAC receptor channel activity through interaction with a different site from that of GABA, and that the number of carbohydrate attached to quercetin might play an important role in the regulation of GABAC receptor channel activity.

  9. Three new sulphur glycosides from the seeds of Descurainia sophia.

    PubMed

    Feng, Wei-Sheng; Li, Chun-Ge; Zheng, Xiao-Ke; Li, Ling-Ling; Chen, Wen-Jing; Zhang, Yan-Li; Cao, Yan-Gang; Gong, Jian-Hong; Kuang, Hai-Xue

    2016-08-01

    Three new sulphur glycosides, raphanuside B-D (1-3), together with a known sulphur glycoside, raphanuside (4) were isolated from the decoction of the seeds of Descurainia sophia (L.) Webb ex Prantl, and the compound 4 was reported for the first time from this plant. Their structures were identified by means of UV, IR, 1D, 2D NMR (HSQC, HMBC and NOESY) and HR-ESI-MS spectroscopic data.

  10. Steroidal saponins and pregnane glycosides from Smilax microphylla.

    PubMed

    Lin, Tao; Huang, Hui-Lian; Liu, Rong-Hua; Shu, Ji-Cheng; Ren, Gang; Shao, Feng; Liu, Li-sha

    2012-12-01

    Six steroidal saponins and two pregnane glycosides were isolated from the BuOH subfraction of 70% EtOH extract of Smilax microphylla C.H.Wright, among them two were new compounds (1 and 7). Pregnane glycosides were firstly isolated from the genus Smilax (Smilacaceae). Structures of the new compounds were determined on the basis of HR-ESI-MS, 1D and 2D NMR spectroscopic analysis.

  11. Phenolic glycosides from sugar maple (Acer saccharum) bark.

    PubMed

    Yuan, Tao; Wan, Chunpeng; González-Sarrías, Antonio; Kandhi, Vamsikrishna; Cech, Nadja B; Seeram, Navindra P

    2011-11-28

    Four new phenolic glycosides, saccharumosides A-D (1-4), along with eight known phenolic glycosides, were isolated from the bark of sugar maple (Acer saccharum). The structures of 1-4 were elucidated on the basis of spectroscopic data analysis. All compounds isolated were evaluated for cytotoxicity effects against human colon tumorigenic (HCT-116 and Caco-2) and nontumorigenic (CCD-18Co) cell lines.

  12. Use of cardiac glycosides and risk of glioma.

    PubMed

    Seliger, Corinna; Meier, Christoph R; Jick, Susan S; Uhl, Martin; Bogdahn, Ulrich; Hau, Peter; Leitzmann, M F

    2016-04-01

    Cardiac glycosides induce apoptotic effects on glioma cells, but whether cardiac glycosides protect against risk for glioma is unknown. We therefore explored the relation between glycoside use and glioma risk using a large and validated database. We performed a case-control analysis using the Clinical Practice Research Datalink involving 2005 glioma cases diagnosed between 1995 and 2012 that were individually matched to 20,050 controls on age, gender, general practice, and number of years of active history in the database. Conditional logistic regression analysis was used to evaluate the association between cardiac glycosides and the risk of glioma adjusting for body mass index and smoking. We also examined use of common heart failure and arrhythmia medications to differentiate between a specific glycoside effect and a generic effect of treatment for congestive heart failure or arrhythmia. Cardiac glycoside use was inversely related to glioma incidence. After adjustment for congestive heart failure, arrhythmia, diabetes, and common medications used to treat those conditions, the OR of glioma was 0.47 (95% CI 0.27-0.81, Bonferroni-corrected p value = 0.024) for use versus non-use of cardiac glycosides, based on 17 exposed cases. In contrast, no associations were noted for other medications used to treat congestive heart failure or arrhythmias. The OR of glioma in people with congestive heart failure was 0.65 (95% CI 0.40-1.04), and for arrhythmia it was 1.01 (95% CI 0.78-1.31). These data indicate that cardiac glycoside use is independently associated with reduced glioma risk.

  13. Three New Steroidal Glycosides from the Roots of Cynanchum stauntonii

    PubMed Central

    Yu, Jin-Qian; Zhang, Zhi-Hui; Deng, An-Jun; Qin, Hai-Lin

    2013-01-01

    Three new steroidal glycosides, named as stauntosides L, M, and N (1–3), along with one known C21 steroidal glycoside, anhydrohirundigenin monothevetoside (4), were isolated from the 95% ethanol extract of the roots of Cynanchum stauntonii. The structures of these new compounds were elucidated on the basis of extensive spectroscopic analyses, mainly 1D and 2D NMR, HRESI-MS, and chemical methods. PMID:23555098

  14. Stability of steviol glycosides in several food matrices.

    PubMed

    Jooken, Etienne; Amery, Ruis; Struyf, Tom; Duquenne, Barbara; Geuns, Jan; Meesschaert, Boudewijn

    2012-10-24

    As steviol glycosides are now allowed as a food additive in the European market, it is important to assess the stability of these steviol glycosides after they have been added to different food matrices. We analyzed and tested the stability of steviol glycosides in semiskimmed milk, soy drink, fermented milk drink, ice cream, full-fat and skimmed set yogurt, dry biscuits, and jam. The fat was removed by centrifugation from the dairy and soy drink samples. Proteins were precipitated by the addition of acetonitrile and also removed by centrifugation. Samples of jam were extracted with water. Dry biscuits were extracted with ethanol. The resulting samples were concentrated with solid-phase extraction and analyzed by high-performance liquid chromatography on a C18 stationary phase and a gradient of acetonitrile/aqueous 25 mM phosphoric acid. The accuracy was checked using a standard addition on some samples. For assessing the stability of the steviol glycosides, samples were stored in conditions relevant to each food matrix and analyzed periodically. The results indicate that steviol glycosides can be analyzed with good precision and accuracy in these food categories. The recovery was between 96 and 103%. The method was also validated by standard addition, which showed excellent agreement with the external calibration curve. No sign of decomposition of steviol glycosides was found in any of the samples.

  15. Microwave-assisted extraction of green coffee oil and quantification of diterpenes by HPLC.

    PubMed

    Tsukui, A; Santos Júnior, H M; Oigman, S S; de Souza, R O M A; Bizzo, H R; Rezende, C M

    2014-12-01

    The microwave-assisted extraction (MAE) of 13 different green coffee beans (Coffea arabica L.) was compared to Soxhlet extraction for oil obtention. The full factorial design applied to the microwave-assisted extraction (MAE), related to time and temperature parameters, allowed to develop a powerful fast and smooth methodology (10 min at 45°C) compared to a 4h Soxhlet extraction. The quantification of cafestol and kahweol diterpenes present in the coffee oil was monitored by HPLC/UV and showed satisfactory linearity (R(2)=0.9979), precision (CV 3.7%), recovery (<93%), limit of detection (0.0130 mg/mL), and limit of quantification (0.0406 mg/mL). The space-time yield calculated on the diterpenes content for sample AT1 (Arabica green coffee) showed a six times higher value compared to the traditional Soxhlet method.

  16. Bacterial diterpene synthases: new opportunities for mechanistic enzymology and engineered biosynthesis.

    PubMed

    Smanski, Michael J; Peterson, Ryan M; Huang, Sheng-Xiong; Shen, Ben

    2012-04-01

    Diterpenoid biosynthesis has been extensively studied in plants and fungi, yet cloning and engineering diterpenoid pathways in these organisms remain challenging. Bacteria are emerging as prolific producers of diterpenoid natural products, and bacterial diterpene synthases are poised to make significant contributions to our understanding of terpenoid biosynthesis. Here we will first survey diterpenoid natural products of bacterial origin and briefly review their biosynthesis with emphasis on diterpene synthases (DTSs) that channel geranylgeranyl diphosphate to various diterpenoid scaffolds. We will then highlight differences of DTSs of bacterial and higher organism origins and discuss the challenges in discovering novel bacterial DTSs. We will conclude by discussing new opportunities for DTS mechanistic enzymology and applications of bacterial DTS in biocatalysis and metabolic pathway engineering.

  17. Bioactive Isopimarane Diterpenes from the Fungus, Epicoccum sp. HS-1, Associated with Apostichopus japonicus

    PubMed Central

    Xia, Xuekui; Qi, Jun; Liu, Yayue; Jia, Airong; Zhang, Yonggang; Liu, Changheng; Gao, Cuiling; She, Zhigang

    2015-01-01

    One new isopimarane diterpene (1), together with two known compounds, 11-deoxydiaporthein A (2) and iso-pimara-8(14),15-diene (3) were isolated from the culture of Epicoccum sp., which was associated with Apostichopus japonicus. Their structures were determined by the analysis of 1D and 2D NMR, as well as mass spectroscopic data. The absolute configuration of Compound 1 was deduced by a single-crystal X-ray diffraction experiment using CuKα radiation. In the bioactivity assay, both Compounds 1 and 2 exhibited α-glucosidase inhibitory activity with IC50 values of 4.6 ± 0.1 and 11.9 ± 0.4 μM, respectively. This was the first report on isopimarane diterpenes with α-glucosidase inhibitory activity. PMID:25738327

  18. On the biotransformation of ent-trachylobane to ent-kaur-11-ene diterpenes.

    PubMed

    Fraga, Braulio M; Gonzalez-Vallejo, Victoria; Guillermo, Ricardo

    2011-09-23

    The microbiological transformation of trachinodiol (1) by the fungus Mucor plumbeus afforded the corresponding 1α, 2α, 3α, and 17-hydroxy derivatives (2-4 and 6), respectively. 7β,16α,18-Trihydroxy-ent-kaur-11-ene (sicanatriol) (5) was also obtained in this feeding. The biotransformation of 1 to give 5 by this fungus may occur by enzymatic abstraction of a hydrogen atom, allylic to the cyclopropane ring, and subsequent cleavage of this ring. This route is similar to that postulated by us in plants of the genus Sideritis, where ent-trachylobane and ent-kaur-11-ene diterpenes coexist. This study confirms that hydroxylation of diterpenes by M. plumbeus occurs preferably at ring A carbons.

  19. Bicunningines A and B, two new dimeric diterpenes from Cunninghamia lanceolata.

    PubMed

    Hou, Xian-Feng; Yao, Sheng; Mándi, Attila; Kurtán, Tibor; Tang, Chun-Ping; Ke, Chang-Qiang; Li, Xi-Qiang; Ye, Yang

    2012-01-20

    Two unprecedented dimeric diterpenoids, with a 2,3-dihydrofuran ring fusing an abietane and a 4,5-seco-abietane diterpene, were isolated from Cunninghamia lanceolata. Their structures were elucidated by spectroscopic measurements, and their absolute configurations were determined by quantum chemical TDDFT ECD calculations, chemical transformations, and Mosher's method. The Mosher method carried out with MPA and MTPA esters of the sterically hindered sec-hydroxyl group gave contradictory results, while MPA afforded the correct absolute configuration.

  20. Bioactivity of Diterpens from the Ethyl Acetate Extract of Kingiodendron pinnatum Rox. Hams

    PubMed Central

    Javarappa, Komal Kumar; Prasad, Attemode Girijanna Devi; Mahadesh Prasad, AJ; Mane, Chetana

    2016-01-01

    Background: Kingiodendron pinnatum Rox. Hams. is an endangered medicinal plant used in gonorrhoe, catarrhal conditions of genito-urinary and respiratory tracts. The scientific and pharmacological formulation of K. pinnatum has not been established so far though it is being traditionally used by tribes of the region. Objective: P hytochemical screening and identification of the bioactive compounds from the ethyl acetate extract of Kingiodendron pinnatum Rox. Hams. Materials and Methods: Chromatographic separation was carried out by thin layer chromatography and column chromatography. Bio-autography of the column fractioned extract and TLC chromatogram were evaluated in vitro for antibacterial activity. The PTLC, HP TLC were used for crude extract and HPLC, LCMS, FTIR, 1HNMR and 13CNMR were employed for the isolated compound in the ethyl acetate extract of K. pinnatum. Results: Evaluation of solvent system for chromatographic separation revealed that ethyl acetate: petroleum ether in the ratio of 7:2.5 ml was the most appropriate one for the separation of diterpene compounds. The antibacterial bio-autography screening of TLC separated compound showed positive activity with Staphylococcus aureus and negative activity with Escherichia coli. Spectroscopic analysis of the isolated compound from the ethyl acetate extract of K. pinnatum revealed the presence of diterpene compound. Conclusion: It is evident from the present study that the ethyl acetate extract of K. pinnatum is rich in diterpene compounds and having potential antibacterial activity. SUMMARY Novel extraction method for phytochemicls from Kingidendron pinnatum at RTAntibacterial property of diterpens extracted from Kingiodendron pinnatum Rox. Hams aganist S. aureus Abbreviations Used: TLC: Thin Layer Chromatography, PTLC: Preparatory Thin Layer Chromatography, HPTLC: High perormence Thin Layer chromatography, HPLC: High Performance Liquid Chromatography, LC-MS: Liquid chromatography Mass Spectra, FTIR

  1. Mode of antibacterial action of totarol, a diterpene from Podocarpus nagi.

    PubMed

    Haraguchi, H; Oike, S; Muroi, H; Kubo, I

    1996-04-01

    The antimicrobial mechanism of totarol was studied using Pseudomonas aeruginosa IFO 3080. This diterpene inhibited oxygen consumption and respiratory-driven proton translocation in whole cells, and oxidation of NADH in membrane preparation. NADH-cytochrome c reductase was inhibited by totarol while cytochrome c oxidase was not. NADH-DPIP reductase and NADH-CoQ reductase were also inhibited. The site of respiratory inhibition of totarol was thought to be near CoQ in the bacterial electron transport chain.

  2. Cassane diterpenes with oxygen bridge from the seeds of Caesalpinia sappan.

    PubMed

    Xu, Xudong; Yuan, Jingquan; Zhou, Xingyang; Li, Weiping; Zhu, Nailiang; Wu, Haifeng; Li, Pengfei; Sun, Zhonghao; Yang, Junshan; Ma, Guoxu

    2016-07-01

    The seeds of the medicinal plant Caesalpinia sappan yielded fourteen cassane-type diterpenes, including six new rearranged ones named as caesalppans A-F (1-6). Their structures were elucidated by spectroscopic analysis and comparison with literature data. The isolated new compounds 1-6 possess lactone-type cassane diterpenoid skeleton with an oxygen bridge between C-19 and C-20, and were tested cytotoxic activity against four cancer cell lines using the MTT method.

  3. Palladium-catalyzed transformations of salvinorin A, a neoclerodane diterpene from Salvia divinorum.

    PubMed

    Riley, Andrew P; Day, Victor W; Navarro, Hernán A; Prisinzano, Thomas E

    2013-12-06

    Transformations that selectively modify the furan ring present in a variety of naturals products would be useful in the synthesis of biological probes but remain largely underexplored. The neoclerodane diterpene salvinorin A, isolated from Salvia divinorum, is an example of a furan-containing natural product. Following selective bromination of salvinorin A, Suzuki-Miyaura and Sonogashira couplings were accomplished in moderate to good yields without hydrolyzing the labile C-2 acetate or altering the stereochemistry of the epimerizable centers.

  4. Palladium-catalyzed Transformations of Salvinorin A, a Neoclerodane Diterpene from Salvia divinorum

    PubMed Central

    Riley, Andrew P.; Day, Victor W.; Navarro, Hernán A.

    2013-01-01

    Transformations that selectively modify the furan ring present in a variety of naturals products would be useful in the synthesis of biological probes but remain largely underexplored. The neoclerodane diterpene salvinorin A, isolated from Salvia divinorum, is an example of a furan-containing natural product. Following selective bromination of salvinorin A, Suzuki-Miyaura and Sonogashira couplings were accomplished in moderate to good yields without hydrolyzing the labile C-2 acetate or altering the stereochemistry of the epimerizable centers. PMID:24246026

  5. Studies on chemical constituents of the leaves of Smallantus sonchifolius (yacon): structures of two new diterpenes.

    PubMed

    Dou, De-Qiang; Tian, Fang; Qiu, Ying-Kun; Xiang, Zheng; Xu, Bi Xia; Kang, Ting Guo; Dong, Feng

    2010-01-01

    The extract from the leaves of Smallantus sonchifolius (yacon) was found to show potent anti-diabetic activity. Two new diterpenes, named ent-kaurane-3beta,16beta,17, 19-tetrol (1) and ent-kaurane-16beta,17,18,19-tetrol (2), were isolated from the extract, together with six known compounds. The structures of the new compounds were determined on the basis of chemical and physicochemical evidence.

  6. Hepatoprotective prenylaromadendrane-type diterpenes from the gum resin of Boswellia carterii.

    PubMed

    Wang, Yan-gai; Ren, Jin; Wang, Ai-guo; Yang, Jian-bo; Ji, Teng-fei; Ma, Qin-Ge; Tian, Jin; Su, Ya-lun

    2013-11-22

    Chemical examination of the exuded gum resin of Boswellia carterii resulted in the isolation of nine new prenylaromadendrane-type diterpenes, boscartols A-I (1-9). The structures of these compounds were established by extensive 1D and 2D NMR spectroscopic analyses, mass spectrometric data, and circular dichroism spectra. Compounds 1-3, 5, 6, 8, and 9 (10 μM) showed moderate hepatoprotective activity against d-galactosamine-induced HL-7702 cell damage.

  7. Clerodane type diterpene as a novel antifungal agent from Polyalthia longifolia var. pendula.

    PubMed

    Bhattacharya, Asish K; Chand, Hemender R; John, Jyothis; Deshpande, Mukund V

    2015-04-13

    Bioactivity-guided chemical examination of methanolic extract of leaves of Polyalthia longifolia var. pendula led to the isolation of the active constituent, a diterpene 1 which was identified as 16α-hydroxycleroda-3,13(14)Z-dien-15,16-olide on the basis of its spectral data. Among the tested strains, diterpene 1 was found to exhibit antifungal activities having MIC90 values of 50.3, 100.6 and 201.2 μM against Candida albicans NCIM3557, Cryptococcus neoformans NCIM3542 (human pathogens) and Neurospora crassa NCIM870 (saprophyte), respectively. Initial, structure-activity-relationship (SAR) data generated by synthesizing some derivatives revealed that the double bond between C3-C4 and the free hydroxyl group at C16 are crucial for the antifungal activity of the diterpene 1. The mode of action of 1 in C. albicans is due to compromised cell membrane permeability and also probably due to disruption of cell wall structures. The red blood cell haemolysis of all the compounds (1-4) did not show any significant haemolysis and was found to be less than 15% for all the compounds when tested at highest concentration, i.e. 1200 μM. Interestingly, all the tested compounds inhibited Y-H transition in dimorphic C. albicans NCIM3557 at much lower concentration than their MIC90 values. Determination of ROS generation by diterpene 1 using DCFH-DA and DHR123 (dihydrorhodamine) staining of C. albicans NCIM3557 indicated production of intracellular ROS as a mechanism of antifungal activity.

  8. Studies on the localization of the cardiac glycoside receptor

    PubMed Central

    Smith, Thomas W.; Wagner, Henry; Markis, John E.; Young, Michael

    1972-01-01

    The purpose of this study was to see whether the receptor for cardiac glycosides might be localized upon or within the plasma membrane of digitalis-sensitive cells. Ouabain and digoxin were joined covalently to several large protein molecules. These macromolecular conjugates are too large to enter intact cells; consequently, any pharmacologic or biochemical effects which they display should arise from interaction with a cell surface receptor. Conjugates were tested in several cardiac glycoside-sensitive systems: (a), contractility response of isolated cardiac muscle; (b), active 86Rb+ uptake by red cells; (c), enzymatic activity of isolated myocardial microsomal (Na+ + K+)-activated adenosine triphosphatase (ATPase); and (d), enzymatic activity of solubilized red cell (Na+ + K+)-activated ATPase. Results demonstrated that in all of these systems, the macromolecular-glycoside conjugates were 100- to 1000-fold less active than the free glycosides. Careful chromatographic examination of the various conjugates revealed that they contained a small but persistent free cardiac glycoside contaminant. The amount of this species ranged from 0.1 to 1.0% of the total macromolecule-bound glycoside, and its presence fully explains the levels of biologic activity observed with the conjugates. To try to minimize steric factors which could interfere with glycoside-receptor interaction, digoxin and ouabain were also coupled to macromolecule via long, flexible polyamide side-chains. These extended chain conjugates, in which the cardiac glycoside potentially lay some 30 A removed from the surface of the macromolecule, also exhibited negligible digitalis-like effects when tested upon isolated cardiac muscle, red cell 86Rb+ uptake, and enzymatic activity of cardiac microsomal (Na+ + K+)-ATPase. However, the extended chain conjugates were fully active when examined with the solubilized red cell (Na+ + K+)-ATPase system. To further ensure that the chemical reactions used to couple

  9. Mild and selective deprotection method of acetylated steroids and diterpenes by dibutyltin oxide.

    PubMed

    Wang, Shao-Min; Zhang, Yan-Bing; Liu, Hong-Min; Yu, Guo-Bin; Wang, Ke-Rang

    2007-01-01

    Dibutyltin oxide (DBTO) was first utilized for the deacetylation of steroid and diterpene esters. The results showed the deprotection of acetylated steroids and diterpenes separately with moderate catalysis dibutyltin oxide in methanol selectively removed part acetyl groups of these substrates, whereas several functional groups of the steroids and diterpenes were retained and neither isomerization nor degradation of these substrates was observed. It seems that the acetyl groups with lower steric hindrance or near carbonyl, alkoxy, or hydroxyl groups can be cleaved by the reaction, whereas the acetyl groups with higher steric hindrance or without carbonyl, alkoxy, or hydroxyl groups neighboring were retained under the same conditions. One of the interesting results obtained was the selective hydrolysis of the 3beta-O-acetyl group in the presence of the 6beta group in 3beta,6beta-Di-O-acetyl-5alpha-hydroxypregn-16-en-20-one. This allows for subsequent introduction of one unit at C-3 and the other unit at C-6. This procedure is useful for the synthesis of a series of closely related isomers of 3beta,5alpha,6beta-trihydroxypregn-16-en-20-one and other widespread polyhydroxysteroids in marine organisms and some terrestrial species.

  10. Identification of diterpenes in canvas painting varnishes by gas chromatography-mass spectrometry with combined derivatisation.

    PubMed

    Osete-Cortina, L; Doménech-Carbó, M T; Mateo-Castro, R; Gimeno-Adelantado, J V; Bosch-Reig, F

    2004-01-23

    A derivatisation method that combines the formation of ethyl esters from the carboxylic groups and trimethylsilyl ethers from hydroxyl groups of the components of diterpenic resins is presented in this paper. This methodology involves two experimental steps: (1) formation of ethyl esters using ethyl chloroformate; and (2) the esterified compounds are lead to react with trimethylsilylimidazole to form the corresponding trimethylsilyl ethers. The main advantage of the proposed method is the possibility of performing simultaneously the analysis of amino acids from proteins, fatty acids from drying oils, and diterpenic compounds from natural resins usually found in works of art. This methodology is of considerable interest due to the requirements of minimum sampling that usually involves the analysis of works of art. A chemometric study has been developed to adjust the optimal working conditions of the proposed derivatisation method in which chromatographic peak areas of the larixyl acetate derivative and the abietic acid derivative referred to n-hexadecane as internal standard have been compared. Samples of Venetian turpentine naturally aged have been used in this study. Finally, the efficiency of the proposed derivatisation method has been tested on other diterpenic resins and pigments commonly used in fine arts such as Strasbourg turpentine, Canada balsam, colophony, copper resinate and a sample from a Renaissance Altarpiece.

  11. ent-Kaurane diterpenes from the stem bark of Annona vepretorum (Annonaceae) and cytotoxic evaluation.

    PubMed

    Dutra, Lívia M; Bomfim, Larissa M; Rocha, Suellen L A; Nepel, Angelita; Soares, Milena B P; Barison, Andersson; Costa, Emmanoel V; Bezerra, Daniel P

    2014-08-01

    This work describes a novel ent-kaurane diterpene, ent-3β-hydroxy-kaur-16-en-19-al along with five known ent-kaurane diterpenes, ent-3β,19-dihydroxy-kaur-16-eno, ent-3β-hydroxy-kaur-16-eno, ent-3β-acetoxy-kaur-16-eno, ent-3β-hydroxy-kaurenoic acid and kaurenoic acid, as well as caryophyllene oxide, humulene epoxide II, β-sitosterol, stigmasterol and campesterol from the stem bark of Annona vepretorum Mart. (Annonaceae). Cytotoxic activities towards tumor B16-F10, HepG2, K562 and HL60 and non-tumor PBMC cell lines were evaluated for ent-kaurane diterpenes. Among them, ent-3β-hydroxy-kaur-16-en-19-al was the most active compound with higher cytotoxic effect over K562 cell line (IC50 of 2.49 μg/mL) and lower over B16-F10 cell line (IC50 of 21.02 μg/mL).

  12. Kaurane and pimarane-type diterpenes from the Viguiera species inhibit vascular smooth muscle contractility.

    PubMed

    Ambrosio, Sergio R; Tirapelli, Carlos R; da Costa, Fernando B; de Oliveira, Ana M

    2006-08-01

    The research, development and use of natural products as therapeutic agents, especially those derived from plants, have been increasing in recent years. Despite the fact that plants provide a rich source of novel biologically active compounds, only a small percentage have been phytochemically investigated and studied for their medical potential. Viguiera is a genus that belongs to the family Asteraceae and to the sunflower tribe Heliantheae, which is widespread mostly in Mexico and in other areas of the Andes and upland areas of Brazil. A review on the secondary metabolites pointed out that sesquiterpene lactones and diterpenes, of the kaurane and pimarane-type, are the main compounds produced by these plants. Some reports have shown that kaurane- and pimarane-type diterpenes exert several biological activities such as anti-inflammatory action, antimicrobial and antispasmodic activities. Kaurenoic and pimaradienoic acids, which are the main secondary metabolites isolated by our research group from the roots of Viguiera robusta and V. arenaria, respectively, have been evaluated on vascular smooth muscle contractility. We showed that these diterpenoids are able to inhibit the vascular contractility mainly by blocking extracellular Ca(2+) influx. Additionally, in this review we discuss the structure-activity relationship of the diterpenes regarding their inhibitory activity on vascular contractility.

  13. Antiviral Activity of Diterpene Esters on Chikungunya Virus and HIV Replication.

    PubMed

    Nothias-Scaglia, Louis-Félix; Pannecouque, Christophe; Renucci, Franck; Delang, Leen; Neyts, Johan; Roussi, Fanny; Costa, Jean; Leyssen, Pieter; Litaudon, Marc; Paolini, Julien

    2015-06-26

    Recently, new daphnane, tigliane, and jatrophane diterpenoids have been isolated from various Euphorbiaceae species, of which some have been shown to be potent inhibitors of chikungunya virus (CHIKV) replication. To further explore this type of compound, the antiviral activity of a series of 29 commercially available natural diterpenoids was evaluated. Phorbol-12,13-didecanoate (11) proved to be the most potent inhibitor, with an EC50 value of 6.0 ± 0.9 nM and a selectivity index (SI) of 686, which is in line with the previously reported anti-CHIKV potency for the structurally related 12-O-tetradecanoylphorbol-13-acetate (13). Most of the other compounds exhibited low to moderate activity, including an ingenane-type diterpene ester, compound 28, with an EC50 value of 1.2 ± 0.1 μM and SI = 6.4. Diterpene compounds are known also to inhibit HIV replication, so the antiviral activities of compounds 1-29 were evaluated also against HIV-1 and HIV-2. Tigliane- (4β-hydroxyphorbol analogues 10, 11, 13, 15, 16, and 18) and ingenane-type (27 and 28) diterpene esters were shown to inhibit HIV replication in vitro at the nanomolar level. A Pearson analysis performed with the anti-CHIKV and anti-HIV data sets demonstrated a linear relationship, which supported the hypothesis made that PKC may be an important target in CHIKV replication.

  14. Resin Glycosides from the Morning Glory Family

    NASA Astrophysics Data System (ADS)

    Pereda-Miranda, Rogelio; Rosas-Ramírez, Daniel; Castañeda-Gómez, Jhon

    Resin glycosides are part of a very extensive family of secondary metabolites known as glycolipids or lipo-oligosaccharides and are constituents of complex resins (glycoresins) (1) unique to the morning glory family, Convolvulaceae (2). These active principles are responsible for the drastic purgative action of all the important Convolvulaceous species used in traditional medicine throughout the world since ancient times. Several commercial purgative crude drugs can be prepared from the roots of different species of Mexican morning glories. Their incorporation as therapeutic agents in Europe is an outstanding example of the assimilation of botanical drugs from the Americas as substitutes for traditional Old World remedies (3). Even though phytochemical investigations on the constituents of these drugs were initiated during the second half of the nineteenth century, the structure of their active ingredients still remains poorly known for some examples of these purgative roots. During the last two decades, the higher resolution capabilities of modern analytical isolation techniques used in conjunction with powerful spectroscopic methods have facilitated the elucidation of the active principles of these relevant herbal products.

  15. Antioxidant flavonol glycosides from Schinus molle.

    PubMed

    Marzouk, Mohamed S; Moharram, Fatma A; Haggag, Eman G; Ibrahim, Magda T; Badary, Osama A

    2006-03-01

    Chromatographic separation of aqueous MeOH extract of the leaves of Schinus molle L. has yielded two new acylated quercetin glycosides, named isoquercitrin 6''-O-p-hydroxybenzoate (12) and 2''-O-alpha-L-rhamnopyranosyl-hyperin 6''-O-gallate (13), together with 12 known polyphenolic metabolites for the first time from this species, namely gallic acid (1), methyl gallate (2), chlorogenic acid (3), 2''-alpha-L-rhamnopyranosyl-hyperin (4), quercetin 3-O-beta-D-neohesperidoside (5), miquelianin (6), quercetin 3-O-beta-D-galacturonopyranoside (7), isoquercitrin (8), hyperin (9), isoquercitrin 6''-gallate (10), hyperin 6''-O-gallate (11) and (+)-catechin (14). Their structures were established on the basis of chromatographic properties, chemical, spectroscopic (UV, 1H, 13C NMR) and ESI-MS (positive and negative modes) analyses. Compounds 4-9 and 11 exhibited moderate to strong radical scavenging properties on lipid peroxidation, hydroxyl radical and superoxide anion generations with the highest activities shown by 6 and 7 in comparison with that of quercetin as a positive control in vitro.

  16. Three new flavonol glycosides from Suaeda maritima.

    PubMed

    Abd El-Latif, Rasha R; Mansour, Ragaa M A; Sharaf, Mohamed; Farag, Ahmad

    2014-01-01

    Three new flavonol glycosides isolated from the 70% methanol extract of Suaeda maritima (Chenopodiaceae) were characterized based on spectroscopic and chemical methods as quercetin 3-O-α-l-rhamnopyranosyl(1″' → 6″)-β-d-galactopyranoside-7-O-β-d-glucopyranosyl(1″″' → 2″″)-glucopyranoside, kaempferol 3-O-α-l-rhamnopyranosyl(1″' → 6″)-β-d-galactopyranoside-7-O-β-d-glucopyranosyl(1″″' → 2″″)-glucopyranoside, and kaempferol 3-O-α-l-rhamnopyranosyl(1″' → 6″)-β-d-galactopyranoside-7-O-(2″″'-O-trans-feruloyl)-β-d-glucopyranosyl-(1″″' → 2″″)-β-d-glucopyranoside. In addition, four known compounds, namely, quercetin and kaempferol, methyl cis, trans-ferulate, and methyl trans-ferulate were identified. The plant extract and these compounds showed cytotoxic activity against the human tumor cell lines MCF7, HCT116, and HEPG2.

  17. Acylated pregnane glycosides from Caralluma quadrangula.

    PubMed

    Abdallah, Hossam M; Osman, Abdel-Moneim M; Almehdar, Hussein; Abdel-Sattar, Essam

    2013-04-01

    In a previous study, the methanolic extract as well as the chloroform fraction of the aerial parts of Caralluma quadrangula (Forssk.) N.E.Br. indigenous to Saudi Arabia showed significant in vitro cytotoxic activity against breast cancer (MCF7) cell line. In a biologically-guided fractionation approach, four acylated pregnane glycosides were isolated from the chloroform fraction of C. quadrangula. The structures of the isolated compounds were elucidated by the analysis of their MS and NMR data. The compounds were identified as 12,20-di-O-benzoylboucerin 3-O-β-D-digitoxopyranosyl-(1→4)-β-D-canaropyranosyl-(1→4)-β-D-cymaropyranoside (1), 12,20-di-O-benzoylboucerin 3-O-β-D-cymaropyranosyl-(1→4)-β-D-canaropyranosyl-(1→4)-β-D-cymaropyranoside (2), 12,20-di-O-benzoylboucerin 3-O-β-D-glucopyranosyl-(1→4)-β-D-digitoxopyranosyl-(1→4)-β-D-canaropyranosyl-(1→4)-β-D-cymaropyranoside (3) and 12,20-di-O-benzoyl-3β,5α,12β,14β,20-pentahydroxy-(20R)-pregn-6-ene 3-O-β-D-glucopyranosyl-(1→4)-β-D-digitoxopyranosyl-(1→4)-β-D-canaropyranosyl-(1→4)-β-D-cymaropyranoside (4). The isolated compounds were tested for their cytotoxic activity against breast cancer (MCF7) cell line.

  18. Glycosidic inhibitors of melanogenesis from leaves of Passiflora edulis.

    PubMed

    Zhang, Jie; Koike, Ryosuke; Yamamoto, Ayako; Ukiya, Motohiko; Fukatsu, Makoto; Banno, Norihiro; Miura, Motofumi; Motohashi, Shigeyasu; Tokuda, Harukuni; Akihisa, Toshihiro

    2013-10-01

    A new flavonoid glycoside, chrysin 6-C-β-rutinoside (chrysin α-L-rhamnopyranosyl-(1→6)-C-β-glucopyranoside; 2), and two new triterpene glycosides, (31R)-31-O-methylpassiflorine (7) and (31S)-31-O-methylpassiflorine (8), along with 14 known glycosides, including three flavonoid glycosides, 1, 3, and 4, six triterpene glycosides, 5, 6, and 9-12, three cyano glycosides, 13-15, and two other glycosides, 16 and 17, were isolated from a MeOH extract of the leaves of Passiflora edulis (passion flower; Passifloraceae). The structures of new compounds were elucidated on the basis of extensive spectroscopic analysis and comparison with literature data. Upon evaluation of compounds 1-17 against the melanogenesis in the B16 melanoma cells induced with α-melanocyte-stimulating hormone (α-MSH), three compounds, isoorientin (1), 2, and (6S,9R)-roseoside (17), exhibited inhibitory effects with 37.3-47.2% reduction of melanin content with no, or almost no, toxicity to the cells (90.8-100.2% cell viability) at 100 μM. Western blot analysis showed that compound 2 reduced the protein levels of MITF, TRP-1, and tyrosinase, in a concentration-dependent manner while exerted almost no influence on the level of TRP-2, suggesting that this compound inhibits melanogenesis on the α-MSH-stimulated B16 melanoma cells by, at least in part, inhibiting the expression of MITF, followed by decreasing the expression of TRP-1 and tyrosinase. In addition, compounds 1-17 were evaluated for their inhibitory effects against the EpsteinBarr virus early antigen (EBV-EA) activation induced by 12-O-tetradecanoylphorbol-13-acetate (TPA) in Raji cells.

  19. Base substitution mutations in uridinediphosphate-dependent glycosyltransferase 76G1 gene of Stevia rebaudiana causes the low levels of rebaudioside A: mutations in UGT76G1, a key gene of steviol glycosides synthesis.

    PubMed

    Yang, Yong-Heng; Huang, Su-Zhen; Han, Yu-Lin; Yuan, Hai-Yan; Gu, Chun-Sun; Zhao, Yan-Hai

    2014-07-01

    Steviol glycosides, extracted from the leaves of Stevia rebaudiana (Bert) Bertoni, are calorie-free sugar substitute of natural origin with intensely sweet (Boileau et al., 2012). Stevioside and rebaudioside A are the two main kinds of the diterpenic glycosides. We analyzed the concentration of stevioside and rebaudioside A in Stevia leaves of about 500 samples (hybrid progenies) and discovered a mutation plant "Z05" with very low levels of rebaudioside A. Because UGT76G1, a uridinediphosphate-dependent glycosyltransferases, is responsible for the conversion from stevioside to rebaudioside A (Richman et al., 2005), so mutation identification was done by sequencing the candidate gene, UGT76G1. In this study molecular analysis of two strains revealed a heterozygotic nonsense mutation of c.389T > G (p.L121X) in UGT76G1. Meanwhile, we found some amino acid substitutions significant change the protein structure. And the difference of enzyme activity between two strains proved the lack of functionality of UGT76G1 of the mutation "Z05". So the nonsense mutation and amino acid substitution mutation resulted in the low levels of rebaudioside A.

  20. Rapid Solid-Liquid Dynamic Extraction (RSLDE): a New Rapid and Greener Method for Extracting Two Steviol Glycosides (Stevioside and Rebaudioside A) from Stevia Leaves.

    PubMed

    Gallo, Monica; Vitulano, Manuela; Andolfi, Anna; DellaGreca, Marina; Conte, Esterina; Ciaravolo, Martina; Naviglio, Daniele

    2017-01-20

    Stevioside and rebaudioside A are the main diterpene glycosides present in the leaves of the Stevia rebaudiana plant, which is used in the production of foods and low-calorie beverages. The difficulties associated with their extraction and purification are currently a problem for the food processing industries. The objective of this study was to develop an effective and economically viable method to obtain a high-quality product while trying to overcome the disadvantages derived from the conventional transformation processes. For this reason, extractions were carried out using a conventional maceration (CM) and a cyclically pressurized extraction known as rapid solid-liquid dynamic extraction (RSLDE) by the Naviglio extractor (NE). After only 20 min of extraction using the NE, a quantity of rebaudioside A and stevioside equal to 1197.8 and 413.6 mg/L was obtained, respectively, while for the CM, the optimum time was 90 min. From the results, it can be stated that the extraction process by NE and its subsequent purification developed in this study is a simple, economical, environmentally friendly method for producing steviol glycosides. Therefore, this method constitutes a valid alternative to conventional extraction by reducing the extraction time and the consumption of toxic solvents and favouring the use of the extracted metabolites as food additives and/or nutraceuticals. As an added value and of local interest, the experiment was carried out on stevia leaves from the Benevento area (Italy), where a high content of rebaudioside A was observed, which exhibits a sweet taste compared to stevioside, which has a significant bitter aftertaste.

  1. Steviol glycoside safety: is the genotoxicity database sufficient?

    PubMed

    Urban, J D; Carakostas, M C; Brusick, D J

    2013-01-01

    The safety of steviol glycoside sweeteners has been extensively reviewed in the literature. National and international food safety agencies and approximately 20 expert panels have concluded that steviol glycosides, including the widely used sweeteners stevioside and rebaudioside A, are not genotoxic. However, concern has been expressed in recent publications that steviol glycosides may be mutagenic based on select studies representing a small fraction of the overall database, and it has been suggested that further in vivo genotoxicity studies are required to complete their safety profiles. To address the utility of conducting additional in vivo genotoxicity studies, this review evaluates the specific genotoxicity studies that are the sources of concern, and evaluates the adequacy of the database including more recent genotoxicity data not mentioned in those publications. The current database of in vitro and in vivo studies for steviol glycosides is robust and does not indicate that either stevioside or rebaudioside A are genotoxic. This, combined with a lack of evidence for neoplasm development in rat bioassays, establish the safety of all steviol glycosides with respect to their genotoxic/carcinogenic potential.

  2. Human psychometric and taste receptor responses to steviol glycosides.

    PubMed

    Hellfritsch, Caroline; Brockhoff, Anne; Stähler, Frauke; Meyerhof, Wolfgang; Hofmann, Thomas

    2012-07-11

    Steviol glycosides, the sweet principle of Stevia Rebaudiana (Bertoni) Bertoni, have recently been approved as a food additive in the EU. The herbal non-nutritive high-potency sweeteners perfectly meet the rising consumer demand for natural food ingredients in Europe. We have characterized the organoleptic properties of the most common steviol glycosides by an experimental approach combining human sensory studies and cell-based functional taste receptor expression assays. On the basis of their potency to elicit sweet and bitter taste sensations, we identified glycone chain length, pyranose substitution, and the C16 double bond as the structural features giving distinction to the gustatory profile of steviol glycosides. A comprehensive screening of 25 human bitter taste receptors revealed that two receptors, hTAS2R4 and hTAS2R14, mediate the bitter off-taste of steviol glycosides. For some test substances, e.g., stevioside, we observed a decline in sweet intensity at supra-maximum concentrations. This effect did not arise from allosteric modulation of the hTAS1R2/R3 sweet taste receptor but might be explained by intramolecular cross-modal suppression between the sweet and bitter taste component of steviol glycosides. These results might contribute to the production of preferentially sweet and least bitter tasting Stevia extracts by an optimization of breeding and postharvest downstream processing.

  3. Acylated pregnane glycosides from Caralluma sinaica.

    PubMed

    Al-Massarani, Shaza M; Bertrand, Samuel; Nievergelt, Andreas; El-Shafae, Azza M; Al-Howiriny, Tawfeq A; Al-Musayeib, Nawal M; Cuendet, Muriel; Wolfender, Jean-Luc

    2012-07-01

    Caralluma sinaica is sold on local markets of Saudi Arabia for various health benefits however no phytochemical study has specifically been performed on this species. NMR and UHPLC-ESI-TOF-MS profilings of the ethanolic extract of the whole plant reveal a very complex phytochemical composition dominated by pregnanes. Detailed information on its constituents was obtained after isolation. Six pregnane glycosides were obtained and characterized based on the extensive spectroscopic analysis (including IR, ¹H NMR, ¹³C NMR and MS data), in addition to ten known compounds (seven pregnanes and three flavonoids). The compounds were identified as 12β-O-benzoyl-20-O-acetyl boucerin-3-O-6-deoxy-3-O-methyl-β-D-glucopyranosyl-(1-->4)-β-D-cymaropyranosyl-(1-->4)-β-D-cymaropyranoside, 12β-O-tigloyl-20-O-acetyl boucerin-3-O-β-D-glucopyranosyl-(1-->4)-β-D-cymaropyranoside, 12β-O-benzoyl-20-O-acetyl boucerin-3-O-β-D-glucopyranosyl-(1-->4)-β-D-digitalopyranosyl-(1-->4)-β-D-cymaropyranosyl-(1-->4)-β-D-cymaropyranoside, 12β-O-benzoyl-20-O-acetyl boucerin-3-O-β-D-glucopyranosyl-(1-->4)-hevetopyranosyl-(1-->4)-β-D-cymaropyranosyl-(1-->4)-β-D-cymaropyranoside, 12β-O-benzoyl-20-O-tigloyl boucerin-3-O-β-D-glucopyranosyl-(1-->4)-β-D-cymaropyranoside, 12β-20-O-dibenzoyl boucerin-3-O-β-D-glucopyranosyl-(1-->4)-β-D-cymaropyranosyl-(1-->4)-β-D-cymaropyranoside. Finally, the isolated compounds were evaluated for their quinone reductase induction.

  4. Rebaudiosides T and U, minor C-19 xylopyranosyl and arabinopyranosyl steviol glycoside derivatives from Stevia rebaudiana (Bertoni) Bertoni.

    PubMed

    Perera, Wilmer H; Ghiviriga, Ion; Rodenburg, Douglas L; Alves, Kamilla; Bowling, John J; Avula, Bharathi; Khan, Ikhlas A; McChesney, James D

    2017-03-01

    Two diterpene glycosides were isolated from a commercial Stevia rebaudiana leaf extract. One was found to be 13-[(2-O-β-d-glucopyranosyl-3-O-β-d-glucopyranosyl-β-d-glucopyranosyl)oxy]ent-kaur-16-en-19-oic acid-(2-O-β-d-xylopyranosyl-3-O-β-d-glucopyranosyl- β-d-glucopyranosyl) ester (rebaudioside T), whereas the other was determined to be 13-[(2-O-β-d-glucopyranosyl-3-O-β-d-glucopyranosyl-β-d-glucopyranosyl)oxy]ent-kaur-16-en-19-oic acid-(6-O-α-l-arabinopyranosyl-β-d-glucopyranosyl) ester (rebaudioside U). In addition, five C-19 sugar free derivatives were prepared and identified as follows: 13-[(2-O-α-l-rhamnopyranosyl-β-d-glucopyranosyl)]oxy]kaur-16-en-19-oic acid (dulcoside A1); 13-[(2-O-β-d-xylopyranosy-3-O-β-d-glucopyranosyl-β-d-glucopyranosyl)oxy]kaur-16-en-19-oic acid; 13-[(2-O-β-d-xylopyranosyl-β-d-glucopyranosyl-)oxy]kaur-16-en-19-oic acid; 13-[(2-O-β-d-glucopyranosyl-3-O-β-d-glucopyranosyl-β-d-xylopyranosyl-)oxy]kaur-16-en-19-oic acid (rebaudioside R1) and 13-[(2-O-6-deoxy-β-d-glucopyranosyl-3-O-β-d-glucopyranosyl-β-d-glucopyranosyl)oxy]kaur-16-en-19-oic acid, respectively. Chemical structures were determined by NMR experiments. HPLC analyses were also useful to differentiate different steviol-C13 sugar substituent patterns by elution position.

  5. Absorption and metabolism of glycosidic sweeteners of stevia mixture and their aglycone, steviol, in rats and humans.

    PubMed

    Koyama, Eriko; Sakai, Norifumi; Ohori, Yuji; Kitazawa, Ken; Izawa, Osamu; Kakegawa, Kunio; Fujino, Akiharu; Ui, Michio

    2003-06-01

    Stevia mixture, sweeteners extracted from the leaves of Stevia rebaudiana Bertoni, consists mainly of the glycosides of the diterpene derivative steviol. The aims of this study were to investigate the absorption (in rats) and the hepatic metabolism (in rats and humans) of both stevia mixture and steviol. Absorption was investigated both in vivo and ex vivo. In ex vivo experiments using the rat everted sac method, no absorption of stevia mixture was observed, but significant absorption of steviol was noted (equivalent to approximately 70% of the absorption reference- salicylic acid- value). In the in vivo experiment, rats received a single oral administration of either steviol or stevia mixture; a peak steviol concentration in plasma was observed 15 min after its oral administration, demonstrating rapid absorption. However, after oral administration of stevia mixture, the steviol concentration in plasma increased steadily over 8 h, suggesting that stevia mixture components are first degraded and then absorbed as steviol in the rat intestine. Steviol metabolism in humans and rats was examined by incubating steviol with liver microsomes from the two species. Oxidative (monohydroxy and dihydroxy) metabolites of steviol were observed by LC-ESI/MS after incubation with both human and rat liver microsomes. The intrinsic clearance of steviol in human liver microsomes was 4-times lower than that found in rat liver microsomes. In conclusion, this study suggests that there are no major species differences in steviol hepatic metabolism between rats and humans. Absorption from the human intestine can be predicted to occur in an analogous manner to that from the rat intestine.

  6. Nickel-catalyzed proton-deuterium exchange (HDX) procedures for glycosidic linkage analysis of complex carbohydrates

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The structural analysis of complex carbohydrates typically requires the assignment of three parameters: monosaccharide composition, the position of glycosidic linkages between monosaccharides, and the position and nature of non-carbohydrate substituents. The glycosidic linkage positions are often de...

  7. Cytotoxic Steroidal Glycosides from the Whole Plant of Calamus acanthophyllus.

    PubMed

    Prawat, Hunsa; Mahidol, Chulabhorn; Kaweetripob, Wirongrong; Intachote, Pakamas; Pisutjaroenpong, Somchai; Ruchirawat, Somsak

    2016-07-01

    A new steroidal glycoside, callaphylloside (1), together with seven known glycosides (2-8), was isolated from the whole plant of Calamus acanthophyllus. The structure of the new compound was elucidated by spectral data analyses and chemical transformations. Compounds 5 and 8 exhibited strong cytotoxic activity against four cancer cell lines (0.7 ≤ IC50 ≤ 3.4 µM). Evaluation of the structure-activity relationship among steroidal glycosides revealed that the structure of spirostanol with an α-L-rhamnopyranosyl linked to C-2 of the inner glucopyranosyl residue both play a critical role in the effects of these compounds on the cancer cell lines.

  8. [Hypoglycemic and hypolipidemic effects of quercetin and its glycosides].

    PubMed

    Yan, Shu-xia; Li, Xian; Sun, Chong-de; Chen, Kun-song

    2015-12-01

    Quercetin and its glycosides are important flavonols in traditional herbal drugs and plant-derived food, and they have diverse hiological activities such as antioxidant, anticarcinogenic, anti-inflammatory, hypoglycemic and hypolipidemic activities. Numerous studies have demonstrated that quercetin and its glycosides were effective in the prevention and treatment of non-infectious chronic disease such as diabetes, obesity, and hyperlipidemia. They can regulate glucose and lipid metaholism through different mechanisms. They can decrease blood glucose via protecting pancreatic/p cells or/and improving insulin sensitivity. Also, they have lipid-lowering effects, which may be the result of regulation of lipid catabolism or/and anabolism. Their distributions, as well as the hypoglycemic and hypolipidemic effects are reviewed in this paper. In addition, further bioactivities as well as their dose-activity relationship, structure-activity relationship, bioavailability, and future clinical application of quercetin and its glycosides are discussed and proposed.

  9. 2-methyl-L-erythritol glycosides from Gardenia jasminoides.

    PubMed

    Yang, Liguo; Peng, Kaifeng; Zhao, Shizhe; Zhao, Feng; Chen, Lixia; Qiu, Feng

    2013-09-01

    Two new glycosides, 2-methyl-L-erythritol-4-O-(6-O-trans-sinapoyl)-β-D-glucopyranoside (1) and 2-methyl-L-erythritol-1-O-(6-O-trans-sinapoyl)-β-D-glucopyranoside (2), along with two known triterpenoids (3-4), four quinic acid derivatives (5-8) and one flavonoid (9) were isolated from the fruit of Gardenia jasminoides. Their structures were elucidated through MS and 2D NMR experiments (HMQC and HMBC). Inhibitory effects of the isolated compounds on nitric oxide production in lipopolysaccharide-activated macrophages were evaluated. Though 2-methyl-D-erythritol and its glycosides have been reported in a few references, this is the first report about 2-methyl-L-erythritol glycosides. Based on this finding, we propose that 2-methyl-L-erythritol might be a new intermediate in the non-mevalonate biosynthesis of terpenoids.

  10. Sesquiterpene glycosides from the roots of Codonopsis pilosula

    PubMed Central

    Jiang, Yueping; Liu, Yufeng; Guo, Qinglan; Xu, Chengbo; Zhu, Chenggen; Shi, Jiangong

    2015-01-01

    Three new sesquiterpene glycosides, named codonopsesquilosides A−C (1−3), were isolated from an aqueous extract of the dried roots of Codonopsis pilosula. Their structures including absolute configurations were determined by spectroscopic and chemical methods. These glycosides are categorized as C15 carotenoid (1), gymnomitrane (2), and eudesmane (3) types of sesquiterpenoids, respectively. Compound 1 is the first diglycoside of C15 carotenoids to be reported. Compound 2 represents the second reported example of gymnomitrane-type sesquiterpenoids from higher plants. The absolute configurations were supported by comparison of the experimental circular dichroism (CD) spectra with the calculated electronic CD (ECD) spectra of 1−3, their aglycones, and model compounds based on quantum-mechanical time-dependent density functional theory. The influences of the glycosyls on the calculated ECD spectra of the glycosidic sesquiterpenoids, as well as some nomenclature and descriptive problems with gymnomitrane-type sesquiterpenoids are discussed. PMID:26904398

  11. Chemical and biological properties of quinochalcone C-glycosides from the florets of Carthamus tinctorius.

    PubMed

    Yue, Shijun; Tang, Yuping; Li, Shujiao; Duan, Jin-Ao

    2013-12-10

    Quinochalcone C-glycosides are regarded as characteristic components that have only been isolated from the florets of Carthamus tinctorius. Recently, quinochalcone C-glycosides were found to have multiple pharmacological activities, which has attracted the attention of many researchers to explore these compounds. This review aims to summarize quinochalcone C-glycosides' physicochemical properties, chromatographic behavior, spectroscopic characteristics, as well as their biological activities, which will be helpful for further study and development of quinochalcone C-glycosides.

  12. Characterization of two genes for the biosynthesis of abietane-type diterpenes in rosemary (Rosmarinus officinalis) glandular trichomes.

    PubMed

    Brückner, Kathleen; Božić, Dragana; Manzano, David; Papaefthimiou, Dimitra; Pateraki, Irini; Scheler, Ulschan; Ferrer, Albert; de Vos, Ric C H; Kanellis, Angelos K; Tissier, Alain

    2014-05-01

    Rosemary (Rosmarinus officinalis) produces the phenolic diterpenes carnosic acid and carnosol, which, in addition to their general antioxidant activities, have recently been suggested as potential ingredients for the prevention and treatment of neurodegenerative diseases. Little is known about the biosynthesis of these diterpenes. Here we show that the biosynthesis of phenolic diterpenes in rosemary predominantly takes place in the glandular trichomes of young leaves, and used this feature to identify the first committed steps. Thus, a copalyl diphosphate synthase (RoCPS1) and two kaurene synthase-like (RoKSL1 and RoKSL2) encoding genes were identified and characterized. Expression in yeast (Saccharomyces cerevisiae) and Nicotiana benthamiana demonstrate that RoCPS1 converts geranylgeranyl diphosphate (GGDP) to copalyl diphosphate (CDP) of normal stereochemistry and that both RoKSL1 and RoKSL2 use normal CDP to produce an abietane diterpene. Comparison to the already characterized diterpene synthase from Salvia miltiorrhiza (SmKSL) demonstrates that the product of RoKSL1 and RoKSL2 is miltiradiene. Expression analysis supports a major contributing role for RoKSL2. Like SmKSL and the sclareol synthase from Salvia sclarea, RoKSL1/2 are diterpene synthases of the TPS-e group which have lost the internal gamma-domain. Furthermore, phylogenetic analysis indicates that RoKSL1 and RoKSL2 belong to a distinct group of KSL enzymes involved in specialized metabolism which most likely emerged before the dicot-monocot split.

  13. Cytotoxic cardiac glycosides and other compounds from Asclepias syriaca.

    PubMed

    Araya, Juan J; Kindscher, Kelly; Timmermann, Barbara N

    2012-03-23

    Phytochemical investigation of the dried biomass of Asclepias syriaca afforded five new compounds (1-5), along with 19 known structures. Overall, the secondary metabolites isolated and identified from this plant showed a wide structural diversity including pentacyclic triterpenes, cardiac glycosides, flavonoid glycosides, lignans, a phenylethanoid, and a glycosylated megastigmane. In addition, the isolates were tested against the cancer breast cell line Hs578T, and those showing IC(50) values lower than 50 μM (1 and 6-9) were further investigated in three additional breast cancer cell lines (MCF-7, T47D, and Sk-Br-3) and the normal breast cell line Hs578Bst.

  14. A glycoside of Nicotina tabacum affects mouse dopaminergic behavior.

    PubMed

    Masuda, Y; Ohnuma, S; Kawagoe, M; Sugiyama, T

    2003-01-01

    Climbing in the forced swimming test is considered a dopaminergic-specific behavior. A substance of Nicotina tabacum affecting dopamine neuronal activity was investigated using the mouse behavioral system. The substance was found to be a glycoside with the peripheral sugar chain structures Fuc alpha 1-2Gal, Gal beta 1-4GlcNAc and GalNAc alpha 1-3GalNAc and with basic polymannoses. The glycoside dose-dependently increased behavior via D2 neuronal activity, but not D1 activity. This suggests that smoking can affect human brain function not only via the nicotinic cholinergic neuron, but also via the D2 neuron.

  15. Bioactive glycosides from the African medicinal plant Boerhavia erecta L.

    PubMed

    Nugraha, Ari S; Hilou, Adama; Vandegraaff, Nicholas; Rhodes, David I; Haritakun, Rachada; Keller, Paul A

    2015-01-01

    Phytochemical studies of the previously unexplored stem of Boerhavia erecta from Burkina Faso, resulted in the isolation of an unreported glycoside 4, 2,3-dihydroxypropylbenzoate-3-O-β-[4″-methoxy] glucuronide as well as seven known glycosides (1-3, 5-8). The major isolate 5 and 8 indicated a significant inhibition against HIV integrase (IC50 10 and 22 μg/mL, respectively). The extracts and isolates were also tested for anti-malarial activity, but insignificant activity was observed.

  16. New flavonol glycosides from the leaves of Caragana brachyantha.

    PubMed

    Perveen, Shagufta; Al-Taweel, Areej Mohammad; Al-Musayeib, Nawal; Fawzy, Ghada Ahmed; Khan, Afsar; Mehmood, Rashad; Malik, Abdul

    2015-01-01

    Two new flavonol glycosides, brachysides C and D, together with three known flavonol glycosides, were isolated from the leaves of Caragana brachyantha. The structures of brachysides C and D were elucidated on the basis of detailed spectroscopic analysis as quercetin 5-O-[α-L-rhamnopyranosyl-(1 → 6)-β-D-glucopyranoside]-7-O-[α-L-rhamnopyranoside] and quercetin 5-O-[α-L-rhamnopyranosyl-(1 → 6)-β-D-glucopyranoside]-7-O-[α-L-rhamnopyranoside]-4'-O-[α-L-rhamnopyranoside], respectively. The presence of flavonol tetra- and triglycosides bearing a sugar moiety at position 5 was the first report from this genus Caragana.

  17. Steviol glycosides in purified stevia leaf extract sharing the same metabolic fate.

    PubMed

    Purkayastha, Sidd; Markosyan, Avetik; Prakash, Indra; Bhusari, Sachin; Pugh, George; Lynch, Barry; Roberts, Ashley

    2016-06-01

    The safety of steviol glycosides is based on data available on several individual steviol glycosides and on the terminal absorbed metabolite, steviol. Many more steviol glycosides have been identified, but are not yet included in regulatory assessments. Demonstration that these glycosides share the same metabolic fate would indicate applicability of the same regulatory paradigm. In vitro incubation assays with pooled human fecal homogenates, using rebaudiosides A, B, C, D, E, F and M, as well as steviolbioside and dulcoside A, at two concentrations over 24-48 h, were conducted to assess the metabolic fate of various steviol glycoside classes and to demonstrate that likely all steviol glycosides are metabolized to steviol. The data show that glycosidic side chains containing glucose, rhamnose, xylose, fructose and deoxy-glucose, including combinations of α(1-2), β-1, β(1-2), β(1-3), and β(1-6) linkages, were degraded to steviol mostly within 24 h. Given a common metabolite structure and a shared metabolic fate, safety data available for individual steviol glycosides can be used to support safety of purified steviol glycosides in general. Therefore, steviol glycosides specifications adopted by the regulatory authorities should include all steviol glycosides belonging to the five groups of steviol glycosides and a group acceptable daily intake established.

  18. Anti-Angiogenic Properties of Cafestol and Kahweol Palmitate Diterpene Esters.

    PubMed

    Moeenfard, Marzieh; Cortez, Alice; Machado, Vera; Costa, Raquel; Luís, Carla; Coelho, Pedro; Soares, Raquel; Alves, Arminda; Borges, Nuno; Santos, Alejandro

    2016-12-01

    Epidemiological studies support the association of coffee-specific diterpenes, with various beneficial health effects. Although anti-antiangiogenic properties of free cafestol and kahweol have been recently described, available data regarding their esterified form, in particular palmitate esters as the main diterpene esters present in coffee, are still rare. Given that angiogenesis plays an important role in many pathological conditions, including cancer growth and metastasis, this study aimed to assess and compare the potential anti-angiogenic effects of cafestol palmitate (CP) and kahweol palmitate (KP) in an in vitro angiogenesis model. According to our findings, both compounds inhibited angiogenesis steps on human microvascular endothelial cells (HMVECs), although a more significant effect was observed for KP. Compared to control, HMVECs viability decreased in a dose-dependent manner upon incubation either with CP or KP. Concentrations of 75 and 100 μM of each compound were cytotoxic. Cell proliferation was also dramatically reduced by both diterpene esters at 50 μM, although KP had a stronger inhibitory effect. However, CP and KP did not induce apoptosis on HMVECs. Both compounds reduced cell migration, but this effect was only statistically significant after KP incubation. Inhibition of VEGFR2 expression and its downstream effector Akt, but not Erk, was also observed in CP- and KP-treated HMVECs. These findings were confirmed using ELISA assay for phosphorylated (active) VEGFR-2. Taken together, these data indicate that both CP and KP can be considered potent compounds against angiogenesis-dependent disorders. Our findings further indicate that KP exerts more potent anti-angiogenic effects than CP, in most of assays. J. Cell. Biochem. 117: 2748-2756, 2016. © 2016 Wiley Periodicals, Inc.

  19. 4α-Acetoxyamijidictyol - A New Antifeeding Dolastane Diterpene from the Brazilian Brown Alga Canistrocarpus cervicornis.

    PubMed

    Miguel Bianco, Éverson; Martins Francisco, Thiago; Basílio Pinheiro, Carlos; Bagueira de Vasconcellos Azeredo, Rodrigo; Laneuville Teixeira, Valéria; Crespo Pereira, Renato

    2015-11-01

    Chemical investigation of the CH2 Cl2 crude extract from the brown alga Canistrocarpus cervicornis (Dictyotaceae) led to isolation of one new (1) and four previously reported dolastane diterpenes (2-5). Their structures were characterized by 1D- and 2D-NMR spectroscopic techniques, including a full single crystal X-ray diffraction analysis for 1, 2, and 4. In addition, the new structure 1 was assayed as chemical defense inhibiting the feeding by the sea urchin Lytechinus variegatus. This study constitutes an additional report broadening the known spectrum of action and defensive roles of secondary metabolites of the C. cervicornis and Dictyotales species.

  20. Synthetic studies on neoclerodane diterpenes from Salvia splendens: oxidative modifications of ring A.

    PubMed

    Fontana, Gianfranco; Savona, Giuseppe; Rodríguez, Benjamín; Dersch, Christina M; Rothman, Richard B; Prisinzano, Thomas E

    2009-02-21

    Salvinorin A (1), a neoclerodane diterpene from the hallucinogenic mint Salvia divinorum, is the only known naturally occurring non-nitrogenous and specific κ-opioid agonist. Some oxidative modifications of the A ring in the congeners of 1 isolated from Salvia splendens salviarin, splenolide B, splendidin and in the non-natural 8-epi-salviarin gave new derivatives, some of which were tested as agonists at opioid receptors. However, none of these compounds were active. The presence of the C-18, C-19 lactone could be at the origin of the observed lack of binding affinity.

  1. Synthetic studies on neoclerodane diterpenes from Salvia splendens: oxidative modifications of ring A

    PubMed Central

    Fontana, Gianfranco; Savona, Giuseppe; Rodríguez, Benjamín; Dersch, Christina M.; Rothman, Richard B.; Prisinzano, Thomas E.

    2011-01-01

    Salvinorin A (1), a neoclerodane diterpene from the hallucinogenic mint Salvia divinorum, is the only known naturally occurring non-nitrogenous and specific κ-opioid agonist. Some oxidative modifications of the A ring in the congeners of 1 isolated from Salvia splendens salviarin, splenolide B, splendidin and in the non-natural 8-epi-salviarin gave new derivatives, some of which were tested as agonists at opioid receptors. However, none of these compounds were active. The presence of the C-18, C-19 lactone could be at the origin of the observed lack of binding affinity. PMID:21544261

  2. Henrin A: A New Anti-HIV Ent-Kaurane Diterpene from Pteris henryi

    PubMed Central

    Li, Wan-Fei; Wang, Juan; Zhang, Jing-Jie; Song, Xun; Ku, Chuen-Fai; Zou, Juan; Li, Ji-Xin; Rong, Li-Jun; Pan, Lu-Tai; Zhang, Hong-Jie

    2015-01-01

    Henrin A (1), a new ent-kaurane diterpene, was isolated from the leaves of Pteris henryi. The chemical structure was elucidated by analysis of the spectroscopic data including one-dimensional (1D) and two-dimensional (2D) NMR spectra, and was further confirmed by X-ray crystallographic analysis. The compound was evaluated for its biological activities against a panel of cancer cell lines, dental bacterial biofilm formation, and HIV. It displayed anti-HIV potential with an IC50 value of 9.1 µM (SI = 12.2). PMID:26610490

  3. General diastereoselective synthetic approach toward isospongian diterpenes. Synthesis of (-)-marginatafuran, (-)-marginatone, and (-)-20-acetoxymarginatone.

    PubMed

    Gris, Antonio; Cabedo, Nuria; Navarro, Ismael; de Alfonso, Ignacio; Agulló, Consuelo; Abad-Somovilla, Antonio

    2012-07-06

    This work describes a synthetic approach to the carbocyclic skeleton of isospongian diterpenes that uses the commercially available monoterpene (S)-carvone as a C-ring synthon, which is incorporated into the tetracyclic isospongian framework via a C→ABC→ABCD ring annulation strategy using intramolecular Diels-Alder and ring-closing metathesis reactions. This approach has been successfully used to prepare both the title natural isospongians and several nonnatural oxygenated analogues. A preliminary evaluation of the inhibitory activity of the small collection of synthesized isospongians on the mammalian mitochondrial respiratory chain revealed that most were able to inhibit the integrated electron transfer chain (NADH oxidase activity) in the micromolar range.

  4. NMR assignments and X-ray diffraction spectra for two unusual kaurene diterpenes from Erythroxylum barbatum.

    PubMed

    dos Santos, Claudio Costa; Sousa Lima, Mary Anne; Braz-Filho, Raimundo; de Simone, Carlos Alberto; Silveira, Edilberto Rocha

    2005-12-01

    The structural characterization of two new, unusual kaurene diterpenes isolated from roots of Erythroxylum barbatum is described. 1D NMR and several 2D shift-correlated NMR pulse sequences (1H,1H-COSY, HMQC, HMBC and NOESY) were used for structure elucidation and the unambiguous 1H and 13C chemical shifts assignments. Single crystal X-ray diffraction analysis was also used to confirm the final relative configuration of the compounds possessing the C-20 methyl and the CH2-15 methylene groups in cis-orientation.

  5. Glycosidation of Methanol with Ribose: An Interdisciplinary Undergraduate Laboratory Experiment

    ERIC Educational Resources Information Center

    Simon, Erin; Cook, Katie; Pritchard, Meredith R.; Stripe, Wayne; Bruch, Martha; Bendinskas, Kestutis

    2010-01-01

    This exercise provides students hands-on experience with the topics of glycosidation, hemiacetal and acetal formation, proton nuclear magnetic resonance ([superscript 1]H NMR) spectroscopy, and kinetic and thermodynamic product formation. In this laboratory experiment, the methyl acetal of ribose is synthesized, and the kinetic and thermodynamic…

  6. Two new indolopyridoquinazoline alkaloidal glycosides from Ranunculus ternatus.

    PubMed

    Zhang, Lin; Yang, Zhuang; Tian, Jing-Kui

    2007-08-01

    Two new indolopyridoquinazoline alkaloidal glycosides, 11-O-beta-D-glucopyranosyl rutaecarpine (ternatoside C) and 11-O-alpha-L-rhamnosyl-(1-->6)-beta-D-glucopyranosyl rutaecarpine (ternatoside D) were isolated from the roots of Ranunculus ternatus. Their structures were determined on the basis of spectroscopic and chemical methods.

  7. Spirostanol glycosides with hemostatic and antimicrobial activities from Trillium kamtschaticum.

    PubMed

    Chen, Yu; Ni, Wei; Yan, Huan; Qin, Xu-Jie; Khan, Afsar; Liu, Hui; Shu, Tong; Jin, Ling-Yu; Liu, Hai-Yang

    2016-11-01

    Ten spirostanol glycosides, trillikamtosides A-J, together with eleven known analogues, were isolated from the hemostatic fraction of the 75% aqueous EtOH extract of the whole herbs of Trillium kamtschaticum. Their structures were established by extensive spectroscopic data analysis and chemical methods. The aglycones of three of these compounds had unique 3β,17α-dihydroxy-spirostanes featuring a double bond between C-4 and C-5, while two others represent a rare class of spirostanol glycosides which possess a 5(6 → 7) abeo-steroidal aglycone. All the compounds were evaluated for their hemostatic and antimicrobial activities. Three of the spirostanol glycosides exhibited induced-platelet aggregation at a concentration of 300 μg/mL with maximal induced-platelet aggregation rates of 72%, 71%, and 62% in rabbits, respectively, and their EC50 values were 492.7, 203.3, and 109.8 μM. Five of the spirostanol glycosides showed an anti-Candida albicans effect with MIC values of 21.1, 10.6, 8.8, 21.6, and 11.0 μM, respectively.

  8. New glycosides of acetophenone derivatives and phenylpropanoids from Juniperus occidentalis.

    PubMed

    Inatomi, Yuka; Murata, Hiroko; Inada, Akira; Nakanishi, Tsutomu; Lang, Frank A; Murata, Jin; Iinuma, Munekazu

    2013-04-01

    New glycosides of seven acetophenone derivatives (1-7) and two phenylpropanoids (8, 9), named juniperosides III-XI, have been isolated from the MeOH extract of the leaves and stems of Juniperus occidentalis Hook. (Cupressaceae), together with eleven other known compounds. The structures of these compounds have been successfully elucidated using a variety of spectroscopic techniques.

  9. A New Flavanonol Glycoside from Adansonia digitata Roots.

    PubMed

    Chauhan, J S; Kumar, S; Chaturvedi, R

    1984-02-01

    A new flavanonol glycoside isolated from the roots of Adansonia digitata has been characterised as 3,7-dihydroxy flavan-4-one-5-O-beta- D-galactopyranosyl (1 --> 4)-beta- D-glucopyranoside on the basis of degradation, spectral and chemical studies.

  10. Flavonol glycosides from distilled petals of Rosa damascena Mill.

    PubMed

    Schiber, Andreas; Mihalev, Kiril; Berardini, Nicolai; Mollov, Plamen; Carle, Reinhold

    2005-01-01

    Flavonol glycosides were extracted from petals of Rosa damascena Mill. after industrial distillation for essential oil recovery and characterized by high-performance liquid chromatography-electrospray ionization mass spectrometry. Among the 22 major compounds analyzed, only kaempferol and quercetin glycosides were detected. To the best of our knowledge, the presence of quercetin 3-O-galactoside and quercetin 3-O-xyloside has so far not been reported within the genus Rosa. In addition, based on their fragmentation patterns, several acylated quercetin and kaempferol glycosides, some of them being disaccharides, were identified for the first time. The kaempferol glycosides, along with the kaempferol aglycone, accounted for 80% of the total compounds that were quantified, with kaempferol 3-O-glucoside being the predominant component. The high flavonol content of approximately 16 g/kg on a dry weight basis revealed that distilled rose petals represent a promising source of phenolic compounds which might be used as functional food ingredients, as natural antioxidants or as color enhancers.

  11. Three new hecogenin glycosides from fermented leaves of Agave americana.

    PubMed

    Jin, Jian-Ming; Liu, Xi-Kui; Yang, Chong-Ren

    2003-06-01

    Eight steroidal compounds, including three new hecogenin glycosides, agamenosides D-F, were isolated from the fermented leaves of Agave americana. The structures of the new steroidal saponins were elucidated by spectroscopic data and chemical methods. The activity of the isolated compounds on deformations of mycelia germinated from conidia of Pyricularia oaryzae P-2b was evaluated.

  12. Triterpenoid glycosides from the leaves of Meliosma henryi.

    PubMed

    Alabdul Magid, Abdulmagid; Morjani, Hamid; Harakat, Dominique; Madoulet, Claudie; Dumontet, Vincent; Lavaud, Catherine

    2015-01-01

    Seven triterpenoid glycosides, named meliosmosides A-G, were isolated from the leaves of Meliosma henryi Diels (Sabiaceae). Their structures were elucidated by different spectroscopic methods including 1D and 2D NMR experiments as well as HRESIMS analysis. Isolated compounds were evaluated for their cytotoxic activity against KB cell line.

  13. On the differences between ouabain and digitalis glycosides.

    PubMed

    Fuerstenwerth, Hauke

    2014-01-01

    Digoxin and digitoxin are widely used in the treatment of heart diseases. The exact mechanism of action of these drugs has remained an enigma. Ouabain has become the standard tool to investigate the mode of action of cardiotonic steroids, and results with ouabain are regarded as generally valid for all cardiac glycosides. However, there are marked differences between the effects of ouabain and digitalis glycosides. Ouabain has a different therapeutic profile from digitalis derivatives. Unlike digitalis glycosides, ouabain has a fast onset of action and stimulates myocardial metabolism. The inotropic effect of cardiotonic steroids is not related to inhibition of the Na-K-ATPase. Ouabain and digitalis derivatives develop their effects in different cellular spaces. Digitalis glycosides increase the intracellular calcium concentration by entering the cell interior and acting on the ryanodine receptors and by forming transmembrane calcium channels. Ouabain, by activation of the Na-K-ATPase from the extracellular side, triggers release of calcium from intracellular stores via signal transduction pathways and activates myocardial metabolism. These data no longer support the concept that all cardiotonic steroids exhibit their therapeutic effects by partial inhibition of the ion-pumping function of the Na-K-ATPase. Hence, it is suggested that this deeply rooted dogma be revised.

  14. 4'-Methoxyphenacyl-Assisted Synthesis of β-Kdo Glycosides.

    PubMed

    Mazur, Marcelina; Barycza, Barbara; Andriamboavonjy, Hanitra; Lavoie, Serge; Tamigney Kenfack, Marielle; Laroussarie, Anaïs; Blériot, Yves; Gauthier, Charles

    2016-11-18

    3-Deoxy-β-d-manno-oct-2-ulosonic acid (β-Kdo) glycosides are mainly found in capsular polysaccharides and extracellular exopolysaccharides from Gram-negative bacteria. These compounds have profound biological implications in immune response and act as virulence factors. We have developed a novel methodology for the stereoselective synthesis of β-Kdo glycosides via the use of a 4'-methoxyphenacyl (Phen) auxiliary group at the C1 position of a peracetylated β-Kdo thioglycoside. Under the promotion of NIS/AgOTf in acetonitrile, a series of Kdo glycosides was synthesized in good yield and β-selectivity while minimizing the formation of undesirable glycals. Stereoselectivity of the glycosylation was shown to be modulated by various factors such as promotor, solvent, anomeric ratio of donor, nature of acceptor, and Phen substitution. Chemoselective cleavage of the Phen group was performed under the action of Zn/HOAc. DFT calculations together with experimental results suggested that α-triflate and a six-membered α-spiroPhen are plausible intermediates of the reaction, accounting for the enhanced formation of β-Kdo glycosides. The developed methodology could be applied to the synthesis of β-Kdo-containing glycans from pathogenic bacteria.

  15. Structural revision of two flavanonol glycosides from Smilax glabra.

    PubMed

    Zhou, Xiang; Xu, Qiang; Li, Jian-Xin; Chen, Ting

    2009-05-01

    The structures of two flavanonol glycosides isolated from Smilax glabra, named smitilbin and neosmitilbin, have been revised to isoastilbin and neoastilbin, respectively. The revised structures were determined based on intensive studies of chemical interconversion, NMR spectroscopy, and X-ray crystallographic analysis. The latest NMR data were also summarized.

  16. Curation of characterized glycoside hydrolases of Fungal origin

    PubMed Central

    Murphy, Caitlin; Powlowski, Justin; Wu, Min; Butler, Greg; Tsang, Adrian

    2011-01-01

    Fungi produce a wide range of extracellular enzymes to break down plant cell walls, which are composed mainly of cellulose, lignin and hemicellulose. Among them are the glycoside hydrolases (GH), the largest and most diverse family of enzymes active on these substrates. To facilitate research and development of enzymes for the conversion of cell-wall polysaccharides into fermentable sugars, we have manually curated a comprehensive set of characterized fungal glycoside hydrolases. Characterized glycoside hydrolases were retrieved from protein and enzyme databases, as well as literature repositories. A total of 453 characterized glycoside hydrolases have been cataloged. They come from 131 different fungal species, most of which belong to the phylum Ascomycota. These enzymes represent 46 different GH activities and cover 44 of the 115 CAZy GH families. In addition to enzyme source and enzyme family, available biochemical properties such as temperature and pH optima, specific activity, kinetic parameters and substrate specificities were recorded. To simplify comparative studies, enzyme and species abbreviations have been standardized, Gene Ontology terms assigned and reference to supporting evidence provided. The annotated genes have been organized in a searchable, online database called mycoCLAP (Characterized Lignocellulose-Active Proteins of fungal origin). It is anticipated that this manually curated collection of biochemically characterized fungal proteins will be used to enhance functional annotation of novel GH genes. Database URL: http://mycoCLAP.fungalgenomics.ca/ PMID:21622642

  17. A new C-methylated flavonoid glycoside from Pinus densiflora.

    PubMed

    Jung, M J; Choi, J H; Chung, H Y; Jung, J H; Choi, J S

    2001-12-01

    A new C-methyl flavonol glycoside, 5,7,8,4'-tetrahydroxy-3-methoxy-6-methylflavone 8-O-beta-D-glucopyranoside (1), has been isolated from the needles of Pinus densiflora, together with kaempferol 3-O-beta-(6"-acetyl)-galactopyranoside.

  18. A new phenylpropanoid glycoside from Jasminum subtriplinerve Blume.

    PubMed

    Huong, Nguyen Thi Hong; Cu, Nguyen Khac Quynh; Quy, Trinh Van; Zidorn, Christian; Ganzera, Markus; Stuppner, Hermann

    2008-01-01

    From the ethyl acetate extract of the aerial parts of Jasminum subtriplinerve Blume (Oleaceae), 6'-O-menthiafoloylverbascoside (1), rutin (2), isoverbascoside (4), isooleoverbascoside (6), apiosylverbascoside (7), astragalin (9), isoquercitrin (10), and verbascoside (11) were isolated. Their structures were elucidated by extensive MS and NMR spectroscopy. Amongst 6'-O-menthiafoloylverbascoside (1) is a new phenylpropanoid glycoside.

  19. The cardiac glycoside-receptor system in the human heart.

    PubMed

    Erdmann, E; Brown, L

    1983-01-01

    Specific binding sites have been demonstrated to exist in the heart for several drugs and hormones such as beta-blocking agents, cardiac glycosides, catecholamines, insulin, glucagon and acetylcholine. The specific binding sites for cardiac glycosides in the human heart have certain properties which make it likely that they are the pharmacological receptors for the therapeutic and toxic actions of digitalis glycosides: they are located in the cell membrane and bind cardioactive steroids reversibly with high affinity: half-maximal receptor binding occurs at approximately 2 nM (approximately 1.5 ng/ml) for digoxin; potassium decreases receptor affinity, calcium increases it; specific binding of ouabain, digoxin or digitoxin is related to inhibition of (Na+ + K+)-ATPase activity--which is supposed to be the receptor enzyme for cardiac glycosides. Human left ventricle contains approximately 1.5 x 10(14) binding sites/g wet weight, right ventricle approximately 0.9 x 10(14). In disease the number of receptors may decrease (hypothyroid states, myocardial infarction) or increase (hyperthyroidism, chronic hypokalaemia). Certain drugs (such as phenytoin) or different temperatures or pH changes cause a change in digitalis-receptor affinity. Thus, the number of receptors and possibly their properties are subject to regulation in clinically relevant situations. Further investigations will probably reveal those pathophysiological states, which allow the explanation of toxicity or digitalis refractoriness.

  20. Acylated pregnane glycosides from Caralluma tuberculata and their antiparasitic activity.

    PubMed

    Abdel-Sattar, Essam; Harraz, Fathalla M; Al-ansari, Soliman Mohammed Abdullah; El-Mekkawy, Sahar; Ichino, Chikara; Kiyohara, Hiroaki; Ishiyama, Aki; Otoguro, Kazuhiko; Omura, Satoshi; Yamada, Haruki

    2008-08-01

    Five pregnane glycosides were isolated from Caralluma tuberculata (1-5), in addition to a known one (russelioside E, 6). The structures of the isolated compounds were elucidated by the analysis of NMR data and FAB-MS experiments. All the isolated compounds were tested for their antimalarial and antitrypanosomal activities as well as their cytotoxicity against human diploid embryonic cell line (MRC5).

  1. Photochemistry and pharmacology of 9, 19-cyclolanostane glycosides isolated from genus Cimicifuga.

    PubMed

    Su, Yang; Chi, Wen-Cheng; Wu, Lun; Wang, Qiu-Hong; Kuang, Hai-Xue

    2016-10-01

    The constituents of Cimicifuga plants have been extensively investigated, and the principal metabolites are 9, 19-cyclolanostane triterpenoid glycosides, which often exhibit extensive pharmacological activities. 9, 19-Cyclolanostane triterpenoid glycosides are distributed widely in genus Cimicifuga rather than in other members of the Ranunculaceae family. So far, more than 140 cycloartane triterpene glycosides have been isolated from Cimicifuga spp.. The aim of this review was to summarize all 9, 19-cyclolanostane triterpenoid glycosides based on the available relevant scientific literatures from 2000 to 2014. Biological studies of cycloartane triterpene glycosides from Cimicifuga spp. are also discussed.

  2. Anti-malarial, anti-algal, anti-tubercular, anti-bacterial, anti-photosynthetic, and anti-fouling activity of diterpene and diterpene isonitriles from the tropical marine sponge Cymbastela hooperi.

    PubMed

    Wright, Anthony D; McCluskey, Adam; Robertson, Mark J; MacGregor, Kylie A; Gordon, Christopher P; Guenther, Jana

    2011-01-21

    In an investigation into their potential ecological role(s), a group of mainly diterpene isonitriles, nine in total, isolated from the tropical marine sponge Cymbastela hooperi, and the sesquiterpene axisonitrile-3, isolated from the tropical marine sponge Acanthella kletra, were evaluated in a series of bioassays including anti-fouling, anti-algal, anti-photosynthetic, anti-bacterial (Gram +ve and -ve), anti-fungal, and anti-tubercular. The results of these assays showed that all of the tested compounds, with the exception of diterpene 9, were active in at least two of the applied test systems, with axisonitrile-3 (10) and diterpene isonitrile 1 being the two most active compounds overall, closely followed by diterpene isonitrile 3. Based on the results of the photosynthetic study a molecular modelling investigation was undertaken with all of the compounds used in that study. The results showed a positive correlation between reduction in photosynthetic activity and the interaction of the modelled compounds with a potential enzyme active site.

  3. 1H and 13C NMR signal assignments of a novel Baeyer-Villiger originated diterpene lactone.

    PubMed

    Vieira, Henriete S; Takahashi, Jacqueline A; Gunatilaka, A A Leslie; Boaventura, Maria Amélia D

    2006-02-01

    A highly rearranged novel dilactone was the single product isolated from Baeyer-Villiger oxidation of a norketone prepared from grandiflorenic acid, a natural kaurane diterpene. The complete 1H and 13C NMR assignment is presented for this novel compound that showed discrete in vitro antibacterial activity.

  4. Assignment of absolute configurations of highly flexible linear diterpenes from the brown alga Bifurcaria bifurcata by VCD spectroscopy.

    PubMed

    Merten, Christian; Smyrniotopoulos, Vangelis; Tasdemir, Deniz

    2015-11-21

    Correct assignment of the stereogenic centers of highly flexible linear diterpenes (LDs) is challenging. Herein we report the first application of VCD spectroscopy for the absolute configuration determination of LDs of algal origin and provide experimental and computational procedures, such as a fragmentation approach, which will facilitate the use of VCD spectroscopy for configuration assignments of LDs.

  5. Marine Diterpenes: Molecular Modeling of Thrombin Inhibitors with Potential Biotechnological Application as an Antithrombotic

    PubMed Central

    Pereira, Rebeca Cristina Costa; Lourenço, André Luiz; Terra, Luciana; Abreu, Paula Alvarez; Laneuville Teixeira, Valéria; Castro, Helena Carla

    2017-01-01

    Thrombosis related diseases are among the main causes of death and incapacity in the world. Despite the existence of antithrombotic agents available for therapy, they still present adverse effects like hemorrhagic risks which justify the search for new options. Recently, pachydictyol A, isopachydictyol A, and dichotomanol, three diterpenes isolated from Brazilian marine brown alga Dictyota menstrualis were identified as potent antithrombotic molecules through inhibition of thrombin, a key enzyme of coagulation cascade and a platelet agonist. Due to the biotechnological potential of these marine metabolites, in this work we evaluated their binding mode to thrombin in silico and identified structural features related to the activity in order to characterize their molecular mechanism. According to our theoretical studies including structure-activity relationship and molecular docking analysis, the highest dipole moment, polar surface area, and lowest electronic density of dichotomanol are probably involved in its higher inhibition percentage towards thrombin catalytic activity compared to pachydictyol A and isopachydictyol A. Interestingly, the molecular docking studies also revealed a good shape complementarity of pachydictyol A and isopachydictyol A and interactions with important residues and regions (e.g., H57, S195, W215, G216, and loop-60), which probably justify their thrombin inhibitor effects demonstrated in vitro. Finally, this study explored the structural features and binding mode of these three diterpenes in thrombin which reinforced their potential to be further explored and may help in the design of new antithrombotic agents. PMID:28335516

  6. Discovery and biological evaluation of the novel naturally occurring diterpene pepluanone as antiinflammatory agent.

    PubMed

    Corea, Gabriella; Fattorusso, Ernesto; Lanzotti, Virginia; Di Meglio, Paola; Maffia, Pasquale; Grassia, Gianluca; Ialenti, Armando; Ianaro, Angela

    2005-11-03

    From the whole plant of Euphorbia peplus L., a new diterpene based on a rare pepluane skeleton, named pepluanone (1), was isolated together with a known pepluane diterpene (2). The stereostructure of pepluanone was determined on the basis of an extensive NMR study, MS data, and chemical reaction. The ability of these compounds to act as antiinflammatory agents has been evaluated for the first time by in vivo tests on carrageenin-induced rat paw edema, an experimental model of acute inflammation. Comparison of the bioactivity of pepluanone and compound 2 in terms of chemical structure, evidenced the high efficiency of pepluanone and the absence of appreciable activity for compound 2, thus giving a first insight into the structure-activity relationship. Further in vitro experiments performed on pepluanone let us hypothesize that its activity could be explained in reducing the production of nitric oxide, prostaglandin E(2), and TNF-alpha by inhibiting the expression of inducible nitric oxide synthase, cyclooxygenase-2, and TNF-alpha mRNA through the down-regulation of NF-kappaB binding activity.

  7. The Therapeutic Potential of Rosemary (Rosmarinus officinalis) Diterpenes for Alzheimer's Disease

    PubMed Central

    Habtemariam, Solomon

    2016-01-01

    Rosemary (Rosmarinus officinalis L.) is one of the most economically important species of the family Lamiaceae. Native to the Mediterranean region, the plant is now widely distributed all over the world mainly due to its culinary, medicinal, and commercial uses including in the fragrance and food industries. Among the most important group of compounds isolated from the plant are the abietane-type phenolic diterpenes that account for most of the antioxidant and many pharmacological activities of the plant. Rosemary diterpenes have also been shown in recent years to inhibit neuronal cell death induced by a variety of agents both in vitro and in vivo. The therapeutic potential of these compounds for Alzheimer's disease (AD) is reviewed in this communication by giving special attention to the chemistry of the compounds along with the various pharmacological targets of the disease. The multifunctional nature of the compounds from the general antioxidant-mediated neuronal protection to other specific mechanisms including brain inflammation and amyloid beta (Aβ) formation, polymerisation, and pathologies is discussed. PMID:26941822

  8. Marine Diterpenes: Molecular Modeling of Thrombin Inhibitors with Potential Biotechnological Application as an Antithrombotic.

    PubMed

    Pereira, Rebeca Cristina Costa; Lourenço, André Luiz; Terra, Luciana; Abreu, Paula Alvarez; Laneuville Teixeira, Valéria; Castro, Helena Carla

    2017-03-20

    Thrombosis related diseases are among the main causes of death and incapacity in the world. Despite the existence of antithrombotic agents available for therapy, they still present adverse effects like hemorrhagic risks which justify the search for new options. Recently, pachydictyol A, isopachydictyol A, and dichotomanol, three diterpenes isolated from Brazilian marine brown alga Dictyota menstrualis were identified as potent antithrombotic molecules through inhibition of thrombin, a key enzyme of coagulation cascade and a platelet agonist. Due to the biotechnological potential of these marine metabolites, in this work we evaluated their binding mode to thrombin in silico and identified structural features related to the activity in order to characterize their molecular mechanism. According to our theoretical studies including structure-activity relationship and molecular docking analysis, the highest dipole moment, polar surface area, and lowest electronic density of dichotomanol are probably involved in its higher inhibition percentage towards thrombin catalytic activity compared to pachydictyol A and isopachydictyol A. Interestingly, the molecular docking studies also revealed a good shape complementarity of pachydictyol A and isopachydictyol A and interactions with important residues and regions (e.g., H57, S195, W215, G216, and loop-60), which probably justify their thrombin inhibitor effects demonstrated in vitro. Finally, this study explored the structural features and binding mode of these three diterpenes in thrombin which reinforced their potential to be further explored and may help in the design of new antithrombotic agents.

  9. Semi-synthesis of oxygenated dolabellane diterpenes with highly in vitro anti-HIV-1 activity.

    PubMed

    Pardo-Vargas, Alonso; Ramos, Freddy A; Cirne-Santos, Claudio Cesar; Stephens, Paulo Roberto; Paixão, Izabel Christina Palmer; Teixeira, Valeria Laneuville; Castellanos, Leonardo

    2014-09-15

    Research on dolabellane diterpenes of brown algae Dictyota spp. has shown that these diterpenoids have strong anti-HIV-1 activity, but there are not data about antiviral activity of dolabellane diterpenes isolated from octocorals, which are antipodes of those isolated from the brown algae. Dolabellanes 13-keto-1(R),11(S)-dolabella-3(E),7(E),12(18)-triene (1) and β-Araneosene (2) were isolated from the Caribbean octocoral Eunicea laciniata, and both showed low anti-HIV-1 activity and low toxicity. Since it was shown that oxygenated dolabellanes from algae have better anti-HIV-1 activity, in this work some derivatives of the main dolabellane of E. laciniata1 were obtained by epoxidation (3), epoxide opening (4), and allylic oxidation (5). The derivatives showed significant improvement in the anti-HIV-1potency (100-fold), being compounds 3 and 5 the most active ones. Their high antiviral activities, along with their low cytotoxicity, make them promissory antiviral compounds; and it is worth noting that the absolute configuration at the ring junction in the dolabellane skeleton does not seem to be determinant in the antiviral potency of these diterpeneoids.

  10. Divergent synthesis and chemical reactivity of bicyclic lactone fragments of complex rearranged spongian diterpenes.

    PubMed

    Schnermann, Martin J; Beaudry, Christopher M; Genung, Nathan E; Canham, Stephen M; Untiedt, Nicholas L; Karanikolas, Breanne D W; Sütterlin, Christine; Overman, Larry E

    2011-11-02

    The synthesis and direct comparison of the chemical reactivity of the two highly oxidized bicyclic lactone fragments found in rearranged spongian diterpenes (8-substituted 6-acetoxy-2,7-dioxabicyclo[3.2.1]octan-3-one and 6-substituted 7-acetoxy-2,8-dioxabicyclo[3.3.0]octan-3-one) are reported. Details of the first synthesis of the 6-acetoxy-2,7-dioxabicyclo[3.2.1]octan-3-one ring system, including an examination of several possibilities for the key bridging cyclization reaction, are described. In addition, the first synthesis of 7-acetoxy-2,8-dioxabicyclo[3.3.0]octanones containing quaternary carbon substituents at C6 is disclosed. Aspects of the chemical reactivity and Golgi-modifying properties of these bicyclic lactone analogs of rearranged spongian diterpenes are also reported. Under both acidic and basic conditions, 8-substituted 2,7-dioxabicyclo[3.2.1]octanones are converted to 6-substituted-2,8-dioxabicyclo[3.3.0]octanones. Moreover, these dioxabicyclic lactones react with primary amines and lysine side chains of lysozyme to form substituted pyrroles, a conjugation that could be responsible for the unique biological properties of these compounds. These studies demonstrate that acetoxylation adjacent to the lactone carbonyl group, in either the bridged or fused series, is required to produce fragmented Golgi membranes in the pericentriolar region that is characteristic of macfarlandin E.

  11. Sweet antibiotics - the role of glycosidic residues in antibiotic and antitumor activity and their randomization.

    PubMed

    Kren, Vladimír; Rezanka, Tomás

    2008-08-01

    A large number of antibiotics are glycosides. In numerous cases the glycosidic residues are crucial to their activity; sometimes, glycosylation only improves their pharmacokinetic parameters. Recent developments in molecular glycobiology have improved our understanding of aglycone vs. glycoside activities and made it possible to develop new, more active or more effective glycodrugs based on these findings - a very illustrative recent example is vancomycin. The majority of attention has been devoted to glycosidic antibiotics including their past, present, and probably future position in antimicrobial therapy. The role of the glycosidic residue in the biological activity of glycosidic antibiotics, and the attendant targeting and antibiotic selectivity mediated by glycone and aglycone in antibiotics some antitumor agents is discussed here in detail. Chemical and enzymatic modifications of aglycones in antibiotics, including their synthesis, are demonstrated on various examples, with particular emphasis on the role of specific and mutant glycosyltransferases and glycorandomization in the preparation of these compounds. The last section of this review describes and explains the interactions of the glycone moiety of the antibiotics with DNA and especially the design and structure-activity relationship of glycosidic antibiotics, including their classification based on their aglycone and glycosidic moiety. The new enzymatic methodology 'glycorandomization' enabled the preparation of glycoside libraries and opened up new ways to prepare optimized or entirely novel glycoside antibiotics.

  12. New pregnane and phenolic glycosides from Solenostemma argel.

    PubMed

    Ounaissia, Karima; Pertuit, David; Mitaine-Offer, Anne-Claire; Miyamoto, Tomofumi; Tanaka, Chiaki; Delemasure, Stéphanie; Dutartre, Patrick; Smati, Dalila; Lacaille-Dubois, Marie-Aleth

    2016-10-01

    From the aerial parts, pericarps and roots of Solenostemma argel, three new pregnane glycosides (1-3) with two known ones and a new phenolic glycoside (4) have been isolated. Their structures were established by extensive 1D - and 2D NMR and mass spectroscopic analysis. The cytotoxicity of all compounds was evaluated against two human tumor cell lines (SW 480, MCF-7), but none of them was active in the concentration range 0.9-59.0μM. Compounds 2 and the known argeloside F at non toxic concentrations for the PBMCs (27.3μM and 27.6μM, respectively) significantly decreased the Il-1β production by LPS-stimulated PBMCs. All isolated compounds showed a significant antioxidant potential with ORAC values in the concentration range 3481-9617μmoleq. Trolox/100g.

  13. Determination of catechins and flavonol glycosides in Chinese tea varieties.

    PubMed

    Wu, Chunyan; Xu, Hairong; Héritier, Julien; Andlauer, Wilfried

    2012-05-01

    A standardised profiling method based on high performance liquid chromatography combined with ultraviolet (UV) and mass spectrometric detection (MS) was established to analyse the phenolic compounds of selected tea varieties used for manufacturing of green, black and oolong teas. The composition and content of 24 tea constituents were analysed, including catechins, flavonol and flavones glycosides, phenolic acids and purine alkaloids. Each tea variety had a unique chemical profile. The compositions of catechins were lower in the tea varieties for green tea manufacturing, while the content of myricetin glycosides was the lowest in the tea variety for oolong tea manufacturing. The content of individual phenolic compounds in the selected tea varieties is highly variable. However, the content of total catechins is proposed to be helpful to classify tea according to the future application as non fermented green and fermented oolong or black tea.

  14. Four new neuroprotective iridoid glycosides from Scrophularia buergeriana roots.

    PubMed

    Kim, So Ra; Lee, Ki Yong; Koo, Kyung Ah; Sung, Sang Hyun; Lee, Na-Gyong; Kim, Jinwoong; Kim, Young Choong

    2002-11-01

    Four new iridoid glycosides were isolated from a 90% MeOH extract of Scrophularia buergeriana roots and characterized as 8-O-E-p-methoxycinnamoylharpagide (1), 8-O-Z-p-methoxycinnamoylharpagide (2), 6'-O-E-p-methoxycinnamoylharpagide (3), and 6'-O-Z-p-methoxycinnamoylharpagide (4), respectively. In addition, three known iridoids were identified as E-harpagoside (5), Z-harpagoside (6), and harpagide (7). Compounds 1-7 significantly attenuated glutamate-induced neurotoxicity when added to primary cultures of rat cortical cells at concentrations ranging from 100 nM to 10 microM. The results obtained indicate that the iridoid glycosides isolated from S. buergeriana have significant protective effects against glutamate-induced neurodegeneration in primary cultures of rat cortical neurons.

  15. Synthetic Glycosides and Glycoconjugates of Low Molecular Weight Natural Products.

    PubMed

    Grynkiewicz, G; Szeja, W

    2016-01-01

    Enzymatically controlled transfer of saccharide moieties constitutes a fundamental biological process, essential for both primary and secondary metabolism. Natural products, including countless glycosides, with a rich tradition of use in ethnopharmacology, remain a prime source of inspiration for medicinal chemistry and molecular pharmacology, but their availability from biological sources is usually scarce, hampering attempts at application for new drug discovery and development. Chemical glycosylation on the other hand, although continuously undergoing sophisticated mechanistic studies, has nevertheless already matured as a set of methods which are able to provide substantial amounts of pure chemical entities: natural glycosides, as well as their congeners and mimics, necessary for the study of biological activity in quality assurance systems and required for drug development by pharmaceutical regulations. The paper presents a review of natural products and their analogues glycosylation, in a set of arbitrary selected examples, supplemented with comments on general advances in chemical glycosylation methodology and their applicability for particular categories of secondary metabolites.

  16. New terpenoid glycosides obtained from Rosmarinus officinalis L. aerial parts.

    PubMed

    Zhang, Yi; Adelakun, Tiwalade Adegoke; Qu, Lu; Li, Xiaoxia; Li, Jian; Han, Lifeng; Wang, Tao

    2014-12-01

    Five new terpenoid glycosides, named as officinoterpenosides A₁ (1), A₂ (2), B (3), C (4), and D (5), together with 11 known ones, (1S,4S,5S)-5-exo-hydrocamphor 5-O-β-D-glucopyranoside (6), isorosmanol (7), rosmanol (8), 7-methoxyrosmanol (9), epirosmanol (10), ursolic acid (11), micromeric acid (12), oleanolic acid (13), niga-ichigoside F₁ (14), glucosyl tormentate (15), and asteryunnanoside B (16), were obtained from the aerial parts of Rosmarinus officinalis L. Their structures were elucidated by chemical and spectroscopic methods (UV, IR, HRESI-TOF-MS, 1D and 2D NMR). Among the new ones, 1 and 2, 3 and 4 are diterpenoid and triterpenoid glycosides, respectively; and 5 is a normonoterpenoid. For the known ones, 6 was isolated from the Rosmarinus genus first, and 15, 16 were obtained from this species for the first time.

  17. Malonylated flavonol glycosides from the petals of Clitoria ternatea.

    PubMed

    Kazuma, Kohei; Noda, Naonobu; Suzuki, Masahiko

    2003-01-01

    Three flavonol glycosides, kaempferol 3-O-(2"-O-alpha-rhamnosyl-6"-O-malonyl)-beta-glucoside, quercetin 3-O-(2"-O-alpha-rhamnosyl-6"-O-malonyl)-beta-glucoside, and myricetin 3-O-(2",6"-di-O-alpha-rhamnosyl)-beta-glucoside were isolated from the petals of Clitoria ternatea cv. Double Blue, together with eleven known flavonol glycosides. Their structures were identified using UV, MS, and NMR spectroscopy. They were characterized as kaempferol and quercetin 3-(2(G)- rhamnosylrutinoside)s, kaempferol, quercetin, and myricetin 3-neohesperidosides, 3-rutinosides, and 3-glucosides in the same tissue. In addition, the presence of myricetin 3-O-(2"-O-alpha-rhamnosyl-6"-O-malonyl)-beta-glucoside was inferred from LC/MS/MS data for crude petal extracts. The flavonol compounds identified in the petals of C. ternatea differed from those reported in previous studies.

  18. Coumarins of Matricaria chamomilla L.: aglycones and glycosides.

    PubMed

    Petruľová-Poracká, Veronika; Repčák, Miroslav; Vilková, Mária; Imrich, Ján

    2013-11-01

    The identity and quantity of coumarin-like compounds in leaves and anthodia of Matricaria chamomilla L. were studied by LC-DAD and NMR. So far, two monosubstituted coumarins, herniarin and umbelliferone, and two herniarin precursors were identified therein. In this paper, two other coumarin glycosides and one aglycone were confirmed. Skimmin (umbelliferone-7-O-β-d-glucoside), daphnin (daphnetin-7-O-β-d-glucoside) and daphnetin (7,8-dihydroxycoumarin) were found for the first time in diploid and tetraploid leaves and anthodia of M. chamomilla L. Daphnetin is known as a strong sensitizer, so this compound and its glycosidic derivative can contribute to the allergic potential of chamomile. Commercial chamomile preparations were tested for their presence.

  19. Capillary electrophoresis of neutral carbohydrates: mono-, oligosaccharides, glycosides.

    PubMed

    Campa, Cristiana; Rossi, Marco

    2008-01-01

    This chapter reports an overview of the recent advances in the analysis of neutral sugars by capillary electrophoresis (CE); furthermore, some relevant reviews and research articles in the field are tabulated. Comparison of CE with chromatography is also presented, with special attention to separation efficiency and sensitivity. The main routes aimed at pretreatment and CE analysis of uncharged mono-, oligosaccharides, and glycosides are described. Representative examples of such procedures are reported in detail, upon describing robust methodologies for the study of (1) neutral mono- and oligosaccharides derivatized by reductive amination and by formation of glycosylamines; (2) underivatized mono- and di-saccharides analyzed using highly alkaline buffers; and (3) anomeric couples of glycosides separated using borate-based buffers.

  20. Two new pregnane glycoside diesters from Caralluma russeliana.

    PubMed

    Abdel-Mogib, Mamdouh; Raghib, Hanaa M

    2013-01-01

    Two new pregnane glycoside diesters, 1 and 2, in addition to two triterpenoids, 3 and 4, and two sterols, 5 and 6 were isolated and identified from Caralluma russeliana (family Asclepiadaceae). The new pregnane glycosides, 14β-benzoyloxy-15β-isovaleroyloxy-16α-hydroxypregn-20-on-3-O-[β-D-3-O-methyl-6-deoxyoleandrosopyranosyl-(1 → 4)-β-D-cymaropyranosyl-(1 → 4)-β-D-cymaropyranoside] (1) and 14β-isovaleroyloxy-15β-benzoyloxy-16α-hydroxypregn-20-on-3-O-[β-D-3-O-methyl-6-deoxyoleandrosopyranosyl-(1 → 4)-β-D-cymaropyranosyl-(1 → 4)-β-D-cymaropyranoside] (2), are different from those isolated previously from the same species in the sugar moiety, in being diester, in being 20-one and in being 5,6 saturated by hydrogen. The isolated compounds were identified on the basis of spectral data.

  1. Acylated quercetagetin glycosides with antioxidant activity from Tagetes maxima.

    PubMed

    Parejo, Irene; Bastida, Jaume; Viladomat, Francesc; Codina, Carles

    2005-10-01

    The fractionation of a methanolic extract of Tagetes maxima guided for antioxidant activity resulted in the isolation of three acylated quercetagetin glycosides, quercetagetin-7-O-(6-O-caffeoyl-beta-D-glucopyranoside), quercetagetin-7-O-(6-O-p-coumaroyl-beta-D-glucopyranoside) and quercetagetin-7-O-(6-O-galloyl-beta-D-glucopyranoside), as well as four known flavonoid glycosides. The structural elucidation was accomplished by spectroscopic methods (ESI-MS/MS and NMR). The antioxidant activity of fractions and isolated compounds was determined by checking the scavenging activity against three different radicals: 2,2-diphenyl-1-picrylhydrazyl free radical (DPPH*), hydroxyl (*OH), and superoxide (O2*-). The three isolated compounds exhibited a high radical scavenging activity in comparison with reference compounds.

  2. Two new flavonol glycosides from Gymnema sylvestre and Euphorbia ebracteolata.

    PubMed

    Liu, Xin; Ye, Wencai; Yu, Biao; Zhao, Shouxun; Wu, Houming; Che, Chuntao

    2004-03-15

    Two new flavonol glycosides, namely kaempferol 3-O-beta-D-glucopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-galactopyranoside (1) and quercetin 3-O-6"-(3-hydroxyl-3-methylglutaryl)-beta-D-glucopyranoside (2), have been isolated from the aerial parts of Gymnema sylvestre and Euphorbia ebracteolata, respectively. Their structures were determined on the basis of chemical and spectroscopic methods.

  3. Two new lignan glycosides from the fruits of Pyrus ussuriensis.

    PubMed

    Zhao, Ze-Qing; Su, Yan-Fang; Yang, Fei; Gao, Xiu-Mei; Li, Tian-Xiang

    2016-12-01

    Two new lignan glycosides, ussuriensislignan A (1) and ussuriensislignan B (2), together with seventeen known compounds (3-19), were isolated from the fruits of Pyrus ussuriensis. Their structures were determined by various spectroscopic methods. This is the first report of the isolation of lignans (compounds 1-3) from the genus Pyrus, and compounds 3-6, 12-16 were reported from Pyrus for the first time.

  4. A new lignan glycoside from the rhizomes of Imperata cylindrica.

    PubMed

    Lee, Dae-Young; Han, Kyung-Min; Song, Myoung-Chong; Lee, Do-Gyeong; Rho, Yeong-Deok; Baek, Nam-In

    2008-01-01

    A new lignan glycoside, 6-acetyl-1-[1,3-(4,4'-dihydroxy-3,3'-dimethoxy-beta-truxinyl)-beta-d-fructofuranosyl]-alpha-d-glucopyranoside (1), named impecyloside, was isolated from the rhizomes of Imperata cylindrica. The structure of the compound was determined by spectroscopic data including FABMS, UV, IR, 1H NMR and 13C NMR (DEPT) and 2D NMR (COSY, HSQC, HMBC).

  5. A novel cytotoxic flavonoid glycoside from Physalis angulata.

    PubMed

    Ismail, N; Alam, M

    2001-08-01

    A new flavonol glycoside, myricetin 3-O-neohesperidoside (1) was isolated from a cytotoxic MeOH extract of the leaves of Physalis angulata. Compound 1 showed remarkable cytotoxicity in vitro against murine leukemia cell line P-388, epidermoid carcinoma of the nasopharynx KB-16 cells, and lung adenocarcinoma A-549 with ED(50) values of 0.048, 0.50 and 0.55 microg ml(-1), respectively.

  6. Two new monoterpenoid glycosides from Mentha spicata L.

    PubMed

    Zheng, Jian; Wu, Li-Jun; Zheng, Lu; Wu, Bin; Song, Ai-Hua

    2003-03-01

    Two new monoterpenoid glycosides, spicatoside A and spicatoside B, were isolated from the whole herbs of Mentha spicata L. which have anti-inflammatory and hemostatic activities. Their structures have been determined on the basis of spectral and chemical analysis. They are (+)-5-[1-(beta-D-glucopyranosyloxymethyl)ethenyl]-2-methyl-2-cyclohexen-1-one (1), and (-)-5-[[2-(beta-D-glucopyranosyloxy)-1-hydroxy-l-methyl]ethyl]-2-methyl-2-cyclohexen-1-one (2).

  7. New phenolic glycosides from the seeds of Cucurbita moschata.

    PubMed

    Li, Fa-Sheng; Dou, De-Qiang; Xu, Liang; Chi, Xiao-Feng; Kang, Ting-Guo; Kuang, Hai-Xue

    2009-07-01

    Two new phenolic glycosides were isolated from the seeds of Cucurbita moschata. Their structures were elucidated as (2-hydroxy)phenylcarbinyl 5-O-benzoyl-beta-D-apiofuranosyl(1-->2)-beta-D-glucopyranoside (1) and 4-beta-D-(glucopyranosyl hydroxymethyl)phenyl 5-O-benzoyl-beta-D-apiofuranosyl(1-->2)-beta-D-glucopyranoside (2) on the basis of spectroscopic analysis and chemical evidence.

  8. Antitrypanosomal activity of some pregnane glycosides isolated from Caralluma species.

    PubMed

    Abdel-Sattar, Essam; Shehab, Naglaa G; Ichino, Chikara; Kiyohara, Hiroaki; Ishiyama, Aki; Otoguro, Kazuhiko; Omura, Satoshi; Yamada, Haruki

    2009-06-01

    Pregnane glycosides previously isolated from genus Caralluma (C. Penicillata, C. tuberculata and C. russelliana) were tested for their antitrypanosomal activity. Penicilloside E showed the highest antitrypanosomal activity (IC(50) 1.01 microg/ml) followed by caratuberside C (IC(50) 1.85 microg/ml), which exhibited the highest selectivity index (SI 12.04). It was noticed that acylation is required for the antitrypanosomal activity while glycosylation at C-20 has no significant effect on the activity.

  9. Antifungal activity of steroidal glycosides from Yucca gloriosa L.

    PubMed

    Favel, A; Kemertelidze, E; Benidze, M; Fallague, K; Regli, P

    2005-02-01

    The antifungal activity of a crude steroidal glycoside extract from Yucca gloriosa flowers, named alexin, was investigated in vitro against a panel of human pathogenic fungi, yeasts as well as dermatophytes and filamentous species. The minimal inhibitory concentration (MIC) was determined by an agar dilution method. Alexin had a broad spectrum of antifungal activity, found to reside entirely in the spirostanoid fraction. The major tigogenyl glycosides, yuccaloeside B and yuccaloeside C, exhibited MICs between 0.39 and 6.25 microg[sol ]mL for all the tested yeast strains except for two (C. lusitaniae and C. kefyr). They were also active against several clinical Candida isolates known to be resistant to the usual antifungal agents. The MICs for the dermatophytes were between 0.78 and 12.5 microg[sol ]mL. The most sensitive filamentous species was A. fumigatus (MIC = 1.56 microg[sol ]mL). For most of the strains, the MICs of both glycosides were similar to those of the reference antifungal agent.

  10. Enzymatic Biosynthesis of Novel Resveratrol Glucoside and Glycoside Derivatives

    PubMed Central

    Pandey, Ramesh Prasad; Parajuli, Prakash; Shin, Ju Yong; Lee, Jisun; Lee, Seul; Hong, Young-Soo; Park, Yong Il; Kim, Joong Su

    2014-01-01

    A UDP glucosyltransferase from Bacillus licheniformis was overexpressed, purified, and incubated with nucleotide diphosphate (NDP) d- and l-sugars to produce glucose, galactose, 2-deoxyglucose, viosamine, rhamnose, and fucose sugar-conjugated resveratrol glycosides. Significantly higher (90%) bioconversion of resveratrol was achieved with α-d-glucose as the sugar donor to produce four different glucosides of resveratrol: resveratrol 3-O-β-d-glucoside, resveratrol 4′-O-β-d-glucoside, resveratrol 3,5-O-β-d-diglucoside, and resveratrol 3,5,4′-O-β-d-triglucoside. The conversion rates and numbers of products formed were found to vary with the other NDP sugar donors. Resveratrol 3-O-β-d-2-deoxyglucoside and resveratrol 3,5-O-β-d-di-2-deoxyglucoside were found to be produced using TDP-2-deoxyglucose as a donor; however, the monoglycosides resveratrol 4′-O-β-d-galactoside, resveratrol 4′-O-β-d-viosaminoside, resveratrol 3-O-β-l-rhamnoside, and resveratrol 3-O-β-l-fucoside were produced from the respective sugar donors. Altogether, 10 diverse glycoside derivatives of the medically important resveratrol were generated, demonstrating the capacity of YjiC to produce structurally diverse resveratrol glycosides. PMID:25239890

  11. Identification of UV-Induced Diterpenes Including a New Diterpene Phytoalexin, Phytocassane F, from Rice Leaves by Complementary GC/MS and LC/MS Approaches.

    PubMed

    Horie, Kiyotaka; Inoue, Yasuno; Sakai, Miki; Yao, Qun; Tanimoto, Yosuke; Koga, Jinichiro; Toshima, Hiroaki; Hasegawa, Morifumi

    2015-04-29

    Rice phytoalexins are regarded as one of the most important weapons against pathogenic microorganisms. We attempted to identify novel phytoalexins and their derivatives using GC/MS and LC/MS analyses. Diterpene derivatives, 9β-pimara-7,15-diene-3β,6β,19-triol, 1, stemar-13-en-2α-ol, 2, and 1α,2α-dihydroxy-ent-12,15-cassadiene-3,11-dione, 3, were isolated from UV-irradiated rice leaves by chromatographic methods. These structures were confirmed by 1D- and 2D-NMR and MS analyses. Interestingly, all three compounds were accumulated following an infection by the rice blast pathogen Magnaporthe oryzae. Compounds 1 and 2 exhibited weak antifungal activity and may be the biosynthetic intermediates of rice phytoalexins momilactones and oryzalexin S, respectively. Compound 3 exhibited relatively high inhibitory activity against the fungal mycelial growth of M. oryzae to the same extent as the known phytoalexin phytocassane A. We conclude that 3 is a member of the cassane-type phytoalexin family and propose the name phytocassane F.

  12. Antiangiogenic properties of cafestol, a coffee diterpene, in human umbilical vein endothelial cells

    SciTech Connect

    Wang, Shuaiyu; Yoon, Yeo Cho; Sung, Mi-Jeong; Hur, Haeng-Jeon; Park, Jae-Ho

    2012-05-11

    Highlights: Black-Right-Pointing-Pointer Cafestol inhibits tube formation and migration of VEGF-stimulated HUVEC. Black-Right-Pointing-Pointer Cafestol inhibits phosphorylation of FAK and Akt. Black-Right-Pointing-Pointer Cafestol decreases NO production. -- Abstract: As angiogenesis plays important roles in tumor growth and metastasis, searching for antiangiogenic compounds is a promising tactic for treating cancers. Cafestol, a diterpene found mainly in unfiltered coffee, provides benefit through varied biological activity, including antitumorigenic, antioxidative, and anti-inflammatory effects. This study aimed to investigate the effects of cafestol on angiogenesis and to uncover the associated mechanism. We show that cafestol inhibits angiogenesis of human umbilical vascular endothelial cells. This inhibition affects the following specific steps of the angiogenic process: proliferation, migration, and tube formation. The inhibitory effects of cafestol are accompanied by decreasing phosphorylation of FAK and Akt and by a decrease in nitric oxide production. Overall, cafestol inhibits angiogenesis by affecting the angiogenic signaling pathway.

  13. Labdane diterpenes from Aster spathulifolius and their cytotoxic effects on human cancer cell lines.

    PubMed

    Lee, Sung Ok; Choi, Sang Zin; Choi, Sang Un; Lee, Kang Choon; Chin, Young Won; Kim, Jinwoong; Kim, Young Choong; Lee, Kang Ro

    2005-10-01

    Three new labdane diterpenes (1-3), together with eight known diterpenoids, were isolated from a methanol extract of the aerial parts of Aster spathulifolius. The structures of 1-3 were determined as (13R)-labda-7,14-diene 13-O-beta-d-(4'-O-acetyl)fucopyranoside (1), (13R)-labda-7,14-diene 13-O-beta-d-(3'-O-acetyl)fucopyranoside (2), and (13R)-labda-14(15)-en-8,13-diol 13-O-beta-d-fucopyranoside (3), on the basis of spectroscopic and chemical methods. Compounds 1, 2, and four of the known compounds exhibited generally nonspecific cytotoxicity against human A549, SK-OV-3, SK-MEL-2, XF498, and HCT15 tumor cells.

  14. Diterpenes from the Trunk of Abies holophylla and Their Potential Neuroprotective and Anti-inflammatory Activities.

    PubMed

    Kim, Chung Sub; Subedi, Lalita; Kim, Sun Yeou; Choi, Sang Un; Kim, Ki Hyun; Lee, Kang Ro

    2016-02-26

    Eleven new abietane-type diterpenes, holophyllins D-N (1-11), and 17 known analogues (12-28), were isolated from a MeOH extract of the trunk of Abies holophylla. The chemical structures of 1-11 were determined through spectroscopic data analysis, including NMR ((1)H and (13)C NMR, DEPT, (1)H-(1)H COSY, HMQC, HMBC, and NOESY) and HRFABMS methods. All isolated compounds (1-28) were evaluated for their cytotoxicity against four human tumor cell lines (A549, SK-OV-3, SK-MEL-2, and HCT-116), for their potential neuroprotective effects through induction of nerve growth factor in C6 glioma cells, and for their effects on nitric oxide levels in lipopolysaccharide-stimulated murine microglia BV2 cells.

  15. Oxygenated diterpenes and other constituents from Moroccan Juniperus phoenicea and Juniperus thurifera var. africana.

    PubMed

    Barrero, Alejandro F; Quilez del Moral, José F; Herrador, M Mar; Akssira, Mohamed; Bennamara, Ahmed; Akkad, Said; Aitigri, Mohamed

    2004-09-01

    Six new diterpenic acids isolated as their methyl ester derivatives, i.e., methyl 12-oxo-8alpha,15-dihydroxyabiet-13-en-19-oate, methyl 12-oxo-8alpha-hydroxyabiet-13-en-19-oate, methyl 15-hydroperoxy-8alpha,12alpha-epidioxiabiet-13-en-19-oate, methyl 15-hydroxy-8alpha,12alpha-epidioxiabiet-13-en-19-oate, methyl 15-hydroperoxy-8alpha,14alpha,12alpha,13alpha-diepoxiabietan-13-en-19-oate, and methyl 7alpha,12beta-dihydroxysandaracopimarate, together with two new isovalerate derivatives of p-methoxycinnamyl alcohol and linalool, were isolated from the leaves of Juniperus thurifera var. africana and Juniperus phoenicea, grown in Morocco. The structures of these compounds were established by using spectroscopic techniques, including 2D NMR spectra. The cytotoxicity of the abietane diterpenoids was tested against five cell lines.

  16. Determination and potential importance of diterpene (kaur-16-ene) emitted from dominant coniferous trees in Japan.

    PubMed

    Matsunaga, Sou N; Chatani, Satoru; Nakatsuka, Seiji; Kusumoto, Dai; Kubota, Katsuyoshi; Utsumi, Yasuhiro; Enoki, Tsutomu; Tani, Akira; Hiura, Tsutom

    2012-05-01

    Reactive volatile organic compounds (VOCs) are known to affect atmospheric chemistry. Biogenic VOCs (BVOCs) have a significant impact on regional air quality due to their large emission rates and high reactivities. Diterpenes (most particularly, kaur-16-ene) were detected in all of the 205 enclosure air samples collected over multiple seasons at two different sites from Cryptomeria japonica and Chamaecyparis obtusa trees, the dominant coniferous trees in Japan,. The emission rate of kaur-16-ene, was determined to be from 0.01 to 7.1 μg dwg(-1) h(-1) (average: 0.61 μg dwg(-1) h(-1)) employing branch enclosure measurements using adsorbent sampling followed by solid phase-liquid extraction techniques. The emission rate was comparable to that of monoterpenes, which is known major BVOC emissions, collected from the same branches. In addition, total emission of kaur-16-ene at 30°C was estimated to exceed that of total anthropogenic VOC emissions.

  17. Extracellular localization of the diterpene sclareol in clary sage (Salvia sclarea L., Lamiaceae).

    PubMed

    Caissard, Jean-Claude; Olivier, Thomas; Delbecque, Claire; Palle, Sabine; Garry, Pierre-Philippe; Audran, Arthur; Valot, Nadine; Moja, Sandrine; Nicolé, Florence; Magnard, Jean-Louis; Legrand, Sylvain; Baudino, Sylvie; Jullien, Frédéric

    2012-01-01

    Sclareol is a high-value natural product obtained by solid/liquid extraction of clary sage (Salvia sclarea L.) inflorescences. Because processes of excretion and accumulation of this labdane diterpene are unknown, the aim of this work was to gain knowledge on its sites of accumulation in planta. Samples were collected in natura or during different steps of the industrial process of extraction (steam distillation and solid/liquid extraction). Samples were then analysed with a combination of complementary analytical techniques (gas chromatography coupled to a mass spectrometer, polarized light microscopy, environmental scanning electron microscopy, two-photon fluorescence microscopy, second harmonic generation microscopy). According to the literature, it is hypothesized that sclareol is localized in oil pockets of secretory trichomes. This study demonstrates that this is not the case and that sclareol accumulates in a crystalline epicuticular form, mostly on calyces.

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

    PubMed

    Reina, Eduardo; Puentes, Carlos; Rojas, Juan; García, Josué; Ramos, Freddy A; Castellanos, Leonardo; Aragón, Marcela; Ospina, Luis F

    2011-10-01

    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.

  19. Extracellular Localization of the Diterpene Sclareol in Clary Sage (Salvia sclarea L., Lamiaceae)

    PubMed Central

    Caissard, Jean-Claude; Olivier, Thomas; Delbecque, Claire; Palle, Sabine; Garry, Pierre-Philippe; Audran, Arthur; Valot, Nadine; Moja, Sandrine; Nicolé, Florence; Magnard, Jean-Louis; Legrand, Sylvain; Baudino, Sylvie; Jullien, Frédéric

    2012-01-01

    Sclareol is a high-value natural product obtained by solid/liquid extraction of clary sage (Salvia sclarea L.) inflorescences. Because processes of excretion and accumulation of this labdane diterpene are unknown, the aim of this work was to gain knowledge on its sites of accumulation in planta. Samples were collected in natura or during different steps of the industrial process of extraction (steam distillation and solid/liquid extraction). Samples were then analysed with a combination of complementary analytical techniques (gas chromatography coupled to a mass spectrometer, polarized light microscopy, environmental scanning electron microscopy, two-photon fluorescence microscopy, second harmonic generation microscopy). According to the literature, it is hypothesized that sclareol is localized in oil pockets of secretory trichomes. This study demonstrates that this is not the case and that sclareol accumulates in a crystalline epicuticular form, mostly on calyces. PMID:23133579

  20. Formation of beyerene, kaurene, trachylobane, and atiserene diterpenes by rearrangements that avoid secondary carbocations.

    PubMed

    Hong, Young J; Tantillo, Dean J

    2010-04-21

    Quantum chemical calculations on carbocation intermediates encountered during the conversion of ent-copalyl diphosphate to the diterpenes beyerene, kaurene, trachylobane, and atiserene are described. Based on the results of these computations, it is suggested that previously proposed secondary carbocation intermediates are avoided. In some cases, complex rearrangements in which up to three alkyl or hydride shifting events are coupled into concerted processes are predicted to occur instead. The potential effects of electron-rich active site groups on the inherent reactivity of key carbocations are discussed, as are complex rearrangements coupled to deprotonation events. Based on computed electrostatic potential maps, it also is proposed that ammonium ions that were previously designed as mimics of several carbocations are actually better mimics of transition state structures for carbocation deprotonation.

  1. New cladiellane diterpenes from the soft coral Cladiella australis of the Andaman and Nicobar Islands.

    PubMed

    Rao, C B; Rao, D S; Satyanarayana, C; Rao, D V; Kassühlke, K E; Faulkner, D J

    1994-05-01

    Five new cladiellane diterpenes, (1R*,2R*,3R*,6S*,7S*,9R*,10R*,14R*)-3- acetoxy-6-(3-methylbutanoyloxy)cladiell-11(17)-en-7-ol [2], (1R*,2R*,3R*,6S*,7S*,9R*, 10R*,14R*)-3-butanoyloxycladiell-11(17)-en-6,7-diol [3], (1R*,2R*,3R*,6S*,9R*,10R*,14R*)-3-acetoxycladiell-7(16),11(1 7)-dien-6-ol [4], 3-acetoxycladiell-11(17)-en-6-one [5], and its stereoisomer [6], have been isolated from the soft coral Cladiella australis collected on the coasts of the Andaman and Nicobar Islands of the Indian Ocean. In addition, sclerophytins C [7] and E [8], reported earlier from Sclerophytum capitalis, were also isolated. The structures of these metabolites were elucidated by interpretation of spectral data.

  2. A comparison of flavonoid glycosides by electrospray tandem mass spectrometry

    NASA Astrophysics Data System (ADS)

    March, Raymond E.; Lewars, Errol G.; Stadey, Christopher J.; Miao, Xiu-Sheng; Zhao, Xiaoming; Metcalfe, Chris D.

    2006-01-01

    A comparison is presented of product ion mass spectra of protonated and deprotonated molecules of kaempferol-3-O-glucoside, quercitin-3-O-glucoside (isoquercitrin), quercitin-3-O-galactoside (hyperoin), apigenin-7-O-glucoside, luteolin-7-O-glucoside, genistein-7-O-glucoside, naringenin-7-O-glucoside (prunin), luteolin-4'-O-glucoside, luteolin-6-C-glucoside (homoorientin, known also as isoorientin), apigenin-8-C-glucoside (vitexin), and luteolin-8-C-glucoside (orientin) together with the product ion mass spectrum of deprotonated kaempferol-7-O-glucoside. All isomeric ions were distinguishable on the basis of their product ion mass spectra. For protonated 3-O-, 7-O-, and 4'-O-glycosides at a collision energy of 46-47 eV, homolytic cleavage of the O-glycosidic bond yielded aglycon Y+ ions, whereas in deprotonated 3-O-, 7-O-, and 4'-O-glycosides, heterolytic and homolytic cleavage of the O-glycosidic bond yielded radical aglycon (Y-H)- and aglycon (Y-) ions. In each case, fragmentation of either the glycan or the aglycon or both was observed. For 6-C- and 8-C-glycosides at a collision energy of 46-47 eV, fragmentation was restricted almost exclusively to the glycan. For luteolin-6-C-glucoside, the integrity of the aglycon structure is preserved at the expense of the glycan for which some 30 fragmentations were observed. Breakdown curves were determined as a function of collision energy for protonated and deprotonated luteolin-6-C-glucoside. An attempt has been made to rationalize the product ion mass spectra derived from C-O- and C-C-luteolin glucosides in terms of computed structures that indicate significant intramolecular hydrogen bonding and rotation of the B-ring to form a coplanar luteolin structure. It is proposed that protonated and deprotonated luteolin-6-C-glucoside may afford examples of cooperative interactive bonding that plays a major role in directing fragmentation.

  3. Annotation and comparative analysis of the glycoside hydrolase genes in Brachypodium distachyon

    SciTech Connect

    Tyler, Ludmila; Bragg, Jennifer; Wu, Jiajie; Yang, Xiaohan; Tuskan, Gerald A; Vogel, John

    2010-01-01

    Background Glycoside hydrolases cleave the bond between a carbohydrate and another carbohydrate, a protein, lipid or other moiety. Genes encoding glycoside hydrolases are found in a wide range of organisms, from archea to animals, and are relatively abundant in plant genomes. In plants, these enzymes are involved in diverse processes, including starch metabolism, defense, and cell-wall remodeling. Glycoside hydrolase genes have been previously cataloged for Oryza sativa (rice), the model dicotyledonous plant Arabidopsis thaliana, and the fast-growing tree Populus trichocarpa (poplar). To improve our understanding of glycoside hydrolases in plants generally and in grasses specifically, we annotated the glycoside hydrolase genes in the grasses Brachypodium distachyon (an emerging monocotyledonous model) and Sorghum bicolor (sorghum). We then compared the glycoside hydrolases across species, both at the whole-genome level and at the level of individual glycoside hydrolase families. Results We identified 356 glycoside hydrolase genes in Brachypodium and 404 in sorghum. The corresponding proteins fell into the same 34 families that are represented in rice, Arabidopsis, and poplar, helping to define a glycoside hydrolase family profile which may be common to flowering plants. Examination of individual glycoside hydrolase familes (GH5, GH13, GH18, GH19, GH28, and GH51) revealed both similarities and distinctions between monocots and dicots, as well as between species. Shared evolutionary histories appear to be modified by lineage-specific expansions or deletions. Within families, the Brachypodium and sorghum proteins generally cluster with those from other monocots. Conclusions This work provides the foundation for further comparative and functional analyses of plant glycoside hydrolases. Defining the Brachypodium glycoside hydrolases sets the stage for Brachypodium to be a monocot model for investigations of these enzymes and their diverse roles in planta. Insights

  4. Elicitation of Diterpene Biosynthesis in Rice (Oryza sativa L.) by Chitin 1

    PubMed Central

    Ren, Yue-Ying; West, Charles A.

    1992-01-01

    Cell-free extracts of UV-irradiated rice (Oryza sativa L.) leaves have a much greater capacity for the synthesis from geranylgeranyl pyrophosphate of diterpene hydrocarbons, including the putative precursors of rice phytoalexins, than extracts of unstressed leaves (KA Wickham, CA West [1992] Arch Biochem Biophys 293: 320-332). An elicitor bioassay was developed on the basis of these observations in which 6-day-old rice cell suspension cultures were incubated for 40 hours with the substance to be tested, and an enzyme extract of the treated cells was assayed for its diterpene hydrocarbon synthesis activity as a measure of the response to elicitor. Four types of cell wall polysaccharides and oligosaccharide fragments that have elicitor activity for other plants were tested. Of these, polymeric chitin was the most active; a suspension concentration of approximately 7 micrograms per milliliter gave 50% of the maximum response in the bioassay. Chitosan and a branched β-1,3-glucan fraction from Phytophthora megasperma f. sp. glycinea cell walls were only weakly active, and a mixture of oligogalacturonides was only slightly active. A crude mycelial cell wall preparation from the rice pathogen, Fusarium moniliforme, gave a response comparable to that of chitin, and this activity was sensitive to predigestion of the cell wall material with chitinase before the elicitor assay. N-Acetylglucosamine, chitobiose, chitotriose, and chitotetrose were inactive as elicitors, whereas a mixture of chitin fragments solubilized from insoluble chitin by partial acid hydrolysis was highly active. Constitutive chitinase activity was detected in the culture filtrate and enzyme extract of cells from a 6-day-old rice cell culture; the amount of chitinase activity increased markedly in both the culture filtrate and cell extracts after treatment of the culture with chitin. We propose on the basis of these results that soluble chitin fragments released from fungal cell walls through the action

  5. Central nervous system activities of two diterpenes isolated from Aloysia virgata.

    PubMed

    Wasowski, Cristina; Marder, Mariel

    2011-03-15

    Using the guide of a competitive assay for the benzodiazepine binding site in the γ-aminobutyric acid type A receptor (GABA(A)), two active diterpenes were isolated from the aerial parts of Aloysia virgata (Ruíz & Pavón) A.L. Jussieu var. platyphylla (Briquet) Moldenke. These compounds, identified as (16R)-16,17,18-trihydroxyphyllocladan-3-one (1) and (16R)-16,17-dihydroxyphyllocladan-3-one (2) on the basis of spectral data, competitively inhibited the binding of [(3)H]-FNZ to the benzodiazepine binding site with K(i)±S.E.M. values of 56±19 μM and 111±13 μM, respectively. The behavioral actions of these diterpenes, intraperitoneally (i.p.) administered in mice, were examined in the plus-maze, holeboard, locomotor activity and light/dark tests. Compound 1 exhibited anxiolytic-like effects in mice evidenced by a significant increase of the parameters measured in the holeboard test (the number of head dips at 0.3 mg/kg and 3 mg/kg, the rears at 1 mg/kg and the time spent head-dipping at 3 mg/kg), in the plus-maze assay (the percentage of open arm entries at 1 mg/kg) and in the light/dark test (the time in light and the number of transitions at 1 mg/kg). Compound 2 augmented the number of rearings in the holeboard apparatus (at 0.3 mg/kg and 1 mg/kg) and the locomotor activity (at 1 mg/kg). These results reveal the presence of neuroactive compounds in Aloysia virgata.

  6. Use of dietary rosemary diterpenes to inhibit rancid volatiles in lamb meat packed under protective atmosphere.

    PubMed

    Ortuño, J; Serrano, R; Bañón, S

    2016-08-01

    The objective of the present study was to determine the inhibitory effect of dietary rosemary diterpenes on the formation of the volatile organic compounds (VOCs) responsible for rancid flavour in raw lamb meat. The lamb diet was supplemented during the fattening stage with two levels (200 and 400 mg/kg feed) of a dietary rosemary extract (DRE) containing carnosic acid and carnosol (1 : 1, w/w). The formation of VOCs (determined by headspace solid-phase microextraction at 40°C and MS) and odour deterioration (assessed by quantitative descriptive analysis) were monitored in meat fillets (longissimus dorsi-lumborum muscle) packed in a 70/30 O2/CO2 protective atmosphere and kept at 2°C for up to 14 days. The raw meat odour deteriorated under pro-oxidizing conditions due to the development of an incipient rancidity caused by the formation of volatiles from lipid oxidation. A total of 46 volatile compounds were determined in lamb headspace: 18 aldehydes, seven alcohols, seven organic acids, six ketones, four furan compounds, two benzene compounds, one ester and one terpenoid. The use of DRE contributed to inhibit VOC formation and rancidity. Heptanal, octanal, nonanal and 2-pentyl-furan were the only VOCs affected (P0.75; P<0.001), although similar values were obtained for the coefficients of a large number of carbonyl, alcohols and furan compounds, among other volatiles, which can be considered molecular markers of rancidity in raw lamb meat. Principal component analysis confirmed that the differences in the VOC profile make it possible to identify whether or not samples have been reinforced with dietary rosemary diterpenes. Thus, VOC profiling can be regarded as a useful tool for assessing the dietary treatments used in sheep to improve the oxidative stability of lamb meat.

  7. Pyrrole Derivatives and Diterpene Alkaloids from the South China Sea Sponge Agelas nakamurai.

    PubMed

    Chu, Mei-Jun; Tang, Xu-Li; Qin, Guo-Fei; Sun, Yan-Ting; Li, Lei; de Voogd, Nicole J; Li, Ping-Lin; Li, Guo-Qiang

    2017-02-21

    Two pairs of new non-brominated racematic pyrrole derivatives, (±)-nakamurine D (1) and (±)-nakamurine E (2), two new diterpene alkaloids, iso-agelasine C (16), and iso-agelasidine B (21), together with fifteen known pyrrole derivatives((±)-3 - 15), five known diterpene alkaloids (17 - 20, 22) were isolated from the South China Sea sponge Agelas nakamurai. The racemic mixtures, compounds 1 - 4, were resolved into four pairs of enantiomers, (+)-1 and (-)-1, (+)-2 and (-)-2, (+)-3 and (-)-3, and (+)-4 and (-)-4, by chiral HPLC. The structures and absolute configurations were elucidated on the basis of comprehensive spectroscopic analyses, quantum chemical calculations, quantitative measurements of molar rotations, application of van't Hoff's principle of optical superposition, and comparison with the literature data. The NMR and MS data of compound 3 are reported for the first time, as the structure was listed in SciFinder Scholar with no associated reference. These non-brominated pyrrole derivatives were found in this species for the first time. Compound 18 showed valuable cytotoxicities against HL-60, K562, and HCT-116 cell lines with IC50 values of 12.4, 16.0, and 19.8 μM, respectively. Compounds 16 - 19, 21, and 22 showed potent antifungal activities against Candida albicans with MIC values ranging from 0.59 to 4.69 μg/mL. Compounds 16 - 19 exhibited moderate antibacterial activities against Proteusbacillus vulgaris (MIC values ranging from 9.38 to 18.75 μg/mL). This article is protected by copyright. All rights reserved.

  8. Insights into Diterpene Cyclization from Structure of Bifunctional Abietadiene Synthase from Abies grandis

    SciTech Connect

    Zhou, Ke; Gao, Yang; Hoy, Julie A.; Mann, Francis M.; Honzatko, Richard B.; Peters, Reuben J.

    2013-09-24

    Abietadiene synthase from Abies grandis (AgAS) is a model system for diterpene synthase activity, catalyzing class I (ionization-initiated) and class II (protonation-initiated) cyclization reactions. Reported here is the crystal structure of AgAS at 2.3 {angstrom} resolution and molecular dynamics simulations of that structure with and without active site ligands. AgAS has three domains ({alpha}, {beta}, and {gamma}). The class I active site is within the C-terminal {alpha} domain, and the class II active site is between the N-terminal {gamma} and {beta} domains. The domain organization resembles that of monofunctional diterpene synthases and is consistent with proposed evolutionary origins of terpene synthases. Molecular dynamics simulations were carried out to determine the effect of substrate binding on enzymatic structure. Although such studies of the class I active site do lead to an enclosed substrate-Mg{sup 2+} complex similar to that observed in crystal structures of related plant enzymes, it does not enforce a single substrate conformation consistent with the known product stereochemistry. Simulations of the class II active site were more informative, with observation of a well ordered external loop migration. This 'loop-in' conformation not only limits solvent access but also greatly increases the number of conformational states accessible to the substrate while destabilizing the nonproductive substrate conformation present in the 'loop-out' conformation. Moreover, these conformational changes at the class II active site drive the substrate toward the proposed transition state. Docked substrate complexes were further assessed with regard to the effects of site-directed mutations on class I and II activities.

  9. Three new alkaloids and three new phenolic glycosides from Liparis odorata.

    PubMed

    Jiang, Piao; Liu, Hongdong; Xu, Xianghong; Liu, Bo; Zhang, Dongming; Lai, Xuewen; Zhu, Genghua; Xu, Peng; Li, Bin

    2015-12-01

    Three new alkaloids, liparis alkaloid A (1), B (2), C (3), and three new phenolic glycosides, liparis glycoside H (4), I (5), J (6), together with three known phenolic glycosides (7-9) were isolated from the whole plant of Liparis odorata. Their structures were characterized on the basis of extensive 1D-, 2D-NMR and HR-ESI-MS experiments. In addition, compounds 1-3 revealed hypolipidemic effects in the in vitro bioassays, and the ability to inhibit LPS-induced NO production of these isolated phenolic glycosides (4-9) was also evaluated.

  10. Glycosides from marine sponges (Porifera, Demospongiae): structures, taxonomical distribution, biological activities and biological roles.

    PubMed

    Kalinin, Vladimir I; Ivanchina, Natalia V; Krasokhin, Vladimir B; Makarieva, Tatyana N; Stonik, Valentin A

    2012-08-01

    Literature data about glycosides from sponges (Porifera, Demospongiae) are reviewed. Structural diversity, biological activities, taxonomic distribution and biological functions of these natural products are discussed.

  11. Selective separation of flavonoid glycosides in Dalbergia odorifera by matrix solid-phase dispersion using titania.

    PubMed

    Xu, Lingyan; Shi, Hui; Liang, Tu; Feng, Jiatao; Jin, Yu; Ke, Yanxiong; Liang, Xinmiao

    2011-06-01

    Dalbergia odorifera contains high concentrations of flavonoid aglycones and trace flavonoid glycosides. In this study, trace flavonoid glycosides were separated from D. odorifera by titania with matrix solid-phase dispersion (MSPD). Before the MSPD experiment, four standards, including two isoflavone glycosides (genistin and formononetin-8-C-apiosyl (1-6)-glucoside) and their aglycones (genistein and formononetin), were used to compare their retention on a titania column. The effect of acetonitrile concentration and pH on their retention was investigated and a conclusion was drawn that high acetonitrile concentration and pH lead to the greatest difference in the retention of flavonoid as glycosides and aglycones. Besides hydrophilic interaction and ligand-exchange interaction may exist between sugar moiety of flavonoid glycoside and titania, so that flavonoid glycosides have stronger retention than that of aglycones. Based on the chromatographic rule of flavonoid as glycosides and aglycones on the titania column, the MSPD method was optimized to elute high concentration flavonoid aglycones first with 90% acetonitrile and 10% water containing 100 mM ammonium acetate buffer, and then to elute trace flavonoid glycosides with 20% acetonitrile and 80% water containing 1% trifluoroacetate (TFA). Isolated flavonoid glycosides were further analyzed by UPLC-MS/MS, and their fragmentation in MS(2) showed they are C-glycosyl flavonoids.

  12. Tandem mass spectrometric fragmentation patterns of known and new steviol glycosides with structure proposals.

    PubMed

    Zimmermann, Benno F

    2011-06-15

    Stevia rebaudiana contains several steviol glycosides that have a sweet flavor. They are up to 450 times sweeter than sucrose, but some have an undesirable aftertaste. Up to 2010, ten different steviol glycosides have been described from the leaves or purified extracts of S. rebaudiana. In this paper, the tandem mass spectrometric fragmentation patterns of these ten compounds are compiled, along with a scheme for structural elucidation. This scheme is then applied to 12 steviol glycosides that have not yet been described. The proposed structures of five steviol glycosides have been confirmed by other authors.

  13. Spatio-temporal variation of the diterpene steviol in Stevia rebaudiana grown under different photoperiods.

    PubMed

    Ceunen, Stijn; Geuns, Jan M C

    2013-05-01

    As part of an ongoing study on the effects of photoperiodism on the metabolism of steviol glycosides (SVglys) in Stevia rebaudiana, the spatio-temporal variations of free steviol (SV) have now been evaluated. For its quantitation, an internal standard method was used, based upon a specific fluorometric detection of SV as its methoxycoumarinyl derivative. The level of free SV in leaves did not exceed 30 μg/g dry wt and was at least 1000-fold smaller than that of its glycosidic conjugates. In other organs, free SV was mainly measured in stem tissue and apices, with relatively large amounts measured in the latter. Similarly to SVglys, the content of free SV was influenced by photoperiod and genotype. In plants grown under long-days (LD) of 16 h, more spatial variations were seen compared to those under short-days (SD) of 8h. In the former, upper leaves contained almost four times more free SV compared to lower ones near the end of vegetative growth. In addition, the correlation between SV and its glycosidic conjugates was more linear under SD. Despite the variability of SV levels, a decrease was noted in all conditions after flower opening, which can be related a decreased transcription of the biosynthetic genes involved.

  14. Dactyloditerpenol acetate, a new prenylbisabolane-type diterpene from Aplysia dactylomela with significant in vitro anti-neuroinflammatory activity.

    PubMed

    Jiménez-Romero, Carlos; Mayer, Alejandro M S; Rodríguez, Abimael D

    2014-01-01

    A new regular diterpene possessing an unusual 1,6-anti-3-methylcyclohex-2-en-1-ol ring system, dactyloditerpenol acetate (1), has been extracted from the tropical sea hare Aplysia dactylomela and its stereostructure elucidated by spectroscopic methods. The absolute configuration of 1 was determined as 1S, 6S, 7R, 10S, and 11R by application of Kishi's method for the assignment of absolute configuration of alcohols. The new diterpene potently inhibited in vitro thromboxane B2 (TXB2) (IC50 0.4μM) and superoxide anion (O2(-)) (IC50 1μM) generation from Escherichia coli lipopolysaccharide (LPS)-activated rat neonatal microglia, with concomitant low short-term toxicity.

  15. Biochemical characterization of the castor bean ent-kaurene synthase(-like) family supports quantum chemical view of diterpene cyclization

    PubMed Central

    Jackson, Alana J.; Hershey, David M.; Chesnut, Taylor; Xu, Meimei; Peters, Reuben J.

    2014-01-01

    It has become apparent that plants have extensively diversified their arsenal of labdane-related diterpenoids (LRDs), in part via gene duplication and neo-functionalization of the ancestral ent-kaurene synthase (KS) required for gibberellin metabolism. For example, castor bean (Ricinus communis) was previously shown to produce an interesting set of biosynthetically related diterpenes, specifically ent-sandracopimaradiene, ent-beyerene, and ent-trachylobane, in addition to ent-kaurene, using four separate diterpene synthases, albeit these remain unidentified. Notably, despite mechanistic similarity of the underlying reaction to that catalyzed by KSs, ent-beyerene and ent-trachylobane synthases have not yet been identified. Given our interest in LRD biosynthesis, and the recent availability of the castor bean genome sequence, we applied a synthetic biology approach to biochemically characterize the four KS(-like) enzymes [KS(L)s] found in Ricinus communis [i.e., the RcKS(L)s]. In particular, using bacteria engineered to produce the relevant ent-copalyl diphosphate precursor and synthetic genes based on the predicted RcKS(L)s, although this ultimately required correction of a “splicing” error in one of the predicted genes, highlighting the dependence of such a synthetic biology approach on accurate gene sequences. Nevertheless, we can assign each of the four RcKS(L)s to one of the previously observed diterpene synthase activities, providing access to functionally novel enzymes. Intriguingly, the product distribution of the RcKS(L)s seems to support the distinct diterpene synthase reaction mechanism proposed by quantum chemical calculations, rather than the classically proposed pathway. PMID:24810014

  16. Helikaurolides A-D with a Diterpene-Sesquiterpene Skeleton from Supercritical Fluid Extracts of Helianthus annuus L. var. Arianna.

    PubMed

    Torres, Ascensión; Molinillo, José M G; Varela, Rosa M; Casas, Lourdes; Mantell, Casimiro; Martínez de la Ossa, Enrique J; Macías, Francisco A

    2015-10-02

    Four novel compounds (1-4) with an unprecedented skeleton that combines a sesquiterpene lactone and a kaurane diterpene acid were isolated from Helianthus annuus L. var. Arianna extract, which was obtained under supercritical conditions. The structures of 1-4 were elucidated by NMR and MS analyses. The biosynthetic routes involve sesquiterpene lactones and kauranic acid, both of which were previously isolated from this species.

  17. Biochemical characterization of the castor bean ent-kaurene synthase(-like) family supports quantum chemical view of diterpene cyclization.

    PubMed

    Jackson, Alana J; Hershey, David M; Chesnut, Taylor; Xu, Meimei; Peters, Reuben J

    2014-07-01

    It has become apparent that plants have extensively diversified their arsenal of labdane-related diterpenoids (LRDs), in part via gene duplication and neo-functionalization of the ancestral ent-kaurene synthase (KS) required for gibberellin metabolism. For example, castor bean (Ricinus communis) was previously shown to produce an interesting set of biosynthetically related diterpenes, specifically ent-sandracopimaradiene, ent-beyerene, and ent-trachylobane, in addition to ent-kaurene, using four separate diterpene synthases, albeit these remain unidentified. Notably, despite mechanistic similarity of the underlying reaction to that catalyzed by KSs, ent-beyerene and ent-trachylobane synthases have not yet been identified. Given our interest in LRD biosynthesis, and the recent availability of the castor bean genome sequence, a synthetic biology approach was applied to biochemically characterize the four KS(-like) enzymes [KS(L)s] found in Ricinus communis [i.e., the RcKS(L)s]. In particular, using bacteria engineered to produce the relevant ent-copalyl diphosphate precursor and synthetic genes based on the predicted RcKS(L)s, although this ultimately required correction of a "splicing" error in one of the predicted genes, highlighting the dependence of such a synthetic biology approach on accurate gene sequences. Nevertheless, it is possible to assign each of the four RcKS(L)s to one of the previously observed diterpene synthase activities, providing access to functionally enzymes. Intriguingly, the product distribution of the RcKS(L)s seems to support the distinct diterpene synthase reaction mechanism proposed by quantum chemical calculations, rather than the classically proposed pathway.

  18. Flavonol glycosides in the petal of Rosa species as chemotaxonomic markers.

    PubMed

    Sarangowa, Ochir; Kanazawa, Tsutomu; Nishizawa, Makoto; Myoda, Takao; Bai, Changxi; Yamagishi, Takashi

    2014-11-01

    Thirteen flavonol glycosides were isolated from the petals of Rosa species belonging to the section Gallicanae, and their structures were identified from their spectroscopic data. These flavonol glycosides, along with two flavonol glycosides isolated from Rosa rugosa, in the petals of 31 Rosa species belonging to sections Gallicanae, Cinnamomeae, Caninae, and Synstylae were quantitatively analyzed by UPLC. The results indicated that the species belonging to these sections could be classified into four types (Type A, B, C and D) based on the pattern of flavonol glycoside contents, whereas the R. rugosa flavonol glycosides were detected only in section Cinnamomeae. A principal components analysis (PCA) calculated from the 15 flavonol glycosides contained in these samples supported the presence of four types. The distribution of the species in Type D (a group of Cinnamomeae) was shown to reflect close interrelationships, but species in Type B (one group of Gallicanae) could be subdivided into two groups, one of which contained species in section Synstylae. Moreover, the flavonol glycosides were grouped by sugar moieties: a disaccharide composed of two hexoses (S1), a hexose (S2), including a hexose with galloyl group, a pentose (S3), and a disaccharide composed of a hexose and a pentose (S4). The ratios of the amounts of S1-S4 to total flavonol glycoside content indicated that differences among the four sections were more distinctive than the amounts of the 15 flavonol glycosides. The 31 samples were divided into Type B, composed of one type of Gallicanae and Synstylae, Type A+C, composed of another type of Gallicanae and Caninae, and Type D, composed of Cinnamomeae. The R. rugosa flavonol glycosides were shown to be important chemotaxonomic markers for the classification of species in Cinnamomeae, and this method of using flavonol glycosides as chemotaxonomic markers could be useful for the identification of Rosa species belonging to sections Gallicanae, Cinnamomeae

  19. A novel diterpene skeleton: identification of a highly aromatic, cytotoxic and antioxidant 5-methyl-10-demethyl-abietane-type diterpene from Premna serratifolia.

    PubMed

    Habtemariam, Solomon; Varghese, George K

    2015-01-01

    Premna serratifolia Linn. (syn: . P. corymbosa (Burm. f.) Merr., P. integrifolia L. and P. obtusifolia R. Br.) is a member of the Verbenaceae family that is extensively used in the Ayurvedic system of medicine in India. As part of our continuous pharmacological and phytochemical studies on medicinal plants, we have screened the methanolic extracts of leaves, root bark (RB) and root wood of P. serratifolia for cytotoxic activity against two cancer cell lines: SHSY-5Y neuroblastoma and B16 melanoma cells. The RB extract that showed promising activity was fractionated using solvents of increasing polarity followed by a combination of Sephadex LH-20 column and Combiflash chromatography as well as HPLC to afford the active principle. Comprehensive spectroscopic analysis including 1D and 2D NMR (COSY, HMQC, HMBC, NOESY) and MS analysis revealed the identity of the isolated compound as 11,12,16-trihydroxy-2-oxo-5-methyl-10-demethyl-abieta-1[10],6,8,11,13-pentene that appears to be a novel compound based on a new diterpene skeleton. The cytotoxic activity of the isolated compound was 21 and 23 times higher than the crude extract against the SHSY-5Y and B16 cells, respectively. The novel compound also possesses in vitro antioxidant effects as evidenced by the DPPH (2,2-diphenyl-1-picrylhydrazyl) radical scavenging effect where an IC50 value of 20.4 ± 1.3 μM was obtained. In comparison, the positive control, caffeic acid, showed an IC50 value of 14.4 ± 1.6 μM.

  20. Modularity of Conifer Diterpene Resin Acid Biosynthesis: P450 Enzymes of Different CYP720B Clades Use Alternative Substrates and Converge on the Same Products1[OPEN

    PubMed Central

    Yuen, Macaire M.S.; Bohlmann, Jörg

    2016-01-01

    Cytochrome P450 enzymes of the CYP720B subfamily play a central role in the biosynthesis of diterpene resin acids (DRAs), which are a major component of the conifer oleoresin defense system. CYP720Bs exist in families of up to a dozen different members in conifer genomes and fall into four different clades (I–IV). Only two CYP720B members, loblolly pine (Pinus taeda) PtCYP720B1 and Sitka spruce (Picea sitchensis) PsCYP720B4, have been characterized previously. Both are multisubstrate and multifunctional clade III enzymes, which catalyze consecutive three-step oxidations in the conversion of diterpene olefins to DRAs. These reactions resemble the sequential diterpene oxidations affording ent-kaurenoic acid from ent-kaurene in gibberellin biosynthesis. Here, we functionally characterized the CYP720B clade I enzymes CYP720B2 and CYP720B12 in three different conifer species, Sitka spruce, lodgepole pine (Pinus contorta), and jack pine (Pinus banksiana), and compared their activities with those of the clade III enzymes CYP720B1 and CYP720B4 of the same species. Unlike the clade III enzymes, clade I enzymes were ultimately found not to be active with diterpene olefins but converted the recently discovered, unstable diterpene synthase product 13-hydroxy-8(14)-abietene. Through alternative routes, CYP720B enzymes of both clades produce some of the same profiles of conifer oleoresin DRAs (abietic acid, neoabietic acid, levopimaric acid, and palustric acid), while clade III enzymes also function in the formation of pimaric acid, isopimaric acid, and sandaracopimaric acid. These results highlight the modularity of the specialized (i.e. secondary) diterpene metabolism, which produces conifer defense metabolites through variable combinations of different diterpene synthase and CYP720B enzymes. PMID:26936895

  1. Antiamoebic and Antigiardial Activity of Clerodane Diterpenes from Mexican Salvia Species Used for the Treatment of Diarrhea.

    PubMed

    Calzada, Fernando; Bautista, Elihú; Yépez-Mulia, Lilian; García-Hernandez, Normand; Ortega, Alfredo

    2015-10-01

    Terpenoids from Salvia species have been identified to possess biological properties as antiprotozoal agents. Here, we evaluated the antiamoebic and antigiardial activities of 14 known clerodane and modified clerodane-type diterpenes isolated from five Mexican Salvia species against Entamoeba histolytica and Giardia lamblia, and analyzed the effects of the functionalities in decalin ring or in the whole clerodane framework to visualize the structural requirements necessary to produce an antiprotozoal activity. Among these, linearolactone was the most active clerodane diterpene against both protozoa with IC50 values of 22.9 μM for E. histolytica and of 28.2 μM in the case of G. lamblia. In this context it may be a lead compound for the development of novel therapeutic agent for the treatment of diarrhea and dysentery. The remaining diterpenes assayed showed moderate to weak activity against both protozoa. These findings give support to the use of Salvia species in the traditional medicine from México for the treatment of diarrhea.

  2. Steroidal glycosides with antiproliferative activities from Digitalis trojana.

    PubMed

    Kirmizibekmez, Hasan; Masullo, Milena; Festa, Michela; Capasso, Anna; Piacente, Sonia

    2014-04-01

    The phytochemical investigation of Digitalis trojana led to the isolation of two cardiac glycosides (1, 2), one pregnane glycoside (3), three furostanol type saponins (4-6), along with three cleroindicins (7-9), four phenylethanoid glycosides (10-13), two flavonoids (14, 15) and two phenolic acid derivatives (16, 17). The structure elucidation of the isolates was carried out by NMR experiments as well as ESI-MS. The cytotoxic activity of compounds 1-13 against a small panel of cancer cell lines, namely MCF-7, T98G, HT-29, PC-3, A375 and SH-SY5Y, was investigated. Compounds 1-6 showed antiproliferative activity against human breast MCF-7 and colon HT-29 cancer cell lines with IC50 values ranging from 8.3 to 50 μM. In order to understand the mechanism involved in the cell death, the active compounds were tested as pro-apoptotic agents using propidium iodide staining by flow cytometry method. No significant increase was observed in the apoptosis of the MCF-7 and HT-29 cancer cells. Moreover, the effects of the active compounds on cell proliferation were assessed on the same cancer cell lines by cell cycle analysis of DNA content using flow cytometry. No significative changes were observed in the cell cycle of MCF-7, while significant changes in G2 /M cell cycle phase of HT-29 cells were observed after treatment with digitalin (1), cariensoside (3) and 22-O-methylparvispinoside B (6) at 10 μM.

  3. Active Site and Laminarin Binding in Glycoside Hydrolase Family 55*

    PubMed Central

    Bianchetti, Christopher M.; Takasuka, Taichi E.; Deutsch, Sam; Udell, Hannah S.; Yik, Eric J.; Bergeman, Lai F.; Fox, Brian G.

    2015-01-01

    The Carbohydrate Active Enzyme (CAZy) database indicates that glycoside hydrolase family 55 (GH55) contains both endo- and exo-β-1,3-glucanases. The founding structure in the GH55 is PcLam55A from the white rot fungus Phanerochaete chrysosporium (Ishida, T., Fushinobu, S., Kawai, R., Kitaoka, M., Igarashi, K., and Samejima, M. (2009) Crystal structure of glycoside hydrolase family 55 β-1,3-glucanase from the basidiomycete Phanerochaete chrysosporium. J. Biol. Chem. 284, 10100–10109). Here, we present high resolution crystal structures of bacterial SacteLam55A from the highly cellulolytic Streptomyces sp. SirexAA-E with bound substrates and product. These structures, along with mutagenesis and kinetic studies, implicate Glu-502 as the catalytic acid (as proposed earlier for Glu-663 in PcLam55A) and a proton relay network of four residues in activating water as the nucleophile. Further, a set of conserved aromatic residues that define the active site apparently enforce an exo-glucanase reactivity as demonstrated by exhaustive hydrolysis reactions with purified laminarioligosaccharides. Two additional aromatic residues that line the substrate-binding channel show substrate-dependent conformational flexibility that may promote processive reactivity of the bound oligosaccharide in the bacterial enzymes. Gene synthesis carried out on ∼30% of the GH55 family gave 34 active enzymes (19% functional coverage of the nonredundant members of GH55). These active enzymes reacted with only laminarin from a panel of 10 different soluble and insoluble polysaccharides and displayed a broad range of specific activities and optima for pH and temperature. Application of this experimental method provides a new, systematic way to annotate glycoside hydrolase phylogenetic space for functional properties. PMID:25752603

  4. Determination of flavone C-glycosides in tea.

    PubMed

    Engelhardt, U H; Finger, A; Kuhr, S

    1993-09-01

    An HPLC method for the determination of flavone C-glycosides (FCG) from black tea has been developed. Sample clean-up was accomplished by means of polyamide column chromatography, followed by enzyme hydrolysis of interfering compounds such was flavonol glycosides and a second polyamide column chromatographic step. Using HPLC with gradient elution and photodiode array detection eight FCG were separated. Seven FCG were isolated by means of preparative HPLC. Identification was carried out using co-chromatography, FAB(Fast Atom Bombardment)-mass spectrometry and various nuclear magnetic resonance techniques. Apigenin 6-C-glucosyl-8-arabinoside (schaftoside) and apigenin 6-C-arabinosyl-8-C-glucoside (isoschaftoside) as well as luteolin 8-C-glucoside (orientin) and luteolin 6-C-glucoside (isoorientin) have been detected in tea for the first time. Three of the other compounds have been identified as apigenin 8-C-glucoside (vitexin), apigenin 6-C-glucoside (isovitexin) and apigenin 6,8-di-C-glucoside (vicenin-2). Their occurrence in tea has been previously reported. From its UV spectrum another compound was concluded to be an apigenin glycoside. The FCG were quantified in a variety of teas of different origins (16 black, two green and one oolong). The total amounts of the FCG were 0.48-2.69 g/kg dry weight. The FCG pattern of teas of different origins were similar to each other and no origin-dependent characteristics have yet been observed. Small amounts of FCG (1.2-2.2 mg/kg) were detected in hydrolysates of high relative molecular mass fractions (Mr > 5000) of a black tea liquor.

  5. C21 steroidal glycosides from the roots of Cynanchum saccatum.

    PubMed

    Zhang, Mi; Rao, Li-Li; Xiang, Cheng; Li, Bao-Cai; Li, Peng

    2015-09-01

    Eight new C21 steroidal glycosides, named cynsaccatols A-H (1-8), along with two known analogs (9-10), were isolated from the roots of Cynanchum saccatum. Their structures were determined on the basis of detailed spectroscopic analysis, as well as HRESIMS. All compounds (1-10) were tested for their cytotoxicity in vitro using three human cancer cell lines (HepG2, Hela and U251), and compounds 1, 4, 5, 9, 10 showed weak inhibitory activities against different cell lines, respectively.

  6. 7-O-Methylated anthocyanidin glycosides from Catharanthus roseus.

    PubMed

    Toki, Kenjiro; Saito, Norio; Irie, Yuki; Tatsuzawa, Fumi; Shigihara, Atsushi; Honda, Toshio

    2008-03-01

    Anthocyanins were isolated from orange-red flowers of Catharanthus roseus cv 'Equator Deep Apricot', and identified as rosinidin 3-O-[6-O-(alpha-rhamnopyranosyl)-beta-galactopyranoside] (1), and also 7-O-methylcyanidin 3-O-[6-O-(alpha-rhamnopyranosyl)-beta-galactopyranoside] (2) by chemical and spectroscopic methods. Pigment 1 was found to be a major anthocyanin in the flowers of this cultivar. By contrast, the distribution of rosinidin glycosides is very limited in plants, and reported only in the flowers of Primula. Pigment 2 was found in smaller concentrations, but its aglycone, 7-O-methylcyanidin, has been reported only once before, from the fruit of mango.

  7. Acylated flavonol glycosides from the flower of Elaeagnus angustifolia L.

    PubMed

    Bendaikha, Sarah; Gadaut, Méredith; Harakat, Dominique; Magid, Alabdul

    2014-07-01

    Seven acylated flavonol glycosides named elaeagnosides A-G, in addition to seven known flavonoids were isolated from the flowers of Elaeagnus angustifolia. Their structures were elucidated by different spectroscopic methods including 1D, 2D NMR experiments and HR-ESI-MS analysis. In order to identify natural antioxidant and tyrosinase inhibitor agents, the abilities of these flavonoids to scavenge the 1,1-diphenyl-2-picrylhydrazyl radical (DPPH) and to inhibit tyrosinase activity were evaluated. Results revealed that two of these compounds had significant anti-oxidant effect and one compound showed weak tyrosinase-inhibitory activity compared with kojic acid, quercetin, or ascorbic acid, which were used as positive control.

  8. Flavonoid glycosides in bergamot juice (Citrus bergamia Risso).

    PubMed

    Gattuso, Giuseppe; Caristi, Corrado; Gargiulli, Claudia; Bellocco, Ersilia; Toscano, Giovanni; Leuzzi, Ugo

    2006-05-31

    A comprehensive profile of flavonoids in bergamot juice was obtained by a single DAD-ESI-LC-MS-MS course. Eight flavonoids were found for the first time, five of these are C-glucosides (lucenin-2, stellarin-2, isovitexin, scoparin, and orientin 4'-methyl ether), and three are O-glycosides (rhoifolin 4'-O-glucoside, chrysoeriol 7-O-neohesperidoside-4'-O-glucoside, and chrysoeriol 7-O-neohesperidoside). A method is proposed to differentiate chrysoeriol and diosmetin derivatives, which are often indistinguishable by LC-MS-MS. In-depth knowledge of the flavonoid content is the starting point for bergamot juice exploitation in food industry applications.

  9. New isoflavone glycosides from the stems of Dalbergia vietnamensis.

    PubMed

    Loan, Pham Thanh; Le Anh, Hoang Tuan; Cuc, Nguyen Thi; Yen, Duong Thi Hai; Hang, Dan Thi Thuy; Ha, Tran Minh; Nhiem, Nguyen Xuan; Van Du, Nguyen; Thai, Tran Huy; Van Minh, Chau; Van Kiem, Phan

    2014-06-01

    Two new isoflavone glycosides, dalspinosin 7-O-beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyranoside (1) and caviunin 7-O-(5-O-trans-p-coumaroyl)-beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyranoside (2), and two known compounds, caviunin 7-O-beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyranoside (3) and caviunin (4) were isolated from the stems of Dalbergia vietnamensis. Their structures were determined by the combination of spectroscopic and chemical methods, including 1D- and 2D-NMR spectroscopy, as well as by comparing with the NMR data reported in the literature.

  10. A new benzophenone glycoside from the leaves of Mitracarpus villosus.

    PubMed

    Ngwoke, Kenneth G; Orame, Njideka; Liu, Shuai; Okoye, Festus B C; Daletos, Georgios; Proksch, Peter

    2017-03-22

    A new benzophenone glycoside, mitraphenone A (1), together with three known compounds (2-4) were isolated from the leaves of the traditionally used medicinal plant Mitracarpus villosus (Rubiaceae) collected in Nigeria. A combination of one- and two-dimensional NMR spectroscopic and mass spectrometric measurements were carried out to identify the structure of 1. All isolated compounds (1-4) were screened for their antibacterial activity against several Gram-positive and Gram-negative bacteria. Compound 1 exhibited moderate activity against Enterococcus faecium (strains ATCC 35667 and ATCC 700221) and Staphylococcus aureus ATCC 25923 with MIC values ranging from 25 to 50 μM.

  11. [Iridoid glycosides from buds of Jasminum officinale L. var. grandiflorum].

    PubMed

    Zhao, Gui-qin; Yin, Zhi-feng; Liu, Yu-cui; Li, Hong-bo

    2011-10-01

    The study on the buds of Jasminum officinale L. var. grandiflorum was carried out to look for anti-HBV constituents. The isolation and purification were performed by HPLC and chromatography on silica gel, polyamide and Sephadex LH-20 column. The structures were elucidated on the basis of physicochemical properties and spectral analysis. Six iridoid glycosides were identified as jasgranoside B (1), 6-O-methy-catalpol (2), deacetyl asperulosidic acid (3), aucubin (4), 8-dehydroxy shanzhiside (5), and loganin (6). Jasgranoside B (1) is a new compound. Compounds 2-6 were isolated from Jasminum officinale L. var. grandiflorum for the first time.

  12. New cyclopeptide alkaloid and lignan glycoside from Justicia procumbens.

    PubMed

    Jin, Hong; Chen, Li; Tian, Ying; Li, Bin; Dong, Jun-Xing

    2015-01-01

    This study reported a new cyclopeptide alkaloid, justicianene A (1), and a new lignan glycoside, procumbenoside H (2), isolated from Justicia procumbens. The structures of the new compounds were elucidated by means of spectroscopic analysis, including extensive 2D NMR studies and mass spectrometry. Cyclopeptide alkaloids were first observed from the genus Justicia. Compound 2 was cytotoxic against human LoVo colon carcinoma cells with an IC50 value of 17.908 ± 1.949 μM.

  13. Three New Cytotoxic Polyhydroxysteroidal Glycosides from Starfish Craspidaster hesperus

    PubMed Central

    Kang, Jun-Xia; Kang, Yong-Feng; Han, Hua

    2016-01-01

    Three new polyhydroxysteroidal glycosides, hesperuside A (1), B (2), and C (3), as well as a known novaeguinoside A (4), were isolated from the ethanol extract of starfish Craspidaster hesperus collected from the South China Sea. Their structures were elucidated by extensive spectroscopic methods and chemical evidence. The compounds 1–3 present unprecedented carbohydrate chain 3-O-methyl-β-d-galactopyranose, which differ from each other in the side chains. These compounds exhibited cytotoxicity against human tumor cells BEL-7402, MOLT-4, and A-549 in vitro. PMID:27775561

  14. Additional new minor cucurbitane glycosides from Siraitia grosvenorii.

    PubMed

    Prakash, Indra; Chaturvedula, Venkata Sai Prakash

    2014-03-24

    Continuous phytochemical studies of the crude extract of Luo Han Guo (Siraitia grosvenorii) furnished three additional new cucurbitane triterpene glycosides, namely 11-deoxymogroside V, 11-deoxyisomogroside V, and 11-deoxymogroside VI. The structures of all the isolated compounds were characterized on the basis of extensive NMR and mass spectral data as well as hydrolysis studies. The complete ¹H- and ¹³C-NMR spectral assignments of the three unknown compounds are reported for the first time based on COSY, TOCSY, HSQC, and HMBC spectroscopic data.

  15. A new pregnane glycoside from Gomphocarpus fruticosus growing in Egypt.

    PubMed

    Marzouk, Amani M; Osman, Samir M; Gohar, Ahmed A

    2016-01-01

    Phytochemical investigation of Gomphocarpus fruticosus (L.) Ait. of Egyptian origin afforded the new pregnane glycoside lineolon-3-O-[β-D-oleandropyranosyl-(1-4)-β-D-cymaropyranosyl-(1-4)-β-D-cymaropyranoside], along with six known compounds. The structures of the isolated compounds were elucidated on the basis of extensive spectroscopic evidences derived from 1D, 2D NMR experiments, mass spectrometry and by comparing their physical and spectroscopic data to literature. These included the triterpenoids 3β-taraxerol, 3β-taraxerol acetate and betulinic acid, which are identified for the first time in G. fruticosus and the cardenolides uzarigenin, gomphoside and calotropin.

  16. New pregnane glycoside derivative from Caralluma retrospiciens (Ehrenb).

    PubMed

    Elsebai, Mahmoud Fahmi; Mohamed, Ietidal El-Tahir

    2015-01-01

    Retrospinoside (1) is a new polyoxy pregnane glycoside which was isolated and characterised from the aerial parts of Caralluma retrospiciens (Ehrenb.) N. E. Br., family Apocynaceae. The structure was established as 3-O-[β-D-glucopyranosyl-(1 → 4)-β-D-(3-O-methyl-6-desoxygalactopyranosy)]-14,15,20-trihydroxy-4β-pregnane. Its structural elucidation was performed through extensive spectroscopic measurements including 1D- and 2D-NMR, and HRMS, in addition to chemical methods.

  17. Phenylpropanoid Glycosides from the Leaves of Ananas comosus.

    PubMed

    Chen, Wen-Hao; Huang, Xiao-Juan; Shu, Huo-Ming; Hui, Yang; Guo, Fei-Yan; Song, Xiao-Ping; Ji, Ming-Hui; Chen, Guang-Ying

    2015-12-01

    Two new phenylpropanoid glycosides, named β-D-(1-O-acetyl-3,6-O-diferuloyl) fructofuranosyl β-D-6'-O-acetylglucopyranoside (1) and β-D-(1-O-acetyl-3,6-O-diferuloyl) fructofuranosyl α-D-glucopyranoside (2), along with two known analogues (3-4) and four glycerides (5-8), were isolated from the EtOAc extract of the leaves of Ananas comosus. Their structures were elucidated on the basis of 1D- and 2D-NMR analyses, as well as HR-ESI-MS experiments. Compounds 1-4 showed significant antibacterial activities against Staphylococcus aureus and Escherichia coli.

  18. New Knowledge About Old Drugs: The Anti-Inflammatory Properties of Cardiac Glycosides.

    PubMed

    Fürst, Robert; Zündorf, Ilse; Dingermann, Theo

    2017-03-15

    In the 19th century, cardio-active steroid glycosides, shortly cardiac glycosides, were scientifically established as drugs against heart failure. Their in vivo, cellular, and molecular actions as well as their predominant target, Na(+)-K(+)-ATPase, have been comprehensively investigated in the 20th century and the discovery of endogenous cardiac glycosides has fostered this research field. In the last years, however, results from clinical trials and meta-analyses have questioned their therapeutic value due to efficacy and safety issues. This has led to a considerable decline of their usage. Beyond the cardiovascular system, cardiac glycosides have been increasingly recognized as antitumor compounds and Na(+)-K(+)-ATPase has evolved into a promising drug target in oncology. A wealth of review articles exists that intensively discuss these topics. Surprisingly, the anti-inflammatory actions of cardiac glycosides, which were discovered in the 1960s, have so far hardly been perceived and have not yet been summarized. This review provides an overview of the in vivo and in vitro actions of cardiac glycosides on inflammatory processes and of the signaling mechanisms responsible for these effects: cardiac glycosides have been found to decrease inflammatory symptoms in different animal models of acute and chronic inflammation. Regarding the underlying mechanisms most research has focused on leukocytes. In these cells, cardiac glycosides primarily inhibit cell proliferation and the secretion of proinflammatory cytokines.

  19. Dalvelutinoside, a new isoflavone glycoside from the methanol extract of Dalbergia velutina roots.

    PubMed

    Kaennakam, Sutin; Siripong, Pongpun; Tip-Pyang, Santi

    2016-07-01

    A new isoflavone glycoside, dalvelutinoside (1), together with one known isoflavone (2) and five known isoflavone glycosides (3-7) were isolated from the methanol extract of the roots of Dalbergia velutina. Their structures were determined by spectroscopic analysis. All isolated compounds were evaluated for their cytotoxicity against KB and HeLa cell lines.

  20. Two new nor-triterpene glycosides from peruvian "Uña de Gato" (Uncaria tomentosa).

    PubMed

    Kitajima, Mariko; Hashimoto, Ken-Ichiro; Yokoya, Masashi; Takayama, Hiromitsu; Sandoval, Manuel; Aimi, Norio

    2003-02-01

    Two new 27-nor-triterpene glycosides, tomentosides A (1) and B (2), were isolated from Peruvian "Uña de Gato" (cat's claw, plant of origin: Uncaria tomentosa), a traditional herbal medicine in Peru. Their structures were determined by spectroscopic analysis and chemical interconversions. This is the first report of naturally occurring pyroquinovic acid glycosides.

  1. A new cembrane glycoside in Asterothamnus centrali-asiaticus from Gobi Desert.

    PubMed

    Todorova, Milka; Trendafilova, Antoaneta; Javsmaa, Namshir; Altantsetseg, Shatarin; Shatar, Sanduin

    2013-09-01

    A new cembrane glycoside, nephthenol 15-O-β-d-quinovoside, was isolated from the aerial parts of Asterothamnus centrali-asiaticus. Its structure was elucidated by 1D and 2D NMR spectroscopic analysis, as well as by mass spectrometry. This is the first report of the occurrence of a cembrane glycoside in vascular plants.

  2. Annotation and comparative analysis of the glycoside hydrolase genes in Brachypodium distachyon

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Glycoside hydrolase genes have been previously cataloged for Oryza sativa (rice), the model dicotyledonous plant Arabidopsis thaliana, and the fast-growing tree Populus trichocarpa (poplar). To improve our understanding of glycoside hydrolases in plants generally and in grasses specifically, we ann...

  3. Synthesis of cardiac glycoside analogs by catalyst-controlled, regioselective glycosylation of digitoxin.

    PubMed

    Beale, Thomas M; Taylor, Mark S

    2013-03-15

    The cardiac glycoside natural product digitoxin was selectively glycosylated at one of its five hydroxyl groups using a borinic acid derived catalyst. This method provided access to the glycosylation pattern characteristic of a subclass of natural products from Digitalis purpurea. Variation of the glycosyl donor was tolerated, enabling the synthesis of novel cardiac glycoside analogs from readily available materials.

  4. 2-C-branched glycosides from 2'-carbonylalkyl 2-O-Ms(Ts)-C-glycosides. A tandem SN2-SN2 reaction via 1,2-cyclopropanated sugars.

    PubMed

    Shao, Huawu; Ekthawatchai, Sanchai; Wu, Shih-Hsiung; Zou, Wei

    2004-09-30

    [reaction: see text] Under basic conditions, 2'-aldehydo (acetonyl) 2-O-Ms(Ts)-alpha-C-glycosides undergo an intramolecular S(N)2 reaction to form 1,2-cyclopropanated sugars, which react with nucleophiles (alcohols, thiols, and azide) at the anomeric carbon to give 2-C-branched glycosides. By way of contrast, the 1,2-cyclopropanes derived from 2'-ketones only react with thiols to give 2-C-branched thioglycosides.

  5. Mass spectrometric imaging of flavonoid glycosides and biflavonoids in Ginkgo biloba L.

    PubMed

    Beck, Sebastian; Stengel, Julia

    2016-10-01

    Ginkgo biloba L. is known to be rich in flavonoids and flavonoid glycosides. However, the distribution within specific plant organs (e.g. within leaves) is not known. By using HPLC-MS and MS/MS we have identified a number of previously known G. biloba flavonoid glycosides and biflavonoids from leaves. Namely, kaempferol, quercetin, isorhamnetin, myricetin, laricitrin/mearnsetin and apigenin glycosides were identified. Furthermore, biflavonoids like ginkgetin/isoginkgetin were also detected. The application of MALDI mass spectrometric imaging, enabled the compilation of concentration profiles of flavonoid glycosides and biflavonoids in G. biloba L. leaves. Both, flavonoid glycosides and biflavonoids show a distinct distribution in leaf thin sections of G. biloba L.

  6. Merremins A-G, resin glycosides from Merremia hederacea with multidrug resistance reversal activity.

    PubMed

    Wang, Wen-qiong; Song, Wei-bin; Lan, Xiao-jing; Huang, Min; Xuan, Li-jiang

    2014-10-24

    Five new pentasaccharide resin glycosides, named merremins A-E (1-5), two new pentasaccharide resin glycoside methyl esters, named merremins F and G (6, 7), and four known resin glycosides, murucoidin IV, murucoidin V, stoloniferin IV, and murucoidin XVII, were obtained from the aerial parts of Merremia hederacea. This is the first report of resin glycosides obtained from M. hederacea. In addition, the new compounds can be divided into three types: those possessing an 18-membered ring (1-4), compound 5 with a 20-membered ring, and those with an acyclic core (6, 7). Furthermore, the different types of resin glycosides were evaluated for their multidrug resistance reversal activities. Compounds 1, 5, 6, and murucoidin V were noncytotoxic and enhanced the cytotoxicity of vinblastine by 2.3-142.5-fold at 25 μM. Compound 5 and murucoidin V, with 20-membered rings, were more active than compound 1, with an 18-membered ring.

  7. Synthesis of gold nanoparticles with glycosides: synthetic trends based on the structures of glycones and aglycones.

    PubMed

    Jung, Jisung; Park, Suryeon; Hong, Suckchang; Ha, Min Woo; Park, Hyeung-geun; Park, Youmie; Lee, Hyo-Jong; Park, Yohan

    2014-03-11

    A new, room temperature synthetic method for gold nanoparticles from auric acid with glycosides as reducing agents in aqueous NaOH is presented. As a mechanistic study of the oxidation sites on the glycosides, eight sugar-containing reductants (glycoside, glucose, glucuronic acid) have been tested in the synthesis of gold nanoparticles to determine their trends based on the structures of glycones and aglycones. As a result of the comparison among the eight sugar-containing reductants, it was determined that C-6 of glycosides is oxidized to a carboxylic acid during the reduction of auric acid. To detect the oxidized compounds of the glycosides, the reaction mixtures were monitored by (13)C NMR. Among the eight sugar-containing reductants, phenyl β-D-glucoside generated the highest synthetic yield of mono-dispersed, round gold nanoparticles (13.15±1.30 nm, 99.7% yield).

  8. Hydration of vinyl ether groups by unsaturated glycoside hydrolases and their role in bacterial pathogenesis.

    PubMed

    Hashimoto, Wataru; Itoh, Takafumi; Maruyama, Yukie; Mikami, Bunzo; Murata, Kousaku

    2007-12-01

    Many pathogenic microorganisms invade mammalian and/or plant cells by producing polysaccharide-degrading enzymes (lyases and hydrolases). Mammalian glycosaminoglycans and plant pectins that form part of the cell surface matrix are typical targets for these microbial enzymes. Unsaturated glycoside hydrolase catalyzes the hydrolytic release of an unsaturated uronic acid from oligosaccharides, which are produced through the reaction of matrix-degrading polysaccharide lyase. This enzymatic ability suggests that unsaturated glycoside hydrolases function as virulence factors in microbial infection. This review focuses on the molecular identification, bacterial distribution, and structure/function relationships of these enzymes. In contrast to general glycoside hydrolases, in which the catalytic mechanism involves the retention or inversion of an anomeric configuration, unsaturated glycoside hydrolases uniquely trigger the hydrolysis of vinyl ether groups in unsaturated saccharides but not of their glycosidic bonds.

  9. Stimulation of steviol glycoside accumulation in Stevia rebaudiana by red LED light.

    PubMed

    Ceunen, Stijn; Werbrouck, Stefaan; Geuns, Jan M C

    2012-05-01

    The aim of this study was to determine whether steviol glycoside accumulation is under phytochrome control. The results indicate that Stevia rebaudiana Bertoni plants grown under short-day conditions showed precocious flowering and stagnation of steviol glycoside accumulation. Long night interruption by red LED light stimulated and sustained the vegetative growth as well as the accumulation of steviol glycosides in the leaves. After 7 weeks of treatment, steviol glycoside content was about two-fold higher in LED-treated plants than in the short-day control group. The effects of red LED light were measured both in a greenhouse and in a phytotron, irrespective of cultivar-specific differences. Therefore, it can be concluded that a mid-night interruption by red LED light during short photoperiods provides an easy and inexpensive method to increase vegetative leaf biomass production with an increased steviol glycoside yield.

  10. Quantitation of sweet steviol glycosides by means of a HILIC-MS/MS-SIDA approach.

    PubMed

    Well, Caroline; Frank, Oliver; Hofmann, Thomas

    2013-11-27

    Meeting the rising consumer demand for natural food ingredients, steviol glycosides, the sweet principle of Stevia rebaudiana Bertoni (Bertoni), have recently been approved as food additives in the European Union. As regulatory constraints require sensitive methods to analyze the sweet-tasting steviol glycosides in foods and beverages, a HILIC-MS/MS method was developed enabling the accurate and reliable quantitation of the major steviol glycosides stevioside, rebaudiosides A-F, steviolbioside, rubusoside, and dulcoside A by using the corresponding deuterated 16,17-dihydrosteviol glycosides as suitable internal standards. This quantitation not only enables the analysis of the individual steviol glycosides in foods and beverages but also can support the optimization of breeding and postharvest downstream processing of Stevia plants to produce preferentially sweet and least bitter tasting Stevia extracts.

  11. Contrasting Patterns of Diterpene Acid Induction by Red Pine and White Spruce to Simulated Bark Beetle Attack, and Interspecific Differences in Sensitivity Among Fungal Associates.

    PubMed

    Mason, Charles J; Klepzig, Kier D; Kopper, Brian J; Kersten, Philip J; Illman, Barbara L; Raffa, Kenneth F

    2015-06-01

    Conifers possess a suite of physiochemical defenses that protect their subcortical tissues from bark beetle - fungal complexes. These defenses include rapid induction of terpenoids and phenolics at the site of attack. Studies of the distribution, induction, and bioactivity of conifer terpenoids have focused heavily on monoterpenes. We assessed induction of diterpene acids in white spruce (Picea glauca) and red pine (Pinus resinosa) to fungal associates of two bark beetles, and the responses of four spruce beetle (Dendroctonus rufipennis)-associated fungi to three diterpene acids. Constitutive phloem contents differed between species, in that red pine had extremely low concentrations of diterpene acids, whereas white spruce had substantial constitutive levels. Induction differed quantitatively. Both red pine and white spruce exhibited marked increases, but red pine underwent greater increases and achieved higher concentrations than white spruce. Induction also differed qualitatively in that red pine showed lower diversity and fewer compositional changes during induction than white spruce. In red pine,fungal inoculation accompanying wounding elicited greater increases than wounding alone, but in white spruce total concentrations were higher following wounding alone. Spruce beetle fungal symbiont growth varied among species and compounds. Some diterpenes elicited both stimulatory and inhibitory effects on fungi, depending on concentration. All four fungi exhibited higher tolerances compared to those associated with pine bark beetles in previous studies. Variation in tolerances to, and potentially metabolism of, diterpene acids by symbionts may reflect differences in constitutive levels between spruce and pine, and partially explain differences in concentrations achieved during induction.

  12. Molecular Cloning and Functional Analysis of Gene Clusters for the Biosynthesis of Indole-Diterpenes in Penicillium crustosum and P. janthinellum

    PubMed Central

    Nicholson, Matthew J.; Eaton, Carla J.; Stärkel, Cornelia; Tapper, Brian A.; Cox, Murray P.; Scott, Barry

    2015-01-01

    The penitremane and janthitremane families of indole-diterpenes are abundant natural products synthesized by Penicillium crustosum and P. janthinellum. Using a combination of PCR, cosmid library screening, and Illumina sequencing we have identified gene clusters encoding enzymes for the synthesis of these compounds. Targeted deletion of penP in P. crustosum abolished the synthesis of penitrems A, B, D, E, and F, and led to accumulation of paspaline, a key intermediate for paxilline biosynthesis in P. paxilli. Similarly, deletion of janP and janD in P. janthinellum abolished the synthesis of prenyl-elaborated indole-diterpenes, and led to accumulation in the latter of 13-desoxypaxilline, a key intermediate for the synthesis of the structurally related aflatremanes synthesized by Aspergillus flavus. This study helps resolve the genetic basis for the complexity of indole-diterpene natural products found within the Penicillium and Aspergillus species. All indole-diterpene gene clusters identified to date have a core set of genes for the synthesis of paspaline and a suite of genes encoding multi-functional cytochrome P450 monooxygenases, FAD dependent monooxygenases, and prenyl transferases that catalyse various regio- and stereo- specific oxidations that give rise to the diversity of indole-diterpene products synthesized by this group of fungi. PMID:26213965

  13. Anti-HIV diphyllin glycosides from Justicia gendarussa.

    PubMed

    Zhang, Hong-Jie; Rumschlag-Booms, Emily; Guan, Yi-Fu; Liu, Kang-Lun; Wang, Dong-Ying; Li, Wan-Fei; Nguyen, Van Hung; Cuong, Nguyen Manh; Soejarto, Djaja Doel; Fong, Harry H S; Rong, Lijun

    2017-04-01

    In a search for new anti-HIV active leads from over several thousands of plant extracts, we have identified a potent plant lead. The active plant is determined as Justicia gendarussa (Acanthaceae), a medicinal plant that has been used for the treatment of injury, arthritis and rheumatism in Asia including China. Our bioassay-guided fractionation of the methanol extract of the stems and barks of the plant led to the isolation of two anti-HIV compounds, justiprocumins A and B. The compounds are identified as new arylnaphthalide lignans (ANL) glycosides. We further determined that the ANL glycosides are the chemical constituents that contribute to the anti-HIV activity of this plant. Justiprocumin B displayed potent activity against a broad spectrum of HIV strains with IC50 values in the range of 15-21 nM (AZT, IC50 77-95 nM). The compound also displayed potent inhibitory activity against the NRTI (nucleoside reverse transcriptase inhibitor)-resistant isolate (HIV-11617-1) of the analogue (AZT) as well as the NNRTI (non-nucleoside reverse transcriptase inhibitor)-resistant isolate (HIV-1N119) of the analogue (nevaripine).

  14. Glycosides from edible sea cucumbers stimulate macrophages via purinergic receptors

    PubMed Central

    Aminin, Dmitry; Pislyagin, Evgeny; Astashev, Maxim; Es’kov, Andrey; Kozhemyako, Valery; Avilov, Sergei; Zelepuga, Elena; Yurchenko, Ekaterina; Kaluzhskiy, Leonid; Kozlovskaya, Emma; Ivanov, Alexis; Stonik, Valentin

    2016-01-01

    Since ancient times, edible sea cucumbers have been considered a jewel of the seabed and used in Asian folk medicine for stimulation of resistance against different diseases. However, the power of this sea food has not been established on a molecular level. A particular group of triterpene glycosides was found to be characteristic metabolites of the animals, responsible for this biological action. Using one of them, cucumarioside A2-2 (CA2-2) from the edible Cucumaria japonica species as an example as well as inhibitory analysis, patch-clamp on single macrophages, small interfering RNA technique, immunoblotting, SPR analysis, computer modeling and other methods, we demonstrate low doses of CA2-2 specifically to interact with P2X receptors (predominantly P2X4) on membranes of mature macrophages, enhancing the reversible ATP-dependent Ca2+ intake and recovering Ca2+ transport at inactivation of these receptors. As result, interaction of glycosides of this type with P2X receptors leads to activation of cellular immunity. PMID:28004778

  15. Allosteric indicator displacement enzyme assay for a cyanogenic glycoside.

    PubMed

    Jose, D Amilan; Elstner, Martin; Schiller, Alexander

    2013-10-18

    Indicator displacement assays (IDAs) represent an elegant approach in supramolecular analytical chemistry. Herein, we report a chemical biosensor for the selective detection of the cyanogenic glycoside amygdalin in aqueous solution. The hybrid sensor consists of the enzyme β-glucosidase and a boronic acid appended viologen together with a fluorescent reporter dye. β-Glucosidase degrades the cyanogenic glycoside amygdalin into hydrogen cyanide, glucose, and benzaldehyde. Only the released cyanide binds at the allosteric site of the receptor (boronic acid) thereby inducing changes in the affinity of a formerly bound fluorescent indicator dye at the other side of the receptor. Thus, the sensing probe performs as allosteric indicator displacement assay (AIDA) for cyanide in water. Interference studies with inorganic anions and glucose revealed that cyanide is solely responsible for the change in the fluorescent signal. DFT calculations on a model compound revealed a 1:1 binding ratio of the boronic acid and cyanide ion. The fluorescent enzyme assay for β-glucosidase uses amygdalin as natural substrate and allows measuring Michaelis-Menten kinetics in microtiter plates. The allosteric indicator displacement assay (AIDA) probe can also be used to detect cyanide traces in commercial amygdalin samples.

  16. New Glycosides and Trypanocidal Metabolites from Vangueria edulis

    PubMed Central

    Mohamed, Shaymaa M. M.; Elokely, Khaled M.; Bachkeet, Enaam Y.; Bayoumi, Soad A. L.; Carnevale, Vincenzo; Klein, Michael L.; Cutler, Stephen J.

    2016-01-01

    A new iridoid glucoside, 10-methoxy apodanthoside (1), and a new monoterpene glycoside, (3S,6S)-cis linalool-3,7-oxide O-β-D-glucopyranosyl-(1″→5′)-β-D-xylofuranoside (2), were isolated from V. edulis (Rubiaceae), along with eighteen known compounds (3–20), including monoterpenes, iridoid glycosides, and a lignin, which were encountered for the first time in the genus Vangueria,. The structural elucidation of the isolates was based on the analysis of spectroscopic (1D and 2D NMR) and HR-ESI-MS data. Detailed stereochemical studies of 1 and related iridoid glucosides (compounds 3, 4 and 8) were made by matching the calculated ECD peaks with the experimental ones. All isolates were tested for their antiprotozoal, antifungal, and antiplasmodial activities. Compounds 9, 15 and 16 showed good trypanocidal activities against Trypanosoma brucei brucei with IC50 values of 8.18, 9.02 and 7.80 μg/mL, respectively and IC90 values of >10, >10 and 9.76 μg/mL, respectively. Compound 16 showed a moderate activity against Candida glabrata with an IC50 value of 8.66 μg/mL. Compound 20 showed a weak antiplasmodial activity against chloroquine-sensitive (D6) and resistant (W2) Plasmodium falciparum with IC50 values of 3.29 (SI, >1.4) and 4.53 (SI, >1) μg/mL, respectively. PMID:26749819

  17. Recovering glycoside hydrolase genes from active tundra cellulolytic bacteria.

    PubMed

    Pinnell, Lee J; Dunford, Eric; Ronan, Patrick; Hausner, Martina; Neufeld, Josh D

    2014-07-01

    Bacteria responsible for cellulose hydrolysis in situ are poorly understood, largely because of the relatively recent development of cultivation-independent methods for their detection and characterization. This study combined DNA stable-isotope probing (DNA-SIP) and metagenomics for identifying active bacterial communities that assimilated carbon from glucose and cellulose in Arctic tundra microcosms. Following DNA-SIP, bacterial fingerprint analysis of gradient fractions confirmed isotopic enrichment. Sequenced fingerprint bands and clone library analysis of 16S rRNA genes identified active bacterial taxa associated with cellulose-associated labelled DNA, including Bacteroidetes (Sphingobacteriales), Betaproteobacteria (Burkholderiales), Alphaproteobacteria (Caulobacteraceae), and Chloroflexi (Anaerolineaceae). We also compared glycoside hydrolase metagenomic profiles from bulk soil and heavy DNA recovered from DNA-SIP incubations. Active populations consuming [(13)C]glucose and [(13)C]cellulose were distinct, based on ordinations of light and heavy DNA. Metagenomic analysis demonstrated a ∼3-fold increase in the relative abundance of glycoside hydrolases in DNA-SIP libraries over bulk-soil libraries. The data also indicate that multiple displacement amplification introduced bias into the resulting metagenomic analysis. This research identified DNA-SIP incubation conditions for glucose and cellulose that were suitable for Arctic tundra soil and confirmed that DNA-SIP enrichment can increase target gene frequencies in metagenomic libraries.

  18. Steviol glycosides modulate glucose transport in different cell types.

    PubMed

    Rizzo, Benedetta; Zambonin, Laura; Angeloni, Cristina; Leoncini, Emanuela; Dalla Sega, Francesco Vieceli; Prata, Cecilia; Fiorentini, Diana; Hrelia, Silvana

    2013-01-01

    Extracts from Stevia rebaudiana Bertoni, a plant native to Central and South America, have been used as a sweetener since ancient times. Currently, Stevia extracts are largely used as a noncaloric high-potency biosweetener alternative to sugar, due to the growing incidence of type 2 diabetes mellitus, obesity, and metabolic disorders worldwide. Despite the large number of studies on Stevia and steviol glycosides in vivo, little is reported concerning the cellular and molecular mechanisms underpinning the beneficial effects on human health. The effect of four commercial Stevia extracts on glucose transport activity was evaluated in HL-60 human leukaemia and in SH-SY5Y human neuroblastoma cells. The extracts were able to enhance glucose uptake in both cellular lines, as efficiently as insulin. Our data suggest that steviol glycosides could act by modulating GLUT translocation through the PI3K/Akt pathway since treatments with both insulin and Stevia extracts increased the phosphorylation of PI3K and Akt. Furthermore, Stevia extracts were able to revert the effect of the reduction of glucose uptake caused by methylglyoxal, an inhibitor of the insulin receptor/PI3K/Akt pathway. These results corroborate the hypothesis that Stevia extracts could mimic insulin effects modulating PI3K/Akt pathway.

  19. Steviol Glycosides Modulate Glucose Transport in Different Cell Types

    PubMed Central

    Rizzo, Benedetta; Zambonin, Laura; Leoncini, Emanuela; Vieceli Dalla Sega, Francesco; Prata, Cecilia; Fiorentini, Diana; Hrelia, Silvana

    2013-01-01

    Extracts from Stevia rebaudiana Bertoni, a plant native to Central and South America, have been used as a sweetener since ancient times. Currently, Stevia extracts are largely used as a noncaloric high-potency biosweetener alternative to sugar, due to the growing incidence of type 2 diabetes mellitus, obesity, and metabolic disorders worldwide. Despite the large number of studies on Stevia and steviol glycosides in vivo, little is reported concerning the cellular and molecular mechanisms underpinning the beneficial effects on human health. The effect of four commercial Stevia extracts on glucose transport activity was evaluated in HL-60 human leukaemia and in SH-SY5Y human neuroblastoma cells. The extracts were able to enhance glucose uptake in both cellular lines, as efficiently as insulin. Our data suggest that steviol glycosides could act by modulating GLUT translocation through the PI3K/Akt pathway since treatments with both insulin and Stevia extracts increased the phosphorylation of PI3K and Akt. Furthermore, Stevia extracts were able to revert the effect of the reduction of glucose uptake caused by methylglyoxal, an inhibitor of the insulin receptor/PI3K/Akt pathway. These results corroborate the hypothesis that Stevia extracts could mimic insulin effects modulating PI3K/Akt pathway. PMID:24327825

  20. Flacourtosides A-F, phenolic glycosides isolated from Flacourtia ramontchi.

    PubMed

    Bourjot, Mélanie; Leyssen, Pieter; Eydoux, Cécilia; Guillemot, Jean-Claude; Canard, Bruno; Rasoanaivo, Philippe; Guéritte, Françoise; Litaudon, Marc

    2012-04-27

    In an effort to identify novel inhibitors of chikungunya (CHIKV) and dengue (DENV) virus replication, a systematic study with 820 ethyl acetate extracts of madagascan plants was performed in a virus-cell-based assay for CHIKV, and a DENV NS5 RNA-dependent RNA polymerase (RdRp) assay. The extract obtained from the stem bark of Flacourtia ramontchi was selected for its significant activity in both assays. Six new phenolic glycosides, named flacourtosides A-F (1-6), phenolic glycosides itoside H, xylosmin, scolochinenoside D, and poliothrysoside, and betulinic acid 3β-caffeate were obtained using the bioassay-guided isolation process. Their structures were elucidated by comprehensive analyses of NMR spectroscopic and mass spectrometric data. Even though several extracts and fractions showed significant selective antiviral activity in the CHIKV virus-cell-based assay, none of the purified compounds did. However, in the DENV RNA polymerase assay, significant inhibition was observed with betulinic acid 3β-caffeate (IC(50) = 0.85 ± 0.1 μM) and to a lesser extent for the flacourtosides A and E (1 and 5, respectively), and scolochinenoside D (IC(50) values ~10 μM).

  1. Evaluation of the content variation of anthraquinone glycosides in rhubarb by UPLC-PDA

    PubMed Central

    2013-01-01

    Background Rhubarb is an important Chinese medicinal herb with a long history of over 2000 years and has been commonly used as a laxative. It is the radix and rhizome of Rheum officinale Baill., R. palmatum L. and R. tanguticum Maxim, all of which are mainly distributed in a broad region in the Tibetan plateau. Anthraquinone glycosides are a series of major active ingredients found in all three species. They are key intermediates in the anthraquinone secondary metabolism and the sennnoside biosynthesis. The variation of the anthraquinone glycoside content in rhubarb in response to specific factors remains an attractive topic. Results A simple and sensitive Ultra Performance Liquid Chromatography with Photo-Diode Array (UPLC-PDA) detector was developed for the simultaneous determination of six anthraquinone glycosides in rhubarb, i.e., aloeemodin-8-O-glucoside, rhein-8-O-glucoside, chrysophanol-1-O-glucoside, emodin-1-O-glucoside, chrysophanol-8-O-glucoside, emodin-8-O-glucoside. Twenty-seven batches from three species were submitted to the multi-component analysis. The results showed that the anthraquinone glycoside content varied significantly even within the same species. The results showed that the anthraquinone glycoside content varied significantly within the same species but not between different species. The PCA and content analysis results confirmed that the plant species has no obvious effect on the content variation. Neither was any significant correlation observed between the anthraquinone glycoside content and the geographic distribution of the rhubarb. Through correlational analysis, altitude was found to be the main factor that affects the anthraquinone glycoside content in rhubarb. Rhubarb grown at higher altitude has higher anthraquinone glycoside content. Conclusions This work provides a rapid, sensitive and accurate UPLC-PDA method for the simultaneous determination of six anthraquinone glycosides in rhubarb. The anthraquinone glycoside content

  2. A new myrsinol-type diterpene polyester from Euphorbia dracunculoides Lam.

    PubMed

    Wang, Li; Yang, Jing; Chi, Yu-Qian; Ouyang, Wen-Bin; Zang, Zhen; Huang, Sheng-Xiong; Cao, Pei; Zhao, Yong

    2015-01-01

    A new myrsinol-type diterpene polyester, 14-deoxo-3β-O-propinoyl-2α,5α,7β,15β-tetra-O-acetyl-14α-O-benzoyl-myrsinol (1), and its known analogue, 14-deoxo-3β-O-prorionyl-5α,15β-di-O-acetyl-7β-O-nicotinoyl-myrsinol-14β-acetate (2), together with a monoterpenoid, pubinernoid A (3), two indole alkaloids, neoechinulin A (4) and dihydroxyisoechinulin A (5), two benzene derivatives, siringin (6) and (3-methoxyphenyl) acetic acid (7), were isolated from the 70% acetone extract of the aerial parts of Euphorbia dracunculoides Lam. Their structures were elucidated on the basis of spectroscopic evidence and comparison with literature reports. The absolute configuration of 1 was deduced by comparing experimental and calculated ECD spectra. Among them, compounds 4 and 5 were first obtained from the plant source. In addition, the (13)C NMR data of compound 2 was reported for the first time.

  3. [Metabolic pathway and metabolites of total diterpene acid isolated from Pseudolarix kaempferi].

    PubMed

    Liu, Peng; Guo, Hong-Zhu; Sun, Jiang-Hao; Xu, Man; Guo, Hui; Sun, Shi-Feng; Guo, De-An

    2014-08-01

    The preliminary metabolic profile of total diterpene acid (TDA) isolated from Pseudolarix kaempferi was investigated by using in vivo and in vitro tests. Pseudolaric acid C2 (PC2) was identified as the predominant metabolite in plasma, urine, bile and feces after both oral and intravenous administrations to rats using HPLC-UV and HPLC-ESI/MS(n), and demethoxydeacetoxypseudolaric acid B (DDPB), a metabolite proposed to be the glucoside of PC2 (PC2G), as well as pseudolaric acid C (PC), pseudolaric acid A (PA), pseudolaric acid A O-beta-D glucopyranoside (PAG), pseudolaric acid B O-beta-D glucopyranoside (PBG) and deacetylpseudolaric acid A (DPA) originated from TDA could also be detected. It was demonstrated by tests that the metabolism of TDA is independent of intestinal microflora, and neither of pepsin and trypsin is in charge of metabolism of TDA, TDA is also stable in both pH environments of gastric tract and intestinal tract. The metabolites of TDA in whole blood in vitro incubation were found to be PC2, DDPB and PC2G, which demonstrated that the metabolic reaction of TDA in vivo is mainly occurred in blood and contributed to be the hydrolysis of plasma esterase to ester bond, as well as the glucosylation reaction. These results clarified the metabolic pathway of TDA for the first time, which is of great significance to the in vivo active form and acting mechanism research of P. kaempferi.

  4. Induction of Mitochondrial Dysfunction and Oxidative Stress in Leishmania donovani by Orally Active Clerodane Diterpene

    PubMed Central

    Kathuria, Manoj; Bhattacharjee, Arindam; Sashidhara, Koneni V.; Singh, Suriya Pratap

    2014-01-01

    This study was performed to investigate the mechanistic aspects of cell death induced by a clerodane diterpene (K-09) in Leishmania donovani promastigotes that was previously demonstrated to be safe and orally active against visceral leishmaniasis (VL). K-09 caused depolarization of the mitochondrion and the generation of reactive oxygen species, triggering an apoptotic response in L. donovani promastigotes. Mitochondrial dysfunction subsequently resulted in the release of cytochrome c into the cytosol, impairing ATP production. Oxidative stress caused the depletion of reduced glutathione, while pretreatment with antioxidant N-acetyl cysteine (NAC) was able to abrogate oxidative stress. However, NAC failed to restore the mitochondrial membrane potential or intracellular calcium homeostasis after K-09 treatment, suggesting that the generation of oxidative stress is a downstream event relative to the other events. Caspase-3/-7-like protease activity and genomic DNA fragmentation were observed. Electron microscopy studies revealed gross morphological alterations typical of apoptosis, including severe mitochondrial damage, pyknosis of the nucleus, structural disruption of the mitochondrion-kinetoplast complex, flagellar pocket alterations, and the displacement of organelles. Moreover, an increased number of lipid droplets was detected after K-09 treatment, which is suggestive of altered lipid metabolism. Our results indicate that K-09 induces mitochondrial dysfunction and oxidative stress-mediated apoptotic cell death in L. donovani promastigotes, sharing many features with metazoan apoptosis. These mechanistic insights provide a basis for further investigation toward the development of K-09 as a potential drug candidate for VL. PMID:25070112

  5. Induction of mitochondrial dysfunction and oxidative stress in Leishmania donovani by orally active clerodane diterpene.

    PubMed

    Kathuria, Manoj; Bhattacharjee, Arindam; Sashidhara, Koneni V; Singh, Suriya Pratap; Mitra, Kalyan

    2014-10-01

    This study was performed to investigate the mechanistic aspects of cell death induced by a clerodane diterpene (K-09) in Leishmania donovani promastigotes that was previously demonstrated to be safe and orally active against visceral leishmaniasis (VL). K-09 caused depolarization of the mitochondrion and the generation of reactive oxygen species, triggering an apoptotic response in L. donovani promastigotes. Mitochondrial dysfunction subsequently resulted in the release of cytochrome c into the cytosol, impairing ATP production. Oxidative stress caused the depletion of reduced glutathione, while pretreatment with antioxidant N-acetyl cysteine (NAC) was able to abrogate oxidative stress. However, NAC failed to restore the mitochondrial membrane potential or intracellular calcium homeostasis after K-09 treatment, suggesting that the generation of oxidative stress is a downstream event relative to the other events. Caspase-3/-7-like protease activity and genomic DNA fragmentation were observed. Electron microscopy studies revealed gross morphological alterations typical of apoptosis, including severe mitochondrial damage, pyknosis of the nucleus, structural disruption of the mitochondrion-kinetoplast complex, flagellar pocket alterations, and the displacement of organelles. Moreover, an increased number of lipid droplets was detected after K-09 treatment, which is suggestive of altered lipid metabolism. Our results indicate that K-09 induces mitochondrial dysfunction and oxidative stress-mediated apoptotic cell death in L. donovani promastigotes, sharing many features with metazoan apoptosis. These mechanistic insights provide a basis for further investigation toward the development of K-09 as a potential drug candidate for VL.

  6. Cafestol, a coffee-specific diterpene, induces peripheral antinociception mediated by endogenous opioid peptides.

    PubMed

    Guzzo, Luciana S; Perez, Andrea C; Romero, Thiago Rl; Azevedo, Adolfo O; Duarte, Igor Dg

    2012-05-01

    The opioid peptides have been implicated in peripheral antinociception induced by non-opioidergic compounds, including non-steroidal anti-inflammatory drugs and α(2) -adrenoceptor agonists. The aims of the present study were to investigate the possible peripheral antinociceptive effect of cafestol, a diterpene present in the oil derived from coffee beans, and to evaluate the involvement of opioid peptides in its effect. The rat paw pressure test was used to assess antinocipeptive effects. Hyperalgesia was induced by intraplantar injection of prostaglandin E(2) (2 μg/paw). All drugs were locally administered into the hind-paws of male Wistar rats. Intraplantar injection of cafestol (20, 40 and 80 μg) induced peripheral antinociception. The antinociceptive effect of cafestol was due to a local action because the higher dose (80 μg/paw) did not produce any effect in the contralateral paw. The opioid receptor antagonist naloxone (25, 50 and 100 μg/paw) prevented the action of cafestol (80 μg/paw), whereas the aminopeptidase inhibitor bestatin (400 μg/paw) potentiated the antinociceptive effect of cafestol (40 μg/paw). The results of the present study provide evidence that cafestol treatment has a peripheral antinociceptive effect and suggest that this effect is mediated by the release of endogenous opioids.

  7. Phenolic diterpenes from rosemary suppress cAMP responsiveness of gluconeogenic gene promoters.

    PubMed

    Yun, Young Sook; Noda, Sachie; Shigemori, Genta; Kuriyama, Ryunosuke; Takahashi, Shigeru; Umemura, Mariko; Takahashi, Yuji; Inoue, Hideshi

    2013-06-01

    The cAMP/protein kinase A/cAMP response element (CRE)-binding protein pathway is important for various physiological aspects including regulation of gluconeogenic gene expression. Rosemary, a well-known herb, has been reported to decrease blood glucose levels. We found that methanol extracts of rosemary suppressed forskolin (FSK)-stimulated luciferase expression under the control of CRE, as well as the promoters for cytosolic phosphoenolpyruvate carboxykinase (PEPCK-C) and glucose-6-phosphatase (G6Pase) catalytic subunit genes in human hepatoma HepG2 cells. Three abietane-type diterpenes and two flavonoids were isolated from the rosemary extracts. Among these, 7-O-methylrosmanol (1) and royleanonic acid (3) effectively suppressed FSK-induced luciferase expression under the control of the CRE, PEPCK-C and G6Pase gene promoters. PEPCK-C and G6Pase, which play a key role in the homeostatic regulation of blood glucose levels, are important for managing type II diabetes mellitus. Therefore, the ability of rosemary and its components to suppress cAMP responsiveness of the PEPCK-C or G6Pase gene may contribute to its antihyperglycemic activity.

  8. Manool, a Salvia officinalis diterpene, induces selective cytotoxicity in cancer cells.

    PubMed

    de Oliveira, Pollyanna Francielli; Munari, Carla Carolina; Nicolella, Heloiza Diniz; Veneziani, Rodrigo Cassio Sola; Tavares, Denise Crispim

    2016-10-01

    Manool, a diterpene isolated from Salvia officinalis, was evaluated by the XTT colorimetric assay for cytotoxicity and selectivity against different cancer cell lines: B16F10 (murine melanoma), MCF-7 (human breast adenocarcinoma), HeLa (human cervical adenocarcinoma), HepG2 (human hepatocellular carcinoma), and MO59J, U343 and U251 (human glioblastoma). A normal cell line (V79, Chinese hamster lung fibroblasts) was used to compare the selectivity of the test substance. Manool exhibited higher cytotoxic activity against HeLa (IC50 = 6.7 ± 1.1 µg/mL) and U343 (IC50 = 6.7 ± 1.2 µg/mL) cells. In addition, in the used experimental protocols, the treatment with manool was significantly more cytotoxic for different tumor cell lines than for the normal cell line V79 (IC50 = 49.3 ± 3.3 µg/mL), and showed high selectivity. These results suggest that manool may be used to treat cancer without affecting normal cells.

  9. Natural diterpenes from Croton ciliatoglanduliferus as photosystem II and photosystem I inhibitors in spinach chloroplasts.

    PubMed

    Morales-Flores, Félix; Aguilar, María Isabel; King-Díaz, Beatriz; de Santiago-Gómez, Jesús-Ricardo; Lotina-Hennsen, Blas

    2007-01-01

    In our search for new natural photosynthetic inhibitors that could lead to the development of "green herbicides" less toxic to environment, the diterpene labdane-8alpha,15-diol (1) and its acetyl derivative (2) were isolated for the first time from Croton ciliatoglanduliferus Ort. They inhibited photophosphorylation, electron transport (basal, phosphorylating and uncoupled) and the partial reactions of both photosystems in spinach thylakoids. Compound 1 inhibits the photosystem II (PS II) partial reaction from water to Na(+) Silicomolibdate (SiMo) and has no effect on partial reaction from diphenylcarbazide (DPC) to 2,6-dichlorophenol indophenol (DCPIP), therefore 1 inhibits at the water splitting enzyme and also inhibits PS I partial reaction from reduced phenylmetasulfate (PMS) to methylviologen (MV). Thus, it also inhibits in the span of P(700) to Iron sulfur center X (F(X)). Compound 2 inhibits both, the PS II partial reactions from water to SiMo and from DPC to DCPIP; besides this, it inhibits the photosystem I (PS I) partial reaction from reduced PMS to MV. With these results, we concluded that the targets of the natural product 2 are located at the water splitting enzyme, and at P(680) in PS II and at the span of P(700) to F(X) in PS I. The results of compounds 1 and 2 on PS II were corroborated by chlorophyll a fluorescence.

  10. Molecular cloning and expression profile analysis of three sunflower (Helianthus annuus) diterpene synthase genes.

    PubMed

    Pugliesi, Claudio; Fambrini, Marco; Salvini, Mariangela

    2011-02-01

    ent-Kaurene, a key precursor of gibberellins, is formed by the action of two diterpene synthases (diTPSs), ent-copalyl diphosphate synthase (CPS), and ent-kaurene synthase (KS). The full-length cDNAs of CPS- (HaCPS1L) and KS-like (HaKS2L and HaKS3L) genes were isolated from sunflower. The amino acid sequences of HaCPS1L, HaKS2L, and HaKS3L exhibit structural features and homology to diTPSs of several plant species involved in gibberellin biosynthesis. RT-PCR analysis indicates that the expression of all genes (HaCPS1L, HaKS2L, and HaKS3L) is highly regulated during growth and development. All three diTPSs are preferentially expressed in rapidly growing tissues. HaKS2L is expressed at a much lower level than the other two diTPS genes. During seed development, the high level of both HaCPS1L and HaKS3L transcripts correlated with the period of rapid growth of the embryo. The three diTPS genes are not subjected to feedback regulation by gibberellin activity.

  11. Kaurene diterpenes from Laetia thamnia inhibit the growth of human cancer cells in vitro.

    PubMed

    Henry, Geneive E; Adams, Lynn S; Rosales, Jose C; Jacobs, Helen; Heber, David; Seeram, Navindra P

    2006-12-08

    Four ent-kaurene diterpenes were isolated from the leaves of Laetia thamnia L.: ent-kaur-16-en-19-oic acid (1a), ent-3beta-hydroxykaur-16-ene (2), ent-kaur-16-en-3alpha,19-diol (3a), and ent-17-hydroxykaur-15-en-19-oic acid (4). The methyl ester (1b) of compound 1a and the acetate diester (3b) of compound 3a were prepared, and all compounds were evaluated for cytotoxicity against human prostate (22Rv1, LNCaP), colon (HT29, HCT116, SW480, SW620), and breast (MCF-7) tumor cells at concentrations ranging from 6 to 50microg/mL. The kaurenes showed activity in all cell lines tested, with the prostate cells demonstrating the most sensitivity as follows: 22 Rv1 cells towards 1a (IC(50) 5.03microg/mL) and 1b (IC(50) 6.81microg/mL), and LNCaP towards 2 (IC(50) 12.83microg/mL) and 4 (IC(50) 17.63microg/mL).

  12. Kaurene diterpene induces apoptosis in human leukemia cells partly through a caspase-8-dependent pathway.

    PubMed

    Kondoh, Masuo; Suzuki, Ikue; Sato, Masao; Nagashima, Fumihiro; Simizu, Siro; Harada, Motoki; Fujii, Makiko; Osada, Hiroyuki; Asakawa, Yoshinori; Watanabe, Yoshiteru

    2004-10-01

    Defects in apoptosis signaling pathways contribute to tumorigenesis and drug resistance, and these defects are often a cause of failure of chemotherapy. Thus, a major goal in chemotherapy is to find cytotoxic agents that restore the ability of tumor cells to undergo apoptosis. We previously found that an Ent-kaurene diterpene, Ent-11alpha-hydroxy-16-kauren-15-one (KD), induced apoptosis in human promyelocytic leukemia HL-60 cells. Here, we found that caspase-8, an apoptotic factor, is involved in KD-induced apoptosis. Although treatment of HL-60 cells with KD resulted in the activation of caspase-8 and -9, a caspase-8-specific inhibitor but not a caspase-9-specific inhibitor attenuated KD-induced apoptosis. Expression of a catalytically inactive caspase-8 partly attenuated KD-induced apoptosis. Treatment with KD led to a time-dependent cleavage of Bid, a substrate of caspase-8, as well as to the proteolytic processing of procaspase-8, indicating that KD treatment induces apoptosis through a caspase-8-dependent pathway. Moreover, overexpression of the drug resistance factor Bcl-2, which is frequently overexpressed in many tumors, failed to confer resistance to KD-induced cytotoxicity. Thus, KD may be a promising experimental cytotoxic agent that possibly points to new strategies to overcome a drug resistance.

  13. Sucutinirane-diterpene derivatives induce apoptosis via oxidative stress in HL-60 cells.

    PubMed

    Deguchi, Jun; Horiguchi, Kaori; Wong, Chin Piow; Hosoya, Takahiro; Iihoshi, Akane; Kaneda, Toshio; Morita, Hiroshi

    2014-10-01

    Previously, we reported the isolation of cassane-type diterpenes, sucutiniranes A-F, from the seeds of Bowdichia nitida. In this study, a series of sucutinirane derivatives was prepared, and their in vitro toxicity in the HL-60 cell line was evaluated. Then the action mechanism of a representative compound that induces cell death was investigated. Whereas C-6 or C-7 diol esters and ether decreased the activity against the HL-60 cell line, furan-oxidized derivatives 12 and 13 showed improvement or retention of the activity compared with those of the natural products sucutinirane A (11), E (1), and F (2). Treatment with sucutinirane derivative 13 elevated caspase 3/7 activity and also decreased expression of Bcl-2 family proteins, Mcl-1, and Bid. Derivative 13 generated reactive oxygen species in HL-60 cells, whose apoptotic effects were attenuated by the addition of an antioxidant, N-acetyl-L-cysteine. These results suggest that cassane butenolide 13 induces apoptosis in HL-60 via its oxidative effects.

  14. Quantification of flavonol glycosides in Camellia sinensis by MRM mode of UPLC-QQQ-MS/MS.

    PubMed

    Wu, Yahui; Jiang, Xiaolan; Zhang, Shuxiang; Dai, Xinlong; Liu, Yajun; Tan, Huarong; Gao, Liping; Xia, Tao

    2016-04-01

    Phenolic compounds are major components of tea flavour, in which catechins and flavonol glycosides play important roles in the astringent taste of tea infusion. However, the flavonol glycosides are difficult to quantify because of the large variety, as well as the inefficient seperation on chromatography. In this paper, a total of 15 flavonol glycosides in the tea plant (Camellia sinensis) were identified by the high performance liquid chromatography (HPLC) coupled to a time-of-flight mass spectrometer (TOF-MS), and a quantitative method was established based on multiple reaction monitoring (MRM) mode of ultra-high performance liquid chromatography (UPLC) coupled to a triple quadrupole mass spectrometer (QQQ-MS/MS). It provided the limit of detection and quantification to the order of picogram, which was more sensitive than the HPLC detection of the order of nanogram. The relative standard deviations of the intra- and inter-day variations in retention time and signal intensity (peak area) of six analytes were less than 0.26% and 4%, respectively. The flavonol glycosides of four tea cultivars were relatively quantified using the signal intensity (peak area) of product ion, in which six flavonol glycosides were quantified by the authentic standards. The results showed that the flavonol mono-, di- and tri-glycoside mostly accumulated in young leaves of the four tea cultivars. Notably, the myricetin 3-O-galactoside was the major component among the six flavonol glycosides detected.

  15. Agrobacterium Mediated Transient Gene Silencing (AMTS) in Stevia rebaudiana: Insights into Steviol Glycoside Biosynthesis Pathway

    PubMed Central

    Guleria, Praveen; Yadav, Sudesh Kumar

    2013-01-01

    Background Steviol glycoside biosynthesis pathway has emerged as bifurcation from ent-kaurenoic acid, substrate of methyl erythritol phosphate pathway that also leads to gibberellin biosynthesis. However, the genetic regulation of steviol glycoside biosynthesis has not been studied. So, in present study RNA interference (RNAi) based Agrobacterium mediated transient gene silencing (AMTS) approach was followed. SrKA13H and three SrUGTs (SrUGT85C2, SrUGT74G1 and SrUGT76G1) genes encoding ent-kaurenoic acid-13 hydroxylase and three UDP glycosyltransferases of steviol glycoside biosynthesis pathway were silenced in Stevia rebaudiana to understand its molecular mechanism and association with gibberellins. Methodology/Principal Findings RNAi mediated AMTS of SrKA13H and three SrUGTs has significantly reduced the expression of targeted endogenous genes as well as total steviol glycoside accumulation. While gibberellins (GA3) content was significantly enhanced on AMTS of SrUGT85C2 and SrKA13H. Silencing of SrKA13H and SrUGT85C2 was found to block the metabolite flux of steviol glycoside pathway and shifted it towards GA3 biosynthesis. Further, molecular docking of three SrUGT proteins has documented highest affinity of SrUGT76G1 for the substrates of alternate pathways synthesizing steviol glycosides. This could be a plausible reason for maximum reduction in steviol glycoside content on silencing of SrUGT76G1 than other genes. Conclusions SrKA13H and SrUGT85C2 were identified as regulatory genes influencing carbon flux between steviol glycoside and gibberellin biosynthesis. This study has also documented the existence of alternate steviol glycoside biosynthesis route. PMID:24023961

  16. Variations in human urinary O-hydroxylysyl glycoside levels and their relationship to collagen metabolism

    PubMed Central

    Segrest, Jere P.; Cunningham, Leon W.

    1970-01-01

    Two O-hydroxylysyl glycosides, Hyl-Gal-Glc and Hyl-Gal, have been isolated from normal human urine and shown to be identical to two glycosides isolated from alkaline hydrolysates of collagen. A relatively sample and reproducible analytical procedure has been devised to measure the levels of these glycosides in human urine. By the use of this procedure it was shown that a normal diet has only a small effect on 24-hr urinary excretion levels of these glycosides indicating an endogenous origin. Urinary glycoside levels appear to be highest in children, roughly paralleling collagen turnover as indicated by urinary hydroxyproline levels. Collagen turnover equivalents calculated from urinary hydroxylysyl glycoside levels were found to be significantly larger than collagen turnover equivalents calculated from urinary hydroxyproline levels. This suggests that urinary glycosides are more quantitative indicators of collagen metabolism than urinary hydroxyproline. The ratio of Hyl-Gal-Glc to Hyl-Gal was measured in urines of diseased as well as normal individuals and a bimodal distribution was found. Alkaline hydrolysates of different human connective tissue collagens showed that only bone collagen, of the collagens examined, had a low ratio of Hyl-Gal-Glc to Hyl-Gal compared to human urine. Other collagens examined had higher ratios than found in human urine. On the basis of these results it is postulated that the bimodal distribution of glycoside ratios represents two populations of collagen turnover, the lower ratio population having a high bone collagen turnover, the lower ratio population having a high bone collagen turnover relative to the second population. Examination of the types of subjects making up the two populations supports this hypothesis. These data suggest that urinary O-hydroxylysyl glycoside excretion, in addition to providing a more quantitative estimate of collagen turnover than urinary hydroxyproline, may prove to be of value as a specific means of

  17. Biochemical ecology of the forest tent caterpillar: responses to dietary protein and phenolic glycosides.

    PubMed

    Lindroth, Richard L; Bloomer, Mark S

    1991-05-01

    Interactions between quaking aspen (Populus tremuloides) and the forest tent caterpillar (Malacosoma disstria) are likely to be influenced by leaf protein and phenolic glycoside levels, and insect detoxication activity. We investigated the direct and interactive effects of dietary protein and phenolic glycosides on larval performance and midgut enzyme activity of forest tent caterpillars. We conducted bioassays with six artificial diets, using both first and fourth stadium larvae. Four of the diets comprised a 2×2 factorial design-two levels of protein, each with and without phenolic glycosides. Additionally, we assayed high protein diets containing S,S,S-tributylphosphorotrithioate (DEF, an esterase inhibitor) and DEF plus phenolic glycosides. Enzyme solutions were prepared from midguts of sixth instars and assayed for β-glucosidase, esterase and glutathione transferase activities. First instar mortality and development times were higher for larvae on diets low in protein or containing phenolic glycosides. Effects of phenolic glycosides were especially pronounced at low protein levels and when administered with DEF. Fourth instar development times were prolonged, and growth rates reduced, in response to consumption of low protein diets. Effects of phenolic glycosides on growth were less pronounced, although the effect for larvae on the low protein diet was nearly significant. Activity of each of the enzyme systems was reduced in larvae reared on low protein diets, and esterase activity was induced in larvae fed phenolic glycosides. Our results suggest that larval performance may be strongly affected by levels of protein and phenolic glycosides commonly occurring in aspen foliage, and that these factors may play a role in differential defoliation of aspen by forest tent caterpillars.

  18. Uncommon Glycosidases for the Enzymatic Preparation of Glycosides

    PubMed Central

    Trincone, Antonio

    2015-01-01

    Most of the reports in literature dedicated to the use of glycosyl hydrolases for the preparation of glycosides are about gluco- (α- and β-form) and galacto-sidase (β-form), reflecting the high-availability of both anomers of glucosides and of β-galactosides and their wide-ranging applications. Hence, the idea of this review was to analyze the literature focusing on hardly-mentioned natural and engineered glycosyl hydrolases. Their performances in the synthetic mode and natural hydrolytic potential are examined. Both the choice of articles and their discussion are from a biomolecular and a biotechnological perspective of the biocatalytic process, shedding light on new applicative ideas and on the assortment of biomolecular diversity. The hope is to elicit new interest for the development of biocatalysis and to gather attention of biocatalyst practitioners for glycosynthesis. PMID:26404386

  19. Antioxidant phenylethanoid glycosides and a neolignan from Jacaranda caucana.

    PubMed

    Martin, Frédéric; Hay, Anne-Emmanuelle; Quinteros Condoretty, Valentin R; Cressend, Delphine; Reist, Marianne; Gupta, Mahabir P; Carrupt, Pierre-Alain; Hostettmann, Kurt

    2009-05-22

    Extracts from several plants of the family Bignoniaceae from Panama were submitted to a rapid DPPH TLC test for the detection of radical-scavenging activity. The MeOH extract of the stems of Jacaranda caucana, a tree that grows from Costa Rica to Colombia, was selected due to its interesting activity and the lack of phytochemical studies on the polar extract. This extract was partitioned between ethyl acetate, butanol, and water. The EtOAc fraction afforded two new phenylethanoid glycosides (1, 2), along with protocatechuic acid, acteoside, and jionoside D. Further purifications yielded isoacteoside and martynoside. The BuOH fraction afforded a new rhamnosyl derivative of sisymbrifolin (8), a neolignan. The structures were determined by means of spectrometric methods, including 1D and 2D NMR experiments and MS analysis.

  20. Two new lignan glycosides from the seeds of Cuscuta chinensis.

    PubMed

    He, Xiang-Hui; Yang, Wen-Zhi; Meng, A-Hui; He, Wen-Ni; Guo, De-An; Ye, Min

    2010-11-01

    Two new lignan glycosides, 2'-hydroxyl asarinin 2'-O-β-D-glucopyranoside (cuscutoside C, 1) and 2'-hydroxyl asarinin 2'-O-β-D-apiofuranosyl-(1 → 2)-[β-D-glucopyranosyl-(1 → 6)]-β-D-glucopyranoside (cuscutoside D, 2), were isolated from the seeds of Cuscuta chinensis Lam., along with six known compounds, 2'-hydroxyl asarinin 2'-O-β-D-glucopyranosyl-(1 → 6)-β-D-glucopyranoside (3), 2'-hydroxyl asarinin 2'-O-β-D-apiofuranosyl-(1 → 2)-β-D-glucopyranoside (cuscutoside A, 4), kaempferol 3,7-di-O-β-D-glucopyranoside (5), 5-caffeoyl quinic acid (6), 4-caffeoyl quinic acid (7), and cinnamic acid (8). Their structures were elucidated on the basis of spectroscopic analyses including HR-ESI-MS, ESI-MS/MS, (1)H and (13)C NMR, HSQC, HMBC, and TOCSY.

  1. C21 steroidal glycosides from the roots of Cynanchum paniculatum.

    PubMed

    Zhao, Dan; Feng, Baomin; Chen, Shaofei; Chen, Gang; Li, Zhifeng; Lu, Xiaojie; Sang, Xianan; An, Xiao; Wang, Haifeng; Pei, Yuehu

    2016-09-01

    As a part of our continuing research for bioactive constituents from Cynanchum plants, four new C21 steroidal glycosides, cynapanoside D-G (1-4), together with six known compounds (5-10) were isolated from the roots of Cynanchum paniculatum (Bge.) Kitag. Their structures were elucidated on the basis of 1D- and 2D-NMR spectroscopic data as well as HR-ESI-MS analysis. Compound 8 exhibited potent inhibitory activities against HL-60, HT-29, PC-3 and MCF-7 cell lines with IC50 values of 8.3, 7.5, 34.3 and 19.4μM, respectively and compounds 1-4 and 9 displayed moderate cytotoxicity against the four cell lines. The in vitro antioxidant activities of compounds 1-4, 8 and 9 were assayed by DPPH radical scavenging activity. Antibacterial and antifungal activities of compounds 1-4, 8 and 9 were also tested.

  2. Aromatic glycosides from the whole plants of Iris japonica.

    PubMed

    Shi, Guo-Ru; Wang, Xin; Liu, Yan-Fei; Zhang, Chun-Lei; Wang, Yan; Li, Li; Ni, Gang; Chen, Ruo-Yun; Yu, De-Quan

    2016-10-01

    Phytochemical investigation on the whole plants of Iris japonica led to the isolation of four new aromatic glycosides. Their structures including the absolute configurations were determined by spectroscopic and chemical methods as (-)-4-hydroxy-3-methoxy acetophenone 4-O-β-d-{6-O-[4-O-(7R,8S)-(4-hydroxy-3-methoxyphenylglycerol-8-yl)-3-methoxybenzoyl]}-glucopyranoside (1), (-)-4-hydroxy-3-methoxy acetophenone 4-O-β-d-{6-O-[4-O-(7S,8R)-(4-hydroxy-3-methoxyphenylglycerol-8-yl)-3-methoxybenzoyl]}-glucopyranoside (2), (-)-4-hydroxy-3-methoxy acetophenone 4-O-β-d-{6-O-[4-O-(7R,8R)-(4-hydroxy-3-methoxyphenylglycerol-8-yl)-3-methoxybenzoyl]}-glucopyranoside (3), (-)-4-hydroxy-3-methoxy acetophenone 4-O-β-d-{6-O-[4-O-(7S,8S)-(4-hydroxy-3-methoxyphenylglycerol-8-yl)-3-methoxybenzoyl]}-glucopyranoside (4), respectively.

  3. Two new sesquiterpenoid glycosides from the leaves of Lycium barbarum.

    PubMed

    Wang, Yan; Zhao, Bo; Ma, Hai-Rong; Aisa, Haji Akber

    2016-09-01

    Two new sesquiterpenoid glycosides, lyciumionosides A-B (1-2), together with four known compounds (3-6), were isolated from the leaves of Lycium barbarum. Their structures were mainly established on the basis of MS, 1D and 2D NMR spectroscopic techniques. The antiproliferative activities of compounds 1-5 were evaluated. Compound 1 showed highest inhibitory activity against A549 cells with IC50 value of 32.6 ± 2.6 μM, compound 3 showed highest inhibitory activity against PC-3 cells with IC50 value of 36.0 ± 2.9 μM, and compound 5 exhibited highest inhibitory activity against HeLa cells with IC50 value of 32.3 ± 4.2 μM.

  4. Cerebrosides and terpene glycosides from the root of Aster scaber.

    PubMed

    Kwon, Hak Cheol; Cho, Ock Ryun; Lee, Kang Choon; Lee, Kang Ro

    2003-02-01

    Three cerebrosides 2, 3, and 5 and two terpene glycosides 1 and 4 have been isolated from the methanol extract of the root of Aster scaber. Their structures were determined as 3-O-beta-D-glucuronopyranosyl-oleanolic acid methyl ester (1), (2S, 3S, 4R, 2'R, 8Z, 15'Z)-N-2'-hydroxy-15'-tetracosenoyl-1-O-beta-D-glucopyranosyl-4-hydroxy-8-sphingenine (2), (2S, 3S, 4R, 8Z)-N-octadecanoyl-1-O-beta-D-glucopyranosyl-4-hydroxy-8-sphingenine (3), 1alpha-hydroxy-6beta-O-beta-D-glucosyl-eudesm-3-ene (4), and (2S, 3S, 4R, 2'R, 8Z)-N-2'-hydroxy-hexadecanoyl-1-O-beta-D-glucopyranosyl-4-hydroxy-8-sphingenine (5) on the basis of spectroscopic methods.

  5. Flavanone Glycosides as Acetylcholinesterase Inhibitors: Computational and Experimental Evidence

    PubMed Central

    Remya, C.; Dileep, K. V.; Tintu, I.; Variyar, E. J.; Sadasivan, C.

    2014-01-01

    Acetylcholinesterase hydrolyzes the neurotransmitter called acetylcholine and is crucially involved in the regulation of neurotransmission. One of the observable facts in the neurodegenerative disorders like Alzheimer's disease is the decrease in the level of acetylcholine. Available drugs that are used for the treatment of Alzheimer's disease are primarily acetylcholinesterase inhibitors with multiple activities. They maintain the level of acetylcholine in the brain by inhibiting the acetylcholinesterase function. Hence acetylcholinesterase inhibitors can be used as lead compounds for the development of drugs against AD. In the present study, the binding potential of four flavanone glycosides such as naringin, hesperidin, poncirin and sakuranin against acetylcholinesterase was analysed by using the method of molecular modeling and docking. The activity of the top scored compound, naringin was further investigated by enzyme inhibition studies and its inhibitory concentration (IC50) towards acetylcholinesterase was also determined. PMID:25593395

  6. [Glycosides from flowers of Jasminum officinale L. var. grandiflorum].

    PubMed

    Zhao, Gui-qin; Xia, Jing-jing; Dong, Jun-xing

    2007-10-01

    To study the chemical constituents of the flower of Jasminum officinale L. var. grandiflorum. The compounds were isolated and purified by re-crystallization and chromatography on silica gel and Sephadex LH-20 column. Their structures were elucidated on the physicochemical properties and spectral analysis. Seven glycosides were identified as kaempferol-3-O-alpha-L-rhamnopyranosyl (1-->3)-[alpha-L-rhamnopyranosyl (1-->6)]-beta-D-galactopyranoside (I), kaempferol-3-O-rutinoside (II), 7-ketologanin (III), oleoside-11-methyl ester (IV), 7-glucosyl-l1-methyl oleoside (V), ligstroside (VI), oleuropein (VII). Compound I is a new compound. Compounds III and V were isolated from the family of Jasminum for the first time and compounds II, IV and VI were isolated from Jasminum officinale L. var. grandiflorum for the first time.

  7. Acutifoliside, a novel benzoic acid glycoside from Salix acutifolia.

    PubMed

    Wu, Yanqi; Dobermann, Darja; Beale, Michael H; Ward, Jane L

    2016-08-01

    Ultra high-performance liquid chromatography-mass spectrometry (UHPLC-MS) profiling of a polar solvent extract of juvenile stem tissue of Salix acutifolia Willd. identified a range of phenolic metabolites. Salicortin, 1, a well-known salicinoid, was the major compound present and the study identified young stem tissue of this species as a potential source of this compound for future studies. Three further known metabolites (salicin 2, catechin 3 and tremuloidin 4) were also present. The UHPLC-MS analysis also revealed the presence of a further, less polar, unknown compound, which was isolated via HPLC peak collection. The structure was elucidated by high-resolution mass spectroscopic analysis, 1- and 2-D NMR analysis and chemical derivatisation and was shown to be a novel benzoic acid glycoside 5, which we have named as acutifoliside.

  8. [Studies on triterpenoids and their glycosides from Aralia dasyphylla Miq].

    PubMed

    Yi, Y H; Gu, J Q; Xiao, K; Wang, Z Z; Lin, H W

    1997-10-01

    The structures of two triterpenoids and their glycosides were isolated from Aralia dasyphylla Miq. Their structures have been identified to be oleanoic acid(I), 16 beta-hydroxy-18 beta-H-oleanoic acid(II), oleanoic acid-28-O-beta-D-glucopyranoside(III) and 16 beta-hydroxy-18 beta-H-oleanoic acid-28-O-beta-D-glucopyranoside(IV), respectively, mainly through interpretation of UV, IR, MS, 1H and 13CNMR, DEPT, HMQC and HMBC spectra data. The stereochemistry of II has been confirmed by NOESY. Pharmacological experiments showed that the total saponins exerted preventative effect on CCl4-induced liver injury of male mice and hypoglycemic effect on a model of alloxan-induced diabetes in rats.

  9. Neuroactive flavonoid glycosides from Tilia petiolaris DC. extracts.

    PubMed

    Loscalzo, Leonardo M; Wasowski, Cristina; Marder, Mariel

    2009-10-01

    Pharmacological assay guided purification of an ethanol extract of Tilia petiolaris DC. inflorescences resulted in the isolation and identification of isoquercitrin (ISO), quercetin 3-O-glucoside-7-O-rhamnoside (QUE) and kaempferol 3-O-glucoside-7-O-rhamnoside (KAE). The behavioral actions of these glycosylated flavonoids were examined in the hole board, locomotor activity and thiopental-induced loss of righting reflex tests in mice. QUE (10 and 30 mg/kg) and KAE (30 mg/kg), intraperitoneally (i.p.) administered to mice, reduced all the parameters measured in the hole board test, but ISO (30 mg/kg) only reduced the number of rearings. Meanwhile QUE at 30 mg/kg i.p. also decreased the ambulatory locomotor activity and increased the sodium thiopental-induced time of loss of the righting reflex suggesting a clear depressant action. The above results demonstrate the occurrence of neuroactive flavonoid glycosides in Tilia.

  10. Steroidal glycosides from the underground parts of Yucca glauca and their cytotoxic activities.

    PubMed

    Yokosuka, Akihito; Suzuki, Tomoka; Tatsuno, Satoru; Mimaki, Yoshihiro

    2014-05-01

    Six steroidal glycosides and 14 known compounds were isolated from the underground parts of Yucca glauca (Agavaceae). Their structures were determined from extensive spectroscopic analysis, including analysis of two-dimensional NMR data, and from chemical transformations. The compounds were also evaluated for cytotoxic activities against HL-60 human leukemia cells and A549 human lung adenocarcinoma cells. Four spirostanol glycosides and three furostanol glycosides exhibited cytotoxic activities against both HL-60 and A549 cells. Two of the compounds induced apoptosis in HL-60 cells.

  11. Allimacrosides A-E, new steroidal glycosides from Allium macrostemon Bunge.

    PubMed

    Kim, Yun Sik; Suh, Won Se; Park, Kyoung Jin; Choi, Sang Un; Lee, Kang Ro

    2017-02-01

    A new pregnane-type steroidal glycoside (1), two new spirostane-type steroidal glycosides (2, 3), and two new furostane-type steroidal glycosides (4, 5), named allimacrosides A-E, together with four known compounds (6-9) were isolated from a 80% MeOH extract of Allium macrostemon Bunge. The identification and structural elucidation of these compounds were based on their 1D- and 2D-NMR spectra, and HR-FAB-MS data analysis. The isolated compounds were tested for cytotoxicity against four human tumor cell lines in vitro using the sulforhodamine B bioassay.

  12. [Study on limit detection of flavones in diterpene ginkgolides meglumine injection materials by LC-MS and HPLC-DAD].

    PubMed

    Bi, Sen; Li, Yan-jing; Huang, Wen-zhe; Kang, Dan-yu; Ding, Gang; Xiao, Wei

    2015-08-01

    Limit test of flavones in diterpene ginkgolides meglumine injection materials by UV-Vis and HPLC-DAD method was studied in this essay. The HPLC-DAD method has lower LOD (about 1% of the UV-Vis), that is, the sensitivity is higher than UV-Vis method. Through the analysis of the kinds of flavonoids ingredients in the samples by LC-MS, the three compounds with highest contents are kaempferol, quercetin and isorhamnetin. Kaempferol, quercetin and isorhamnetin were chosen as reference compounds for HPLC analysis, and the HPLC separation analysis was carried on an Agilent Eclipse plus C18 column (4.6 mm x 250 mm, 5 μm) with methanol and water containing 0.4% phosphoric acid (50: 50) as mobile phase, and the flow rate was 1.0 mL x min(-1). The detection wavelength was set at 360 nm. This method has good specificity, precision and reproducibility. The LODs of quercetin, kaempferide and isorhamnetin were 27.6, 22.3, 29.5 μg x L(-1). The average recovery was 87.9% (RSD 3.3%), 91.7% (RSD 3.1%), 88.3 (RSD 1.3%) for quercetin, kaempferide and isorhamnetin, respectively. Based on the 10 batches of sample results and sensitivity of different HPLC, the content of total flavonoids ingredients of diterpene ginkgolides meglumine injection materials was limited no more than 2 x 10(-5). This method is simple, quick and has good maneuverability, and could be used to the limit test of flavonoids in the diterpene ginkgolides meglumine injection materials.

  13. Involvement of an ent-copalyl diphosphate synthase in tissue-specific accumulation of specialized diterpenes in Andrographis paniculata.

    PubMed

    Misra, Rajesh Chandra; Garg, Anchal; Roy, Sudeep; Chanotiya, Chandan Singh; Vasudev, Prema G; Ghosh, Sumit

    2015-11-01

    Ent-labdane-related diterpene (ent-LRD) specialized (i.e. secondary) metabolites of the medicinal plant kalmegh (Andrographis paniculata) have long been known for several pharmacological activities. However, our understanding of the ent-LRD biosynthetic pathway has remained largely incomplete. Since ent-LRDs accumulate in leaves, we carried out a comparative transcriptional analysis using leaf and root tissues, and identified 389 differentially expressed transcripts, including 223 transcripts that were preferentially expressed in leaf tissue. Analysis of the transcripts revealed various specialized metabolic pathways, including transcripts of the ent-LRD biosynthetic pathway. Two class II diterpene synthases (ApCPS1 and ApCPS2) along with one (ApCPS1') and two (ApCPS2' and ApCPS2″) transcriptional variants that were the outcomes of alternative splicing of the precursor mRNA and alternative transcriptional termination, respectively, were identified. ApCPS1 and ApCPS2 encode for 832- and 817-amino acids proteins, respectively, and are phylogenetically related to the dicotyledons ent-copalyl diphosphate synthases (ent-CPSs). The spatio-temporal patterns of ent-LRD metabolites accumulation and gene expression suggested a likely role for ApCPS1 in general (i.e. primary) metabolism, perhaps by providing precursor for the biosynthesis of phytohormone gibberellin (GA). However, ApCPS2 is potentially involved in tissue-specific accumulation of ent-LRD specialized metabolites. Bacterially expressed recombinant ApCPS2 catalyzed the conversion of (E,E,E)-geranylgeranyl diphosphate (GGPP), the general precursor of diterpenes to ent-copalyl diphosphate (ent-CPP), the precursor of ent-LRDs. Taken together, these results advance our understanding of the tissue-specific accumulation of specialized ent-LRDs of medicinal importance.

  14. Analysis of glycosidically bound aroma precursors in tea leaves. 3. Change in the glycoside content of tea leaves during the oolong tea manufacturing process.

    PubMed

    Wang, D; Kubota, K; Kobayashi, A; Juan, I M

    2001-11-01

    A direct qualitative and quantitative determination of the glycosides of tea aroma compounds at the four stages of the oolong tea manufacturing process (plucking, solar withering, indoor withering, and oolong tea product) was carried out by a capillary gas chromatographic-mass spectrometric analysis after trifluoroacetyl derivatization of the glycosidic fractions. Sixteen glucosides and primeverosides were identified and quantified in cv. Chin-shin-oolong and cv. Chinhsuan-oolong. A comparison of the glycosides in dried fresh leaves between the two cultivars showed significant differences. During the manufacturing process, the amounts of most of these glycosides increased from the solar-withering stage, reaching the highest level at the final stage of oolong tea production. It was noted that no glycoside decreased in its content during the manufacturing process, this being quite different from the manufacture of black tea. In addition, the contents of these alcoholic aroma compounds in the free aroma concentrate from each cultivar remained almost unchanged or slightly decreased, and they constituted only about 12 and 17% in amount of the whole oolong tea aroma compounds. However, jasmine lactone and indole were markedly higher in the final oolong tea products.

  15. Synthetic studies of neoclerodane diterpenes from Salvia divinorum: role of the furan in affinity for opioid receptors.

    PubMed

    Simpson, Denise S; Lovell, Kimberly M; Lozama, Anthony; Han, Nina; Day, Victor W; Dersch, Christina M; Rothman, Richard B; Prisinzano, Thomas E

    2009-09-21

    Further synthetic modification of the furan ring of salvinorin A (1), the major active component of Salvia divinorum, has resulted in novel neoclerodane diterpenes with opioid receptor affinity and activity. A computational study has predicted 1 to be a reproductive toxicant in mammals and is suggestive that use of 1 may be associated with adverse effects. We report in this study that piperidine 21 and thiomorpholine 23 have been identified as selective partial agonists at kappa opioid receptors. This indicates that additional structural modifications of 1 may provide ligands with good selectivity for opioid receptors but with reduced potential for toxicity.

  16. Structural elucidation and evaluation of multidrug-resistance modulatory capability of amarissinins A-C, diterpenes derived from Salvia amarissima.

    PubMed

    Bautista, Elihú; Fragoso-Serrano, Mabel; Ortiz-Pastrana, Naytzé; Toscano, Rubén A; Ortega, Alfredo

    2016-10-01

    Three new diterpenes (amarissinins A-C, 1-3) containing several oxygenated functionalities were isolated from the leaves and flowers of Salvia amarissima. The structures of these compounds were established through the analysis of their NMR spectroscopy and mass spectrometry data. The structures of compounds 1 and 2 were confirmed by single crystal X-ray diffraction. Compound 2 was identified as a C-10 epimer of dugesin F (5). The cytotoxic activity of these compounds against five human cancer cell lines was determined. Additionally, the capability to modulate the multidrug resistance (MDR) in the MCF-7 cancer cell line resistant to vinblastine was tested.

  17. Characterization of cyclitol glycosides by gas chromatography coupled to mass spectrometry.

    PubMed

    Ruiz-Aceituno, L; Carrero-Carralero, C; Ruiz-Matute, A I; Ramos, L; Sanz, M L; Martínez-Castro, I

    2017-02-10

    Several cyclitol glycosides have been characterised as trimethylsilyl derivatives by their gas chromatographic (GC) retention data (linear retention indices) and electron impact mass spectrometric (MS) profiles. Both GC-MS results have been related to cyclitol glycosides structural features. Abundance ratios of characteristic m/z ions 133/129 and 260/265 have been proposed to distinguish glycosyl-inositols from glycosyl-methyl-inositols. These ratios in combination with the presence or absence of m/z 375 ion allowed the unequivocal characterization of cyclitol glycosides. These criteria have been applied to the characterization of new cyclitol glycosides in chickpea (Cicer arietinum) and adzuki bean (Vigna angularis) and in leaves of Coriaria myrtifolia and Coriaria ruscifolia.

  18. High-throughput cloning, expression and purification of glycoside hydrolases using Ligation-Independent Cloning (LIC).

    PubMed

    Camilo, Cesar M; Polikarpov, Igor

    2014-07-01

    Recent advances in DNA sequencing techniques have led to an explosion in the amount of available genome sequencing data and this provided an inexhaustible source of uncharacterized glycoside hydrolases (GH) to be studied both structurally and enzymatically. Ligation-Independent Cloning (LIC), an interesting alternative to traditional, restriction enzyme-based cloning, and commercial recombinatorial cloning, was adopted and optimized successfully for a high throughput cloning, expression and purification pipeline. Using this platform, 130 genes encoding mainly uncharacterized glycoside hydrolases from 13 different organisms were cloned and submitted to a semi-automated protein expression and solubility screening in Escherichia coli, resulting in 73 soluble targets. The high throughput approach proved to be a powerful tool for production of recombinant glycoside hydrolases for further structural and biochemical characterization and confirmed that thioredoxin fusion tag (TRX) is a better choice to increase solubility of recombinant glycoside hydrolases expressed in E. coli, when compared to His-tag alone.

  19. Solubility enhancement of steviol glycosides and characterization of their inclusion complexes with gamma-cyclodextrin.

    PubMed

    Upreti, Mani; Strassburger, Ken; Chen, You L; Wu, Shaoxiong; Prakash, Indra

    2011-01-01

    Steviol glycosidesrebaudioside (reb) A, C and D have low aqueous solubilities. To improve their aqueous solubilities, inclusion complex of steviol glycosides, reb A, C and D and gamma cyclodextrin were prepared by freeze drying method and further characterized by means of differential scanning calorimetry, Fourier transform infrared spectroscopy and Raman spectroscopy. The effect of gamma cyclodextrin on chemical shifts of the steviol glycosides was also studied in proton NMR experiments as well as in solid state (13)C CP/MAS NMR experiments. These results indicated that the steviol glycosides were clearly in inclusion complex formation with the gamma cyclodextrin which also results in solubility enhancement of these steviol glycosides. Phase solubility studies showed that amounts of soluble reb A, C and D increased with increasing amounts of gamma cyclodextrin indicating formation of 1:1 stoichiometric and higher order inclusion complexes.

  20. Solubility Enhancement of Steviol Glycosides and Characterization of Their Inclusion Complexes with Gamma-Cyclodextrin

    PubMed Central

    Upreti, Mani; Strassburger, Ken; Chen, You L.; Wu, Shaoxiong; Prakash, Indra

    2011-01-01

    Steviol glycosidesrebaudioside (reb) A, C and D have low aqueous solubilities. To improve their aqueous solubilities, inclusion complex of steviol glycosides, reb A, C and D and gamma cyclodextrin were prepared by freeze drying method and further characterized by means of differential scanning calorimetry, Fourier transform infrared spectroscopy and Raman spectroscopy. The effect of gamma cyclodextrin on chemical shifts of the steviol glycosides was also studied in proton NMR experiments as well as in solid state 13C CP/MAS NMR experiments. These results indicated that the steviol glycosides were clearly in inclusion complex formation with the gamma cyclodextrin which also results in solubility enhancement of these steviol glycosides. Phase solubility studies showed that amounts of soluble reb A, C and D increased with increasing amounts of gamma cyclodextrin indicating formation of 1:1 stoichiometric and higher order inclusion complexes. PMID:22174615

  1. Analysis of supercooling-facilitating (anti-ice nucleation) activity of flavonol glycosides.

    PubMed

    Kasuga, Jun; Fukushi, Yukiharu; Kuwabara, Chikako; Wang, Donghui; Nishioka, Atsushi; Fujikawa, Emiko; Arakawa, Keita; Fujikawa, Seizo

    2010-04-01

    Deep supercooling xylem parenchyma cells (XPCs) of katsura tree (Cercidiphyllum japonicum) contain four kinds of flavonol glycosides with high supercooling-facilitating (anti-ice nucleation) activities. These flavonol glycosides have very similar structures, but their supercooling-facilitating activities are very different. In this study, we analyzed the supercooling-facilitating activities of 12 kinds of flavonol glycosides in order to determine the chemical structures that might affect supercooling-facilitating activity. All of the flavonol glycosides tested showed supercooling-facilitating activity, although the magnitudes of activity differed among the compounds. It was clear that the combination of the position of attachment of the glycosyl moiety, the kind of attached glycosyl moiety and the structure of aglycone determined the magnitude of anti-ice nucleation activity. However, there is still some ambiguity preventing the exact identification of features that affect the magnitude of supercooling-facilitating activity.

  2. Kaempferol glycosides in the flowers of carnation and their contribution to the creamy white flower color.

    PubMed

    Iwashina, Tsukasa; Yamaguchi, Masa-atsu; Nakayama, Masayoshi; Onozaki, Takashi; Yoshida, Hiroyuki; Kawanobu, Shuji; Onoe, Hiroshi; Okamura, Masachika

    2010-12-01

    Three flavonol glycosides were isolated from the flowers of carnation cultivars 'White Wink' and 'Honey Moon'. They were identified from their UV, MS, 1H and 13C NMR spectra as kaempferol 3-O-neohesperidoside, kaempferol 3-O-sophoroside and kaempferol 3-O-glucosyl-(1 --> 2)-[rhamnosyl-(1 --> 6)-glucoside]. Referring to previous reports, flavonols occurring in carnation flowers are characterized as kaempferol 3-O-glucosides with additional sugars binding at the 2 and/or 6-positions of the glucose. The kaempferol glycoside contents of a nearly pure white flower and some creamy white flower lines were compared. Although the major glycoside was different in each line, the total kaempferol contents of the creamy white lines were from 5.9 to 20.9 times higher than the pure white line. Thus, in carnations, kaempferol glycosides surely contribute to the creamy tone of white flowers.

  3. [STEROIDAL GENINS AND GLYCOSIDES OF SPIROSTAN AND FUROSTAN SERIES AS ANTHELMINTHIC AGENTS].

    PubMed

    Islamova, Zh I; Khushbaktova, Z A; Abdullaev, N D; Syrov, V N

    2016-01-01

    It was established that steroidal genins and their glycosides of the spirostan series and (especially) furostan series show anticestodal activity against Hymeiolepis nana species. Search for anthelminthic agents in the indicated series of compounds is a promising direction of research.

  4. The hallucinogenic diterpene salvinorin A inhibits leukotriene synthesis in experimental models of inflammation.

    PubMed

    Rossi, Antonietta; Pace, Simona; Tedesco, Federica; Pagano, Ester; Guerra, Germano; Troisi, Fabiana; Werner, Markus; Roviezzo, Fiorentina; Zjawiony, Jordan K; Werz, Oliver; Izzo, Angelo A; Capasso, Raffaele

    2016-04-01

    Leukotrienes (LTs) are lipid mediators derived from arachidonic acid (AA) involved in a number of autoimmune/inflammatory disorders including asthma, allergic rhinitis and cardiovascular diseases. Salvinorin A (SA), a diterpene isolated from the hallucinogenic plant Salvia divinorum, is a well-established analgesic compound, but its anti-inflammatory properties are under-researched and its effects on LT production is unknown to date. Here, we studied the possible effect of SA on LT production and verified its actions on experimental models of inflammation in which LTs play a prominent role. Peritoneal macrophages (PM) stimulated by calcium ionophore A23187 were chosen as in vitro system to evaluate the effect of SA on LT production. Zymosan-induced peritonitis in mice and carrageenan-induced pleurisy in rats were selected as LT-related models to evaluate the effect of SA on inflammation as well as on LT biosynthesis. SA inhibited, in a concentration-dependent manner, A23187-induced LTB4 biosynthesis in isolated PM. In zymosan-induced peritonitis, SA inhibited cell infiltration, myeloperoxidase activity, vascular permeability and LTC4 production in the peritoneal cavity without decreasing the production of prostaglandin E2. In carrageenan-induced pleurisy in rats, a more sophisticated model of acute inflammation related to LTs, SA significantly inhibited LTB4 production in the inflammatory exudates, along with reducing the phlogistic process in the lung. In conclusion, SA inhibited LT production and it was effective in experimental models of inflammation in which LTs play a pivotal role. SA might be considered as a lead compound for the development of drugs useful in LTs-related diseases.

  5. Phytol, a Diterpene Alcohol from Chlorophyll, as a Drug against Neglected Tropical Disease Schistosomiasis Mansoni

    PubMed Central

    de Moraes, Josué; de Oliveira, Rosimeire N.; Costa, Jéssica P.; Junior, Antonio L. G.; de Sousa, Damião P.; Freitas, Rivelilson M.; Allegretti, Silmara M.; Pinto, Pedro L. S.

    2014-01-01

    Background Schistosomiasis is a major endemic disease that affects hundreds of millions worldwide. Since the treatment and control of this parasitic disease rely on a single drug, praziquantel, it is imperative that new effective drugs are developed. Here, we report that phytol, a diterpene alcohol from chlorophyll widely used as a food additive and in medicinal fields, possesses promising antischistosomal properties in vitro and in a mouse model of schistosomiasis mansoni. Methods and findings In vitro, phytol reduced the motor activity of worms, caused their death and confocal laser scanning microscopy analysis showed extensive tegumental alterations in a concentration-dependent manner (50 to 100 µg/mL). Additionally, phytol at sublethal doses (25 µg/mL) reduced the number of Schistosoma mansoni eggs. In vivo, a single dose of phytol (40 mg/kg) administered orally to mice infected with adult S. mansoni resulted in total and female worm burden reductions of 51.2% and 70.3%, respectively. Moreover, phytol reduced the number of eggs in faeces (76.6%) and the frequency of immature eggs (oogram pattern) was significantly reduced. The oogram also showed increases in the proportion of dead eggs. Confocal microcopy studies revealed tegumental damage in adult S. mansoni recovered from mice, especially in female worms. Conclusions The significant reduction in parasite burden by this chlorophyll molecule validates phytol as a promising drug and offers the potential of a new direction for chemotherapy of human schistosomiasis. Phytol is a common food additive and nonmutagenic, with satisfactory safety. Thus, phytol has potential as a safe and cost-effective addition to antischistosomal therapy. PMID:24392173

  6. Ent-Kaurane diterpenes from Annona glabra and their cytotoxic activities.

    PubMed

    Anh, Hoang Le Tuan; Hien, Nguyen Thi Thu; Hang, Dan Thi Thuy; Ha, Tran Minh; Nhiem, Nguyen Xuan; Hien, Truong Thi Thu; Thu, Vu Kim; Thao, Do Thi; Van Minh, Chau; Kiem, Phan Van

    2014-12-01

    A new ent-kaurane glycoside, annoglabasin H (1), and three known ent-kauranes, annoglabasin E (2), annoglabasin B (3), and 19-nor-ent-kaurent-4-ol-17-oic acid (4) were isolated from the fruits of Annona glabra. Their structures were determined by the combination of spectroscopic and chemical methods, including 1D- and 2D-NMR spectroscopy, as well as by comparison with the NMR data reported in the literature. The cytotoxic activities of these compounds were evaluated on four human cancer cell lines, LU-1, MCF-7, SK-Mel2, and KB. Compound 1 exhibited significant cytotoxic activity on all tested human cancer cell lines with IC50 values ranging from 3.7 to 4.6 μM.

  7. Characterization and Modeling of the Collision Induced Dissociation Patterns of Deprotonated Glycosphingolipids: Cleavage of the Glycosidic Bond

    NASA Astrophysics Data System (ADS)

    Rožman, Marko

    2016-01-01

    Glycosphingolipid fragmentation behavior was investigated by combining results from analysis of a series of negative ion tandem mass spectra and molecular modeling. Fragmentation patterns extracted from 75 tandem mass spectra of mainly acidic glycosphingolipid species (gangliosides) suggest prominent cleavage of the glycosidic bonds with retention of the glycosidic oxygen atom by the species formed from the reducing end (B and Y ion formation). Dominant product ions arise from dissociation of sialic acids glycosidic bonds whereas product ions resulting from cleavage of other glycosidic bonds are less abundant. Potential energy surfaces and unimolecular reaction rates of several low-energy fragmentation pathways leading to cleavage of glycosidic bonds were estimated in order to explain observed dissociation patterns. Glycosidic bond cleavage in both neutral (unsubstituted glycosyl group) and acidic glycosphingolipids was the outcome of the charge-directed intramolecular nucleophilic substitution (SN2) mechanism. According to the suggested mechanism, the nucleophile in a form of carboxylate or oxyanion attacks the carbon at position one of the sugar ring, simultaneously breaking the glycosidic bond and yielding an epoxide. For gangliosides, unimolecular reaction rates suggest that dominant product ions related to the cleavage of sialic acid glycosidic bonds are formed via direct dissociation channels. On the other hand, low abundant product ions related to the dissociation of other glycosidic bonds are more likely to be the result of sequential dissociation. Although results from this study mainly contribute to the understanding of glycosphingolipid fragmentation chemistry, some mechanistic findings regarding cleavage of the glycosidic bond may be applicable to other glycoconjugates.

  8. Components of the ether-insoluble resin glycoside-like fraction from Cuscuta chinensis.

    PubMed

    Du, X M; Kohinata, K; Kawasaki, T; Guo, Y T; Miyahara, K

    1998-07-01

    A trisaccharide and four new glycosidic acids, named cuscutic acids A-D, along with known organic acids, acetic acid, propionic acid, (2S)-2-methylbutyric acid, tiglic acid, (2R, 3 R)-nilic acid, (11S) convolvulinolic acid and (11S)-jalapinolic acid have been isolated from the alkaline hydrolysate of the ether-insoluble resin glycoside-like fraction of the seeds of Cuscuta chinensis. The compounds were characterized on the basis of chemical and physical data.

  9. Effect of Cuscuta chinensis glycoside on the neuronal differentiation of rat pheochromocytoma PC12 cells.

    PubMed

    Jian-Hui, Liu; Bo, Jiang; Yong-Ming, Bao; Li-Jia, An

    2003-08-01

    Exposure of rat pheochromocytoma PC12 cells to Cuscuta chinensis glycoside induced neuronal differentiation with resulting outgrowth of neurites and increase of acetylcholinesterase activity. A specific inhibitor of mitogen-activated protein kinase (MAPK) kinase, PD98059, prevented this effect of C. chinensis on PC12 cells. These results suggested that C. chinensis glycoside induced neuronal differentiation in PC12 cells linked to the mitogen-activated protein kinase signaling cascade.

  10. Diversity synthesis of tetrahydroprotoberberines glycosides by combined chemical and microbial catalysis.

    PubMed

    Ge, Hai-Xia; Zhang, Jian; Qian, Kun; Yu, Bo-Yang; Chen, Xiao-Ping

    2016-10-01

    The present study was designed to construct the structurally diverse library of tetrahydroprotoberberines (THPBs) by combining the methods of chemical nonselective demethylation and microbial glycosylation. HPLC-MS/MS analyses tentatively identified 12 de-methylated and 9 glycosylated derivates of THPBs and 5 rarely oxidized glycosides of THPBs in the library. Through this effort, we achieved not only a variety of the THPBs and their glycosides but also tested the catalytic characteristics and capabilities of G. deliquescens NRRL 1086.

  11. 6-Hydroxypelargonidin glycosides in the orange-red flowers of Alstroemeria.

    PubMed

    Tatsuzawa, Fumi; Saito, Norio; Murata, Naho; Shinoda, Koichi; Shigihara, Atsushi; Honda, Toshio

    2003-04-01

    Two 6-hydroxypelargonidin glycosides were isolated from the orange-red flowers of Alstroemeria cultivars, and determined to be 6-hydroxypelargonidin 3-O-(beta-D-glucopyranoside) and 3-O-[6-O-(alpha-L-rhamnopyranosyl)-beta-D-glucopyranoside], respectively, by chemical and spectroscopic methods. In addition, five known anthocyanidin glycosides, 6-hydroxycyanidin 3-malonylglucoside, 6-hydroxycyanidin 3-rutinoside, cyanidin 3-malonylglucoside, cyanidin 3-rutinoside and pelargonidin 3-rutinoside were identified in the flowers.

  12. A new flavonoid glycoside from the rhizomes and roots of Smilax scobinicaulis.

    PubMed

    Xu, Jing; Feng, Shixiu; Wang, Qi; Zhang, Min; Zhang, Cunli

    2014-01-01

    A new flavonoid glycoside, hesperetin-7-O-[β-D-glucopyranosyl-(1 → 3)]-β-D-glucopyranosyl (1), was isolated from the n-BuOH extract of Smilax scobinicaulis, together with four known flavonoid glycosides, clematine (2), ononin (3), daidzin (4) and puerarin (5). All of the five compounds were reported from this material for the first time. Their structures were determined on the basis of spectroscopic and spectrometric methods.

  13. Iridoid glycosides isolated from Scrophularia dentata Royle ex Benth. and their anti-inflammatory activity.

    PubMed

    Zhang, Liuqiang; Zhu, Tiantian; Qian, Fei; Xu, Jinwen; Dorje, Gaawe; Zhao, Zhili; Guo, Fujiang; Li, Yiming

    2014-10-01

    Scrodentosides A-E (1-5), five new acylated iridoid glycosides, together with 19 known ones, were isolated from the whole plant of Scrophularia dentata Royle ex Benth. The structures of these isolated glycosides were elucidated by spectroscopic methods. Bioassay showed that compounds 7 and 11 had significant inhibitory effect against NF-κB activation with IC50 value of 43.7 μM and 1.02 μM respectively.

  14. Isorhamnetin glycosides with free radical and ONOO-scavenging activities from the stamens of Nelumbo nucifera.

    PubMed

    Hyun, Sook Kyung; Jung, Yu Jung; Chung, Hae Young; Jung, Hyun Ah; Choi, Jae Sue

    2006-04-01

    In this study, we isolated two new isorhamnetin glycosides, designated as nelumboroside A (3) and nelumboroside B (4), as well as the previously-characterized isorhamnetin glucoside (1) and isorhamnetin rutinoside (2), from the n-BuOH fraction of Nelumbo nucifera stamens. The structures of the two new compounds were then determined, using chemical and spectroscopic techniques. All isolated isorhamnetin glycosides 1-4 showed marked antioxidant activities in the DPPH, and ONOO- assays.

  15. "Ring opening-ring closure" strategy for the synthesis of aryl-C-glycosides.

    PubMed

    Liu, Chen-Fu; Xiong, De-Cai; Ye, Xin-Shan

    2014-05-16

    A new "ring-opening-ring closure" strategy for the synthesis of aryl-C-glycosides was described. This strategy exploited the nickel-catalyzed regioselective β-O elimination of glycals by reactions with various aryl boronic acids or potassium aryltrifluoroborates to yield the ring-opened products, which underwent the Lewis acid, protonic acid, PhSeCl, or NBS mediated ring closure reactions to afford diverse aryl-C-glycosides. After Lewis acids and protonic acids were screened, it was found that, starting from the ring-opened substrates, the Ph3PHBr or Sc(OTf)3 mediated ring closure reaction provided α- or β-preferred aryl-C-Δ(2,3)-glycosides, respectively. Furthermore, β-D-phenyl-C-glycosides were successfully prepared via the PhSeCl-mediated cyclization reaction, whereas the α-D-phenyl-C-glycoside was obtained via the NBS-mediated cyclization reaction. After removal of the 2-substituted functionalities by Bu3SnH/AIBN, the synthesis of 2-deoxy-aryl-C-glycosides was ultimately realized in a stereoselective manner.

  16. Transition of phenolics and cyanogenic glycosides from apricot and cherry fruit kernels into liqueur.

    PubMed

    Senica, Mateja; Stampar, Franci; Veberic, Robert; Mikulic-Petkovsek, Maja

    2016-07-15

    Popular liqueurs made from apricot/cherry pits were evaluated in terms of their phenolic composition and occurrence of cyanogenic glycosides (CGG). Analyses consisted of detailed phenolic and cyanogenic profiles of cherry and apricot seeds as well as beverages prepared from crushed kernels. Phenolic groups and cyanogenic glycosides were analyzed with the aid of high-performance liquid chromatography (HPLC) and mass spectrophotometry (MS). Lower levels of cyanogenic glycosides and phenolics have been quantified in liqueurs compared to fruit kernels. During fruit pits steeping in the alcohol, the phenolics/cyanogenic glycosides ratio increased and at the end of beverage manufacturing process higher levels of total analyzed phenolics were detected compared to cyanogenic glycosides (apricot liqueur: 38.79 μg CGG per ml and 50.57 μg phenolics per ml; cherry liqueur 16.08 μg CGG per ml and 27.73 μg phenolics per ml). Although higher levels of phenolics are characteristic for liqueurs made from apricot and cherry pits these beverages nevertheless contain considerable amounts of cyanogenic glycosides.

  17. Influence of steviol glycosides on the stability of vitamin C and anthocyanins.

    PubMed

    Woźniak, Łukasz; Marszałek, Krystian; Skąpska, Sylwia

    2014-11-19

    A high level of sweetness and health-promoting properties make steviol glycosides an interesting alternative to sugars or artificial sweeteners. The radical oxygen species scavenging activity of these compounds may influence the stability of labile particles present in food. Model buffer solutions containing steviol glycosides, a selected food antioxidant (vitamin C or anthocyanins), and preservative were analyzed during storage. The addition of steviol glycosides at concentrations of 50, 125, and 200 mg/L increased the stability of both ascorbic and dehydroascorbic acid (degradation rates decreased up to 3.4- and 4.5-fold, respectively); the effect was intensified by higher sweetener concentrations and higher acidity of the solutions. Glycosides used alone did not affect the stability of anthocyanins; however, they enhanced the protective effect of sugars; half-life times increased by ca. 33% in the presence of sucrose (100 g/L) and by ca. 52% when both sucrose (100 g/L) and glycosides (total 200 mg/L) were used. Steviol glycosides concentrations remained stable during experiments.

  18. UDP-dependent glycosyltransferases involved in the biosynthesis of steviol glycosides.

    PubMed

    Mohamed, Amal A A; Ceunen, Stijn; Geuns, Jan M C; Van den Ende, Wim; De Ley, Marc

    2011-07-01

    A short-term experiment was designed to measure the transcript levels of downstream genes contributing to the biosynthesis of steviol glycosides. Stevia rebaudiana plants were subjected to long- and short-day conditions for different time intervals. Samples from both lower and upper leaves were collected. Using quantitative real-time polymerase chain reaction, the transcript levels of three UDP-dependent glycosyltransferases, UGT85C2, UGT74G1 and UGT76G1, were studied. The results were compared with the steviol glycoside contents measured in the leaves, which were quantified by reversed phase HPLC. In the same daylength condition, steviol glycoside concentration and the transcript levels of the three UGT genes were higher in upper leaves than in lower leaves. Steviol glycosides accumulated more in plants under short-day conditions. Under these conditions, a highly significant correlation was found between UGT85C2 transcription and total steviol glycoside accumulation in the upper leaves. This suggests that the glycosylation of steviol to form steviolmonoside is the rate-limiting step in the glycosylation pathway of steviol glycosides. In these upper leaves, a relatively high accumulation of rebaudioside A compared to stevioside was also observed, however, without correlation with the transcription of UGT76G1.

  19. Fecalase: a model for activation of dietary glycosides to mutagens by intestinal flora

    SciTech Connect

    Tamura, G.; Gold, C.; Ferro-Luzzi, A.; Ames, B.N.

    1980-08-01

    Many substances in the plant kingdom and in man's diet occur as glycosides. Recent studies have indicated that many glycosides that are not mutagenic in tests such as the Salmonella test become mutagenic upon hydrolysis of the glycosidic linkages. The Salmonella test utilizes a liver homogenate to approximate mammalian metabolism but does not provide a source of the enzymes present in intestinal bacterial flora that hydrolyze the wide variety of glycosides present in nature. We describe a stable cell-free extract of human feces, fecalase, which is shown to contain various glycosidases that allow the in vitro activation of many natural glycosides to mutagens in the Salmonella/liver homogenate test. Many beverages, such as red wine (but apparently not white wine) and tea, contain glycosides of the mutagen quercetin. Red wine, red grape juice, and teas were mutagenic in the test when fecalase was added, and red wine contained considerable direct mutagenic activity in the absence of fecalase. The implications of quercetin mutagenicity and carcinogenicity are discussed.

  20. Taming the Reactivity of Glycosyl Iodides To Achieve Stereoselective Glycosidation.

    PubMed

    Gervay-Hague, Jacquelyn

    2016-01-19

    that even highly functionalized aglycon acceptors add. Following the coupling event, the TMS ethers are readily removed by methanolysis, and since all of the byproducts are volatile, multiple reactions can be performed in a single reaction vessel without isolation of intermediates. In this fashion, per-O-TMS monosaccharides can be converted to biologically relevant α-linked glycolipids in one pot. The stereochemical outcome of these reactions can also be switched to β-glycoside formation by addition of silver to chelate the iodide, thus favoring SN2 displacement of the α-iodide. While iodides derived from benzyl and silyl ether-protected oligosaccharides are susceptible to interglycosidic bond cleavage when treated with TMSI, the introduction of a single acetate protecting group prevents this unwanted side reaction. Partial acetylation of armed glycosyl iodides also attenuates HI elimination side reactions. Conversely, fully acetylated glycosyl iodides are deactivated and require metal catalysis in order for glycosidation to occur. Recent findings indicate that I2 activation of per-O-acetylated mono-, di-, and trisaccharides promotes glycosidation of cyclic ethers to give β-linked iodoalkyl glycoconjugates in one step. Products of these reactions have been converted into multivalent carbohydrate displays. With these synthetic pathways elucidated, chemical reactivity can be exquisitely controlled by the judicious selection of protecting groups to achieve high stereocontrol in step-economical processes.

  1. Identification of diterpene alkaloids from Aconitum napellus subsp. firmum and GIRK channel activities of some Aconitum alkaloids.

    PubMed

    Kiss, Tivadar; Orvos, Péter; Bánsághi, Száva; Forgo, Peter; Jedlinszki, Nikoletta; Tálosi, László; Hohmann, Judit; Csupor, Dezső

    2013-10-01

    Diterpene alkaloids neoline (1), napelline (2), isotalatizidine (3), karakoline (4), senbusine A (5), senbusine C (6), aconitine (7) and taurenine (8) were identified from Aconitum napellus L. subsp. firmum, four (2-4, 6) of which are reported for the first time from this plant. The structures were determined by means of LC-MS, 1D and 2D NMR spectroscopy, including (1)H-(1)H COSY, NOESY, HSQC and HMBC experiments. Electrophysiological effects of the isolated compounds, together with nine diterpene alkaloids previously obtained from Aconitum toxicum and Consolida orientalis were investigated on stable transfected HEK-hERG (Kv11.1) and HEK-GIRK1/4 (Kir3.1 and Kir3.4) cell lines using automated patch clamp equipment. Significant blocking activity on GIRK channel was exerted by aconitine (7) (45% at 10 μM), but no blocking activities of the other investigated compounds were detected. The tested compounds were inactive on hERG channel in the tested concentration. The comparison of the previously reported metabolites of A. napellus subsp. firmum and compounds identified in our experiment reveals substantial variability of the alkaloid profile of this taxon.

  2. Direct and comprehensive analysis of ginsenosides and diterpene alkaloids in Shenfu injection by combinatory liquid chromatography-mass spectrometric techniques.

    PubMed

    Yang, Hua; Liu, Lei; Gao, Wen; Liu, Ke; Qi, Lian-Wen; Li, Ping

    2014-04-01

    Shenfu injection (SFI) is a widely used Chinese herbal formulation for cardiac diseases prepared from red ginseng and processed aconite root. Clinical observations and pharmacological effects on SFI have been well investigated. Chemical analysis and quality control studies of this formulation, however, are relatively limited, especially regarding toxic aconite alkaloids. In this work, a high-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (HPLC-QTOF MS) method was applied to comprehensive analysis of constituents in SFI. Highly sensitive MS allows direct analysis of injections without additional sample pretreatment required. Using diagnostic ions and fragmentation rules, we identified 23 trace diterpene alkaloids, nineteen ginseng saponins, one panaxytriol, and one 5-hydroxymethylfurfural in SFI. A LC-MS method with selected ion monitoring was then used to quantify 24 major alkaloids and ginsenosides. The method was validated in terms of linearity, accuracy and precision. Especially, the limits of quantification were low to 0.4-18ng/mL for diterpene alkaloids. The total concentrations of saponins and alkaloids were about 676-742μg/mL and 3-7μg/mL in five batches of SFI samples, respectively. Finally, cosine ratio and euclidean distance were introduced to evaluate the batch-to-batch reproducibility of SFI samples, and the results demonstrated high quality consistency. Global identification and quantification of complex constituents based on LC-MS promises wide applications in quality control and batch monitoring for herbal products.

  3. Complete structural assignment of serratol, a cembrane-type diterpene from Boswellia serrata, and evaluation of its antiprotozoal activity.

    PubMed

    Schmidt, Thomas J; Kaiser, Marcel; Brun, Reto

    2011-05-01

    From the dichloromethane extract obtained from the gum resin of Boswellia serrata Roxb. (Burseraceae), a well-known medicinal plant resin ("Indian Olibanum"), the cembrane-type diterpene serratol was isolated in high yield. Its structure, previously reported without clear specification of double-bond geometry and without specification of stereochemistry, was reanalysed by means of spectroscopic measurements and unambiguously assigned as S(-)-cembra-3E,7E,11E‑triene-1-ol. Full assignment of all NMR data is reported for the first time. The compound was found to be identical with a cembrenol previously isolated from B. carteri. Serratolwas tested for in vitro activity against four protozoan human pathogens, namely, Trypanosoma brucei rhodesiense (East African Human Trypanosomiasis, sleeping sickness), T. cruzi (Chagas' disease), Leishmania donovani (Kala-Azar), and Plasmodium falciparum (Tropical Malaria). It was found active against T. brucei and P. falciparum. These activities were 10- to 15-fold higher than its cytotoxicity against rat skeletalmyoblasts. While some reports exist on potential anti-inflammatory activity of Boswellia diterpenes, this is the first report on antiprotozoal activity of such a compound.

  4. In vitro cytotoxic activity of abietane diterpenes from Peltodon longipes as well as Salvia miltiorrhiza and Salvia sahendica.

    PubMed

    Fronza, M; Murillo, R; Ślusarczyk, S; Adams, M; Hamburger, M; Heinzmann, B; Laufer, S; Merfort, I

    2011-08-15

    Phytochemical investigations of the n-hexane extract from the roots of Peltodon longipes (Lamiaceae) resulted in the isolation of 12 known abietane diterpenes (1-12). Structures were established on the basis of one and two dimensional nuclear magnetic resonance spectroscopic data ((1)H and (13)C, COSY, HSQC and HMBC), electron ionization mass spectrometric analysis (EIMS) as well as comparison with data from literature. These compounds, as well as eight known diterpenes (13-19) from Salvia miltiorrhiza, and two from Salvia sahendica (20 and 21) were evaluated for their cytotoxic effects in human pancreatic (MIAPaCa-2) and melanoma (MV-3) tumor cell lines using the MTT assay. Tanshinone IIa (13), 7α-acetoxyroyleanone (1), 1,2-dihydrotanshinone (16) and cryptotanshinone (14) had the highest cytotoxic effects in MIAPaCa-2, displaying IC(50) of 1.9, 4.7, 5.6, and 5.8 μM, respectively. Structure-activity relationships of abietane diterpenoid quinones are discussed.

  5. Oleanolic acid and hederagenin glycosides from Weigela stelzneri.

    PubMed

    Rezgui, Abdelmalek; Mitaine-Offer, Anne-Claire; Miyamoto, Tomofumi; Tanaka, Chiaki; Delemasure, Stéphanie; Dutartre, Patrick; Lacaille-Dubois, Marie-Aleth

    2016-03-01

    Four previously undescribed and one known oleanolic acid glycosides were isolated from the roots of Weigela stelzneri, and one previously undescribed and three known hederagenin glycosides were isolated from the leaves. Their structures were elucidated mainly by 2D NMR spectroscopic analysis and mass spectrometry as 3-O-β-D-glucopyranosyl-(1 → 2)-[β-D-xylopyranosyl-(1 → 4)]-β-D-xylopyranosyl-(1 → 4)-β-D-xylopyranosyl-(1 → 3)-α-L-rhamnopyranosyl-(1 → 2)-α-L-arabinopyranosyloleanolic acid, 3-O-β-D-glucopyranosyl-(1 → 2)-[β-D-xylopyranosyl-(1 → 4)]-β-D-xylopyranosyl-(1 → 4)-β-D-xylopyranosyl-(1 → 3)-α-L-rhamnopyranosyl-(1 → 2)-β-D-xylopyranosyloleanolic acid, 3-O-β-D-glucopyranosyl-(1 → 2)-[β-D-glucopyranosyl-(1 → 4)]-β-D-xylopyranosyl-(1 → 4)-β-D-xylopyranosyl-(1 → 3)-α-L-rhamnopyranosyl-(1 → 2)-β-D-xylopyranosyloleanolic acid, 3-O-β-D-glucopyranosyl-(1 → 2)-[β-D-xylopyranosyl-(1 → 4)]-β-D-xylopyranosyl-(1 → 4)-β-D-xylopyranosyl-(1 → 3)-α-L-rhamnopyranosyl-(1 → 2)-α-L-arabinopyranosyloleanolic acid 28-O-β-D-glucopyranosyl-(1 → 6)-β-D-glucopyranosyl ester, and 3-O-β-D-glucopyranosyl-(1 → 2)-α-L-arabinopyranosylhederagenin 28-O-β-D-xylopyranosyl-(1 → 6)-[α-L-rhamnopyranosyl-(1 → 2)]-β-D-glucopyranosyl ester. The majority of the isolated compounds were evaluated for their cytotoxicity against two tumor cell lines (SW480 and EMT-6), and for their anti-inflammatory activity. The compounds 3-O-β-D-glucopyranosyl-(1 → 2)-[β-D-xylopyranosyl-(1 → 4)]-β-D-xylopyranosyl-(1 → 4)-β-D-xylopyranosyl-(1 → 3)-α-L-rhamnopyranosyl-(1 → 2)-α-L-arabinopyranosyloleanolic acid and 3-O-β-D-glucopyranosyl-(1 → 2)-[β-D-xylopyranosyl-(1 → 4)]-β-D-xylopyranosyl-(1 → 4)-β-D-xylopyranosyl-(1 → 3)-α-L-rhamnopyranosyl-(1 → 2)-β-D-xylopyranosyloleanolic acid exhibited the strongest cytotoxicity on both cancer cell lines. They revealed a 50% significant inhibitory effect of the IL-1

  6. Evolution of Diterpene Metabolism: Sitka Spruce CYP720B4 Catalyzes Multiple Oxidations in Resin Acid Biosynthesis of Conifer Defense against Insects1[C][W][OA

    PubMed Central

    Hamberger, Björn; Ohnishi, Toshiyuki; Hamberger, Britta; Séguin, Armand; Bohlmann, Jörg

    2011-01-01

    Diterpene resin acids (DRAs) are specialized (secondary) metabolites of the oleoresin defense of conifers produced by diterpene synthases and cytochrome P450s of the CYP720B family. The evolution of DRA metabolism shares common origins with the biosynthesis of ent-kaurenoic acid, which is highly conserved in general (primary) metabolism of gibberellin biosynthesis. Transcriptome mining in species of spruce (Picea) and pine (Pinus) revealed CYP720Bs of four distinct clades. We cloned a comprehensive set of 12 different Sitka spruce (Picea sitchensis) CYP720Bs as full-length cDNAs. Spatial expression profiles, methyl jasmonate induction, and transcript enrichment in terpenoid-producing resin ducts suggested a role of CYP720B4 in DRA biosynthesis. CYP720B4 was characterized as a multisubstrate, multifunctional enzyme by the formation of oxygenated diterpenoids in metabolically engineered yeast, yeast in vivo transformation of diterpene substrates, in vitro assays with CYP720B4 protein produced in Escherichia coli, and alteration of DRA profiles in RNA interference-suppressed spruce seedlings. CYP720B4 was active with 24 different diterpenoid substrates, catalyzing consecutive C-18 oxidations in the biosynthesis of an array of diterpene alcohols, aldehydes, and acids. CYP720B4 was most active in the formation of dehydroabietic acid, a compound associated with insect resistance of Sitka spruce. We identified patterns of convergent evolution of CYP720B4 in DRA metabolism and ent-kaurene oxidase CYP701 in gibberellin metabolism and revealed differences in the evolution of specialized and general diterpene metabolism in a gymnosperm. The genomic and functional characterization of the gymnosperm CYP720B family highlights that the evolution of specialized metabolism involves substantial diversification relative to conserved, general metabolism. PMID:21994349

  7. Effect of chito-oligosaccharide on the intestinal absorptions of phenylethanoid glycosides in Fructus Forsythiae extract.

    PubMed

    Zhou, Wei; Tan, Xiaobin; Shan, Jinjun; Liu, Ting; Cai, Baochang; Di, Liuqing

    2014-10-15

    Phenylethanoid glycosides, the main active ingredients in Fructus Forsythiae extract possesses strong antibacterial, antioxidant and antiviral effects, and their contents were higher largely than that of other ingredients such as lignans and flavones, but their absolute bioavailability orally was significantly low, which influenced clinical efficacies of its oral preparations seriously. In the present study, the absorption mechanism of phenylethanoid glycosides was studied using in vitro Caco-2 cell model. And the effect of chito-oligosaccharide (COS) on the intestinal absorption of phenylethanoid glycosides in Fructus Forsythiae extract was investigated using in vitro, in situ and in vivo models. The pharmacological effects such as antiviral activity improvement by COS were verified by MDCK cell damage inhibition rate after influenza virus propagation. The observations from in vitro Caco-2 cell showed that the absorption of phenylethanoid glycosides in Fructus Forsythiae extract so with that in monomers was mainly restricted by the tight junctions, and influenced by efflux transporters (P-gp and MRP2). Meanwhile, the absorption of phenylethanoid glycosides in Fructus Forsythiae extract could be improved by COS. Besides, COS at the same low, medium and high concentrations caused a significant, concentration-dependent increase in the Papp-value for phenylethanoid glycosides compared to the control group (p<0.05), and was all safe for the Caco-2 cells. The observations from single-pass intestinal perfusion in situ model showed that the intestinal absorption of phenylethanoid glycosides can be enhanced by COS. Meanwhile, the absorption enhancing effect of phenylethanoid glycosides might be saturable in different intestine sites. In pharmacokinetics study, COS at dosage of 25mg/kg improved the bioavailability of phenylethanoid glycosides in Fructus Forsythiae extract to the greatest extent, and was safe for gastrointestine from morphological observation. In addition

  8. Polyketide Glycosides from Bionectria ochroleuca Inhibit Candida albicans Biofilm Formation

    PubMed Central

    2015-01-01

    One of the challenges presented by Candida infections is that many of the isolates encountered in the clinic produce biofilms, which can decrease these pathogens’ susceptibilities to standard-of-care antibiotic therapies. Inhibitors of fungal biofilm formation offer a potential solution to counteracting some of the problems associated with Candida infections. A screening campaign utilizing samples from our fungal extract library revealed that a Bionectria ochroleuca isolate cultured on Cheerios breakfast cereal produced metabolites that blocked the in vitro formation of Candida albicans biofilms. A scale-up culture of the fungus was undertaken using mycobags (also known as mushroom bags or spawn bags), which afforded four known [TMC-151s C–F (1–4)] and three new [bionectriols B–D (5–7)] polyketide glycosides. All seven metabolites exhibited potent biofilm inhibition against C. albicans SC5314, as well as exerted synergistic antifungal activities in combination with amphotericin B. In this report, we describe the structure determination of the new metabolites, as well as compare the secondary metabolome profiles of fungi grown in flasks and mycobags. These studies demonstrate that mycobags offer a useful alternative to flask-based cultures for the preparative production of fungal secondary metabolites. PMID:25302529

  9. Novel cytotoxic steroidal glycosides from the roots of Liriope muscari.

    PubMed

    Li, Yong-Wei; Qi, Jin; Zhang, Yuan-Yuan; Huang, Zhen; Kou, Jun-Ping; Zhou, Shui-Ping; Zhang, Yu; Yu, Bo-Yang

    2015-06-01

    The present study was designed to investigate the chemical constituents and bioactivities of the roots of Liriope muscari (Decne.) L.H. Bailey. The compounds were isolated through various chromatography techniques, including silica gel, Sephadex LH-20, and semi-preparative HPLC. The structures were elucidated by infrared (IR), mass spectrometric (MS), 1D- and 2D-NMR analyses in comparison with reference data. In addition, the cytotoxicity of these compounds against human breast cancer MDA-MB-435 cells was evaluated by the MTT assay. Two new steroidal glycosides, 25(R, S)-ruscogenin-1-O-[β-D-fucopyranosyl (1→2)]-[β-D-xylopyranosyl(1→3)]β-D-glucopyranoside (Liriopem I, 1) and 25(R, S)- ruscogenin-1-O-[β-D-fucopyranosyl (1→2)]-[β-D-xylopyranosyl(1→4)]-β-D-fucopyranoside (Liriopem II, 2 and two known compounds LM-S6 (3) and DT-13 (4) were isolated and identified. Liriopem I(1), liriopem II(2) and DT-13 (4) showed remarkable cytotoxicity with IC50 values being (0.58 ± 0.08), (0.05 ± 0.10), and (0.15 ± 0.09) μg·mL(-1), respectively. In summary, compounds 1 and 2 identified in the present study exerted cytotoxicity against breast cancer cells, providing a basis for future development of these compounds as novel anticancer agents.

  10. Cytotoxicity of cardenolides and cardenolide glycosides from Asclepias curassavica.

    PubMed

    Li, Jun-Zhu; Qing, Chen; Chen, Chang-Xiang; Hao, Xiao-Jiang; Liu, Hai-Yang

    2009-04-01

    A new cardenolide, 12beta,14beta-dihydroxy-3beta,19-epoxy-3alpha-methoxy-5alpha-card-20(22)-enolide (6), and a new doubly linked cardenolide glycoside, 12beta-hydroxycalotropin (13), together with eleven known compounds, coroglaucigenin (1), 12beta-hydroxycoroglaucigenin (2), calotropagenin (3), desglucouzarin (4), 6'-O-feruloyl-desglucouzarin (5), calotropin (7), uscharidin (8), asclepin (9), 16alpha-hydroxyasclepin (10), 16alpha-acetoxycalotropin (11), and 16alpha-acetoxyasclepin (12), were isolated from the aerial part of ornamental milkweed, Asclepias curassavica and chemically elucidated through spectral analyses. All the isolates were evaluated for their cytotoxic activity against HepG2 and Raji cell lines. The results showed that asclepin (9) had the strongest cytotoxic activity with an IC(50) value of 0.02 microM against the two cancer cell lines and the new compound 13 had significant cytotoxic activity with IC(50) values of 0.69 and 1.46 microM, respectively.

  11. A new flavonol glycoside from the medicinal halophyte Suaeda fruticosa.

    PubMed

    Oueslati, Samia; Ksouri, Riadh; Pichette, André; Lavoie, Serge; Girard-Lalancette, Karl; Mshvildadze, Vakhtang; Abdelly, Chedly; Legault, Jean

    2014-01-01

    A new flavonol glycoside, namely 3-(α-rhamnopyranosyl-(1 → 2)-[β-xylopyranosyl-(1 → 6)]-β-glucopyranosyloxy) isorhamnetin was reported from methanol extracts of aerial parts of Suaeda fruticosa for the first time. In this work, liquid chromatography coupled to atmospheric pressure chemical ionisation mass spectrometry, high-resolution mass spectrometry and nuclear magnetic resonance spectroscopy were used to identify this new compound. Structure was elucidated on the basis of extensive spectroscopic analysis, including HSQC, HMBC and (1)H-(1)H COSY. Antioxidant potentialities of a pure compound were evaluated. The estimation of antioxidant capacities using oxygen radical absorbance capacity (ORAC method) and a cell based-assay (WS1) indicated that this new flavonol exhibited the highest antioxidant activities with an ORAC value of 5.0 ± 0.3 μmol Trolox/μmol and inhibited the tBH-induced oxidation of 2',7'-dichlorofluorescin with an IC50 value of 4.9 ± 0.6 μM.

  12. A new indole glycoside from the seeds of Raphanus sativus.

    PubMed

    Jin, Hong-Guang; Ko, Hae Ju; Chowdhury, Md Anisuzzaman; Lee, Dong-Sung; Woo, Eun-Rhan

    2016-06-01

    A new indole glycoside, β-D-glucopyranosyl 2-(methylthio)-1H-indole-3-carboxylate, named raphanuside A (1), as well as eight known compounds, β-D-fructofuranosyl-(2 → 1)-(6-O-sinapoyl)-α-D-glucopyranoside (2), (3-O-sinapoyl)-β-D-fructofuranosyl-(2 → 1)-α-D-glucopyranoside (3), (3-O-sinapoyl)-β-D-fructofuranosyl-(2 → 1)-(6-O-sinapoyl)-α-D-glucopyranoside (4), (3,4-O-disinapoyl)-β-D-fructofuranosyl-(2 → 1)-(6-O-sinapoyl)-α-D-glucopyranoside (5), isorhamnetin 3,4'-di-O-β-D-glucoside (6), isorhamnetin 3-O-β-D-glucoside-7-O-α-L-rhamnoside (7), isorhamnetin 3-O-β-D-glucoside (8) and 3'-O-methyl-(-)-epicatechin 7-O-β-D-glucoside (9) were isolated from the seeds of Raphanus sativus. Furthermore, compounds 1-3 and 6-9, were isolated from this plant for the first time. The structures of compounds 1-9 were identified using 1D and 2D NMR, including (1)H-(1)H COSY, HSQC, HMBC and NOESY spectroscopic analyses. The inhibitory activity of these isolated compounds against interleukin-6 (IL-6) production in TNF-α stimulated MG-63 cells was also examined.

  13. Flavone C-glycosides from Viola yedoensis MAKINO.

    PubMed

    Xie, Chen; Veitch, Nigel C; Houghton, Peter J; Simmonds, Monique S J

    2003-10-01

    A new flavone C-glycoside, apigenin 6-C-alpha-L-arabinopyranosyl-8-C-beta-L-arabinopyranoside, has been isolated from Viola yedoensis together with the known compounds, apigenin 6,8-di-C-alpha-L-arabinopyranoside, apigenin 6-C-alpha-L-arabinopyranosyl-8-C-beta-D-glucopyranoside (isoschaftoside), apigenin 6-C-beta-D-glucopyranosyl-8-C-alpha-L-arabinopyranoside (schaftoside), apigenin 6-C-beta-D-glucopyranosyl-8-C-beta-L-arabinopyranoside (neoschaftoside), apigenin 6,8-di-C-beta-D-glucopyranoside (vicenin-2), apigenin 6-C-alpha-L-arabinopyranosyl-8-C-beta-D-xylopyranoside, apigenin 6-C-beta-D-xylopyranosyl-8-C-alpha-L-arabinopyranoside, luteolin 6-C-beta-D-glucopyranoside (isoorientin) and luteolin 6-C-alpha-L-arabinopyranosyl-8-C-beta-D-glucopyranoside (isocarlinoside). The structures were determined by spectroscopic methods and new or revised (1)H- and (13)C-NMR spectral assignments are proposed for some compounds.

  14. Antitrypanosomal isothiocyanate and thiocarbamate glycosides from Moringa peregrina.

    PubMed

    Ayyari, Mahdi; Salehi, Peyman; Ebrahimi, Samad Nejad; Zimmermann, Stefanie; Portmann, Lena; Krauth-Siegel, R Luise; Kaiser, Marcel; Brun, Reto; Rezadoost, Hassan; Rezazadeh, Shamsali; Hamburger, Matthias

    2014-01-01

    O-Methyl (1), O-ethyl (2), and O-butyl (3) 4-[(α-L-rhamnosyloxy) benzyl] thiocarbamate (E), along with 4-(α-L-rhamnosyloxy) benzyl isothiocyanate (4) have been isolated from the aerial parts of Moringa peregrina. The compounds were tested for in vitro activity against Trypanosoma brucei rhodesiense and cytotoxicity in rat skeletal myoblasts (L6 cells). The most potent compound was 4 with an IC50 of 0.10 µM against T.b. rhodesiense and a selectivity index of 73, while the thiocarbamate glycosides 1, 2, and 3 showed only moderate activity. Intraperitoneal administration of 50 mg/kg body weight/day of 4 in the T.b. rhodesiense STIB 900 acute mouse model revealed significant in vivo toxicity. Administration of 10 mg/kg body weight/day resulted in a 95% reduction of parasitemia on day 7 postinfection, but did not cure the animals. Because of its high in vitro activity and its ability to irreversibly inhibit trypanothione reductase, an attractive parasite-specific target enzyme, 4-[(α-L-rhamnosyloxy) benzyl] isothiocyanate (4), can be considered as a lead structure for the development and characterization of novel antitrypanosomal drugs.

  15. Thermus thermophilus Glycoside Hydrolase Family 57 Branching Enzyme

    PubMed Central

    Palomo, Marta; Pijning, Tjaard; Booiman, Thijs; Dobruchowska, Justyna M.; van der Vlist, Jeroen; Kralj, Slavko; Planas, Antoni; Loos, Katja; Kamerling, Johannis P.; Dijkstra, Bauke W.; van der Maarel, Marc J. E. C.; Dijkhuizen, Lubbert; Leemhuis, Hans

    2011-01-01

    Branching enzyme (EC 2.4.1.18; glycogen branching enzyme; GBE) catalyzes the formation of α1,6-branching points in glycogen. Until recently it was believed that all GBEs belong to glycoside hydrolase family 13 (GH13). Here we describe the cloning and expression of the Thermus thermophilus family GH57-type GBE and report its biochemical properties and crystal structure at 1.35-Å resolution. The enzyme has a central (β/α)7-fold catalytic domain A with an inserted domain B between β2 and α5 and an α-helix-rich C-terminal domain, which is shown to be essential for substrate binding and catalysis. A maltotriose was modeled in the active site of the enzyme which suggests that there is insufficient space for simultaneously binding of donor and acceptor substrates, and that the donor substrate must be cleaved before acceptor substrate can bind. The biochemical assessment showed that the GH57 GBE possesses about 4% hydrolytic activity with amylose and in vitro forms a glucan product with a novel fine structure, demonstrating that the GH57 GBE is clearly different from the GH13 GBEs characterized to date. PMID:21097495

  16. A recycling pathway for cyanogenic glycosides evidenced by the comparative metabolic profiling in three cyanogenic plant species.

    PubMed

    Pičmanová, Martina; Neilson, Elizabeth H; Motawia, Mohammed S; Olsen, Carl Erik; Agerbirk, Niels; Gray, Christopher J; Flitsch, Sabine; Meier, Sebastian; Silvestro, Daniele; Jørgensen, Kirsten; Sánchez-Pérez, Raquel; Møller, Birger Lindberg; Bjarnholt, Nanna

    2015-08-01

    Cyanogenic glycosides are phytoanticipins involved in plant defence against herbivores by virtue of their ability to release toxic hydrogen cyanide (HCN) upon tissue disruption. In addition, endogenous turnover of cyanogenic glycosides without the liberation of HCN may offer plants an important source of reduced nitrogen at specific developmental stages. To investigate the presence of putative turnover products of cyanogenic glycosides, comparative metabolic profiling using LC-MS/MS and high resolution MS (HR-MS) complemented by ion-mobility MS was carried out in three cyanogenic plant species: cassava, almond and sorghum. In total, the endogenous formation of 36 different chemical structures related to the cyanogenic glucosides linamarin, lotaustralin, prunasin, amygdalin and dhurrin was discovered, including di- and tri-glycosides derived from these compounds. The relative abundance of the compounds was assessed in different tissues and developmental stages. Based on results common to the three phylogenetically unrelated species, a potential recycling endogenous turnover pathway for cyanogenic glycosides is described in which reduced nitrogen and carbon are recovered for primary metabolism without the liberation of free HCN. Glycosides of amides, carboxylic acids and 'anitriles' derived from cyanogenic glycosides appear as common intermediates in this pathway and may also have individual functions in the plant. The recycling of cyanogenic glycosides and the biological significance of the presence of the turnover products in cyanogenic plants open entirely new insights into the multiplicity of biological roles cyanogenic glycosides may play in plants.

  17. FeCl3-promoted and ultrasound-assisted synthesis of resveratrol O-derived glycoside analogs.

    PubMed

    Marzag, Hamid; Robert, Guillaume; Dufies, Maeva; Bougrin, Khalid; Auberger, Patrick; Benhida, Rachid

    2015-01-01

    Phenol derived O-glycosides were synthesized using a direct and convenient O-glycosidation, starting from acetylated sugars in the presence of FeCl3, an inexpensive, mild and benign Lewis acid catalyst. The reactions were carried out under both conventional and ultrasonic irradiation conditions. In general, improvement in rates and yields were observed when reactions were carried out under sonication compared with conventional conditions leading to the corresponding β-O-glycosides as the major anomer. Post-synthetic transformations of iodophenol intermediates led to new resveratrol O-glycoside analogs in good overall yields.

  18. Flavonoid Glycosides of Polygonum capitatum Protect against Inflammation Associated with Helicobacter pylori Infection.

    PubMed

    Zhang, Shu; Mo, Fei; Luo, Zhaoxun; Huang, Jian; Sun, Chaoqin; Zhang, Ran

    2015-01-01

    The antibacterial and anti-inflammatory activities, and protective effects of extracts (flavonoid glycosides) of Polygonum capitatum were investigated to detect the evidence for the utilization of the herb in the clinical therapy of gastritis caused by H. pylori. A mouse gastritis model was established using H. pylori. According to treating methods, model mice were random assigned into a model group (MG group), a triple antibiotics group (TG group, clarithromycin, omeprazole and amoxicillin), low/middle/high concentrations of flavonoid glycosides groups (LF, MF and HF groups) and low/middle/high concentrations of flavonoid glycosides and amoxicillin groups (LFA, MFA and HFA groups). A group with pathogen-free mice was regarded as a control group (CG group). The eradicate rates of H. pylori were 100%, 93%, 89% in TG, MFA and HF groups. The serum levels of IFN-gamma and gastrin were higher in a MG group than those from all other groups (P < 0.05). The serum levels of IFN-gamma and gastrin were reduced significantly in LF, MF and HF groups (P < 0.05) while little changes were observed in LFA, MFA and HFA groups. In contrast, the serum levels of IL-4 were lower and higher in MG and CG groups compared with other groups (P<0.05). The serum levels of IL-4 were increased significantly in LF, MF and HF groups (P < 0.05) while little changes were found in LFA, MFA and HFA groups. According to pathological scores, flavonoid glycosides therapy showed better protection for gastric injuries than the combination of flavonoid glycoside and amoxicillin (P < 0.05). The results suggested that flavonoid glycoside has repairing functions for gastric injuries. The results suggest that the plant can treat gastritis and protect against gastric injuries. The flavonoid glycosides from Polygonum capitatum should be developed as a potential drug for the therapy of gastritis caused by H. pylori.

  19. Flavonoid Glycosides of Polygonum capitatum Protect against Inflammation Associated with Helicobacter pylori Infection

    PubMed Central

    Zhang, Shu; Mo, Fei; Luo, Zhaoxun; Huang, Jian; Sun, Chaoqin; Zhang, Ran

    2015-01-01

    The antibacterial and anti-inflammatory activities, and protective effects of extracts (flavonoid glycosides) of Polygonum capitatum were investigated to detect the evidence for the utilization of the herb in the clinical therapy of gastritis caused by H. pylori. A mouse gastritis model was established using H. pylori. According to treating methods, model mice were random assigned into a model group (MG group), a triple antibiotics group (TG group, clarithromycin, omeprazole and amoxicillin), low/middle/high concentrations of flavonoid glycosides groups (LF, MF and HF groups) and low/middle/high concentrations of flavonoid glycosides and amoxicillin groups (LFA, MFA and HFA groups). A group with pathogen-free mice was regarded as a control group (CG group). The eradicate rates of H. pylori were 100%, 93%, 89% in TG, MFA and HF groups. The serum levels of IFN-gamma and gastrin were higher in a MG group than those from all other groups (P < 0.05). The serum levels of IFN-gamma and gastrin were reduced significantly in LF, MF and HF groups (P < 0.05) while little changes were observed in LFA, MFA and HFA groups. In contrast, the serum levels of IL-4 were lower and higher in MG and CG groups compared with other groups (P<0.05). The serum levels of IL-4 were increased significantly in LF, MF and HF groups (P < 0.05) while little changes were found in LFA, MFA and HFA groups. According to pathological scores, flavonoid glycosides therapy showed better protection for gastric injuries than the combination of flavonoid glycoside and amoxicillin (P < 0.05). The results suggested that flavonoid glycoside has repairing functions for gastric injuries. The results suggest that the plant can treat gastritis and protect against gastric injuries. The flavonoid glycosides from Polygonum capitatum should be developed as a potential drug for the therapy of gastritis caused by H. pylori. PMID:25993258

  20. Biota: sediment partitioning of aluminium smelter related PAHs and pulp mill related diterpenes by intertidal clams at Kitimat, British Columbia.

    PubMed

    Yunker, Mark B; Lachmuth, Cara L; Cretney, Walter J; Fowler, Brian R; Dangerfield, Neil; White, Linda; Ross, Peter S

    2011-09-01

    The question of polycyclic aromatic hydrocarbon (PAH) bioavailability and its relationship to specific PAH sources with different PAH binding characteristics is an important one, because bioavailability drives PAH accumulation in biota and ultimately the biochemical responses to the PAH contaminants. The industrial harbour at Kitimat (British Columbia, Canada) provides an ideal location to study the bioavailability and bioaccumulation of sediment hydrocarbons to low trophic level biota. Samples of soft shell clams (Mya arenaria) and intertidal sediment collected from multiple sites over six years at various distances from an aluminium smelter and a pulp and paper mill were analysed for 106 PAHs, plant diterpenes and other aromatic fraction hydrocarbons. Interpretation using PAH source ratios and multivariate data analysis reveals six principal hydrocarbon sources: PAHs in coke, pitch and emissions from anode combustion from the aluminium smelter, vascular plant terpenes and aromatised terpenes from the pulp and paper mill, petroleum PAHs from shipping and other anthropogenic activities and PAHs from natural plant detritus. Harbour sediments predominantly contain either pitch or pyrogenic PAHs from the smelter, while clams predominantly contain plant derived PAHs and diterpenes from the adjacent pulp mill. PAHs from the smelter have low bioavailability to clams (Biota-Sediment Accumulation Factors; BSAFs <1 for pitch and coke; <10 for anode combustion, decreasing to ∼0.1 for the mass 300 and 302 PAHs), possibly due to binding to pitch or soot carbon matrices. Decreases in PAH isomer ratios between sediments and clams likely reflect a combination of variation in uptake kinetics of petroleum PAHs and compound specific metabolism, with the importance of petroleum PAHs decreasing with increasing molecular weight. Plant derived compounds exhibit little natural bioaccumulation at reference sites, but unsaturated and aromatised diterpenes released from resins by

  1. Proteomic Analysis of a Novel Bacillus Jumbo Phage Revealing Glycoside Hydrolase As Structural Component

    PubMed Central

    Yuan, Yihui; Gao, Meiying

    2016-01-01

    Tailed phages with genomes of larger than 200 kbp are classified as Jumbo phages and exhibited extremely high uncharted diversity. The genomic annotation of Jumbo phage is often disappointing because most of the predicted proteins, including structural proteins, failed to make good hits to the sequences in the databases. In this study, 23 proteins of a novel Bacillus Jumbo phage, vB_BpuM_BpSp, were identified as phage structural proteins by the structural proteome analysis, including 14 proteins of unknown function, 5 proteins with predicted function as structural proteins, a glycoside hydrolase, a Holliday junction resolvase, a RNA-polymerase β-subunit, and a host-coding portal protein, which might be hijacked from the host strain during phage virion assembly. The glycoside hydrolase (Gp255) was identified as phage virion component and was found to interact with the phage baseplate protein. Gp255 shows specific lytic activity against the phage host strain GR8 and has high temperature tolerance. In situ peptidoglycan-hydrolyzing activities analysis revealed that the expressed Gp255 and phage structural proteome exhibited glycoside hydrolysis activity against the tested GR8 cell extracts. This study identified the first functional individual structural glycoside hydrolase in phage virion. The presence of activated glycoside hydrolase in phage virions might facilitate the injection of the phage genome during infection by forming pores on the bacterial cell wall. PMID:27242758

  2. 1-O-vinyl glycosides via Tebbe olefination, their use as chiral auxiliaries and monomers.

    PubMed

    Yuan, Jialong; Lindner, Kristof; Frauenrath, Holger

    2006-07-21

    A series of anomerically pure 1-O-formyl glycosides 1 was prepared and converted into the corresponding 1-O-vinyl glycosides 2 by Tebbe olefination. The unsubstituted vinyl glycosides were obtained as anomerically pure compounds in good yields, and the method of preparation was compatible with the presence of a variety of functional groups. Remarkably, the anomeric formate group was regioselectively converted into the corresponding olefin in the presence of acetate and benzoate protecting groups. With the perspective to use the 1-O-vinyl glycosides as monomers for the preparation of glycosylated poly(vinyl alcohol) derivatives with controlled tacticity, their scope as chiral auxiliaries for a stereodifferentiation in addition reactions to the olefin function was investigated by using the [2+2] cycloaddition to dichloroketene as a model reaction. In particular, vinyl 2,3,4,6-tetra-O-benzoyl-alpha-d-mannopyranoside (2i) exhibited excellent diastereoselectivity. Finally, the 1-O-vinyl glycosides were successfully subjected to radical homopolymerization in bulk or used as electron-rich comonomers in radical copolymerizations with maleic anhydride, yielding alternating, glycosylated poly(vinyl alcohol-alt-maleic anhydride).

  3. Factors influencing the variability of antioxidative phenolic glycosides in Salix species.

    PubMed

    Förster, Nadja; Ulrichs, Christian; Zander, Matthias; Kätzel, Ralf; Mewis, Inga

    2010-07-28

    Phenolic glycosides, especially the salicylates, are important secondary metabolites in the bark of willows (Salix spp.). Because of their anti-inflammatory, analgesic, and fever-reducing properties, they are of particular interest to society. Compared to the fabrication of synthetic salicylacetylic acid, the commercial production of willow bark extracts with adequate amounts of salicylate is very difficult due to several biological and technical reasons. Therefore, one of the objectives was to identify salicylate-rich clones from three species, Salix daphnoides , Salix purpurea , and Salix pentandra , with potentially high amounts of phenolic glycosides. Three hundred different Salix clones were collected, and the chemical profiles of their bark were analyzed by HPLC. Overall, S. daphnoides clones showed the highest phenolic glycoside contents, followed by S. purpurea and S. pentandra. Second, seasonal changes of secondary compounds in willow bark were analyzed to determine the optimal harvesting time. The phenolic glycoside levels decreased over the growing season, with highest contents detected during plant dormancy. The effects of different cultivation conditions were also examined, and none of these treatments were found to have a significant effect on the phenolic glycoside content in willow bark. Biomass accumulation in the clones with grass competition was significantly lower than in the other three treatments.

  4. Bioactive glycosides from the roots of Ilex asprella.

    PubMed

    Peng, Min-Hua; Dai, Wei-Ping; Liu, Si-Jun; Yu, Liang-Wen; Wu, Yi-Na; Liu, Rui; Chen, Xu-Lin; Lai, Xiao-Ping; Li, Xiong; Zhao, Zhong-Xiang; Li, Geng

    2016-10-01

    Context The roots of Ilex asprella (Hook. et Arn.) Champ. ex Benth. (Aquifoliaceae) are widely used in Chinese medicine to treat influenza, amygdalitis, pertussis, etc. Their mechanism of action is still unknown, which raises the need to identify new bioactive compounds in this plant. Objective In this study, we isolated a novel saponin containing sulphonic groups, namely, asprellcoside A (1) and a known phenolic glycoside compound (2) from the roots of Ilex asprella and evaluated their bioactivities. Materials and methods Molecular structures were elucidated by analysing their spectral and chemical properties. The viability of A549 cells was tested using a MTT assay. Ability of the compounds to inhibit viruses was determined using the neuraminidase activity assay. Their anti-inflammatory effects were tested using the IP-10 activity assay using various concentrations (compound 1: 0.6, 0.2, 0.6, 1.70, 5.00 and 15.00 μM; compound 2: 0.4, 1.2, 3.6, 11.0, 33.0 and 100 μM). Their inhibitory effect on platelet aggregation induced by adenosine diphosphate (ADP) in rabbit plasma was determined at 60 and 80 μM. Results Both compounds inhibit influenza virus strain A/PuertoRico/8/1934 (H1N1) strongly with EC50 values of 4.1 and 1.7 μM, respectively. Both compounds inhibit the secretion of IP-10 with EC50 values of 6.6 and 2.5 μM, respectively. Compound 1 alone inhibited platelet aggregation significantly, with the rate of suppression being 47 ± 8 and 38 ± 3%, at 60 and 80 μM, respectively. Conclusions The results suggest that both compounds may be valid therapeutics against influenza virus infection and that compound 1 may be a novel agent for treating thrombosis.

  5. Bioprospecting metagenomics of decaying wood: mining for new glycoside hydrolases

    SciTech Connect

    Li L. L.; van der Lelie D.; Taghavi, S.; McCorkle, S. M.; Zhang, Y.-B.; Blewitt, M. G.; Brunecky, R.; Adney, W. S.; Himmel, M. E.; Brumm, P.; Drinkwater, C.; Mead, D. A.; Tringe, S. G.

    2011-08-01

    To efficiently deconstruct recalcitrant plant biomass to fermentable sugars in industrial processes, biocatalysts of higher performance and lower cost are required. The genetic diversity found in the metagenomes of natural microbial biomass decay communities may harbor such enzymes. Our goal was to discover and characterize new glycoside hydrolases (GHases) from microbial biomass decay communities, especially those from unknown or never previously cultivated microorganisms. From the metagenome sequences of an anaerobic microbial community actively decaying poplar biomass, we identified approximately 4,000 GHase homologs. Based on homology to GHase families/activities of interest and the quality of the sequences, candidates were selected for full-length cloning and subsequent expression. As an alternative strategy, a metagenome expression library was constructed and screened for GHase activities. These combined efforts resulted in the cloning of four novel GHases that could be successfully expressed in Escherichia coli. Further characterization showed that two enzymes showed significant activity on p-nitrophenyl-{alpha}-L-arabinofuranoside, one enzyme had significant activity against p-nitrophenyl-{beta}-D-glucopyranoside, and one enzyme showed significant activity against p-nitrophenyl-{beta}-D-xylopyranoside. Enzymes were also tested in the presence of ionic liquids. Metagenomics provides a good resource for mining novel biomass degrading enzymes and for screening of cellulolytic enzyme activities. The four GHases that were cloned may have potential application for deconstruction of biomass pretreated with ionic liquids, as they remain active in the presence of up to 20% ionic liquid (except for 1-ethyl-3-methylimidazolium diethyl phosphate). Alternatively, ionic liquids might be used to immobilize or stabilize these enzymes for minimal solvent processing of biomass.

  6. Glycosidic specificity of fucosyltransferases present in rat epididymal spermatozoa.

    PubMed

    Raychoudhury, S S; Millette, C F

    1995-01-01

    We have recently demonstrated multiple fucosyltransferase (FT) activity in rat spermatogenic cells. To complement these findings, here we identify and partially characterize the glycosidic linkage specificity of FTs present in spermatozoa from caput and cauda epididymides. Analysis of the acceptor substrate specificity of the FTs by thin-layer chromatography indicated that both caput and cauda sperm expressed alpha(1-2)-, alpha(1-3)-, alpha(1-4)-FTs as demonstrated by fucose incorporation into phenyl-beta-D-galactoside, 2'-fucosyllactose, and lacto-N-fucopentaose-I, respectively. Spermatozoa from the cauda epididymidis exhibited significant decreases in the levels of alpha(1-2)-, alpha(1-3)-, alpha(1-4)-FTs, and of total soluble FTs in comparison to spermatozoa from the caput epididymidis. The relative ratio of alpha(1-3)-FT to total FT activity appeared to be significantly higher than those of alpha(1-2)- or alpha(1-4)-FTs, in spermatozoa both from caput and cauda epididymides. Using different types of low molecular weight acceptors and the selective inhibition of the FT by N- ethylmaleimide, we have demonstrated that at least alpha(1-2)-FT is different from alpha(1-3)- or alpha(1-4)-FTs. Kinetic studies also showed that alpha(1-2)-FT is different from alpha(1-3)- or alpha(1-4)-FTs as demonstrated by apparent Km and Vmax values. Moreover, alpha(1-3)- and alpha(1-4)-FT activities in cauda sperm were found to be highly sensitive to Mn2+ but showed differential responses to divalent cations. In contrast, both alpha(1-3)- and alpha(1-4)-FTs seemed to be relatively less sensitive to Mg2+. Thus, these results not only demonstrate the presence of multiple FTs in rat epididymal sperm but also differentiate individual FTs with regard to their kinetic properties and sensitivity to both inhibitor and divalent cations.

  7. The coffee diterpene kahweol inhibits tumor necrosis factor-{alpha}-induced expression of cell adhesion molecules in human endothelial cells

    SciTech Connect

    Kim, Hyung Gyun; Kim, Ji Young; Hwang, Yong Pil; Lee, Kyung Jin; Lee, Kwang Youl; Kim, Dong Hee; Kim, Dong Hyun; Jeong, Hye Gwang . E-mail: hgjeong@chosun.ac.kr

    2006-12-15

    Endothelial cells produce adhesion molecules after being stimulated with various inflammatory cytokines. These adhesion molecules play an important role in the development of atherogenesis. Recent studies have highlighted the chemoprotective and anti-inflammatory effects of kahweol, a coffee-specific diterpene. This study examined the effects of kahweol on the cytokine-induced monocyte/human endothelial cell interaction, which is a crucial early event in atherogenesis. Kahweol inhibited the adhesion of TNF{alpha}-induced monocytes to endothelial cells and suppressed the TNF{alpha}-induced protein and mRNA expression of the cell adhesion molecules, VCAM-1 and ICAM-1. Furthermore, kahweol inhibited the TNF{alpha}-induced JAK2-PI3K/Akt-NF-{kappa}B activation pathway in these cells. Overall, kahweol has anti-inflammatory and anti-atherosclerotic activities, which occurs partly by down-regulating the pathway that affects the expression and interaction of the cell adhesion molecules on endothelial cells.

  8. Ginkgolides, diterpene trilactones of Ginkgo biloba, as antagonists at recombinant alpha1beta2gamma2L GABAA receptors.

    PubMed

    Huang, Shelley H; Duke, Rujee K; Chebib, Mary; Sasaki, Keiko; Wada, Keiji; Johnston, Graham A R

    2004-06-28

    Ginkgolides A, B, and C are diterpene trilactones and active constituents of the 50:1 Ginkgo biloba leaf extract widely used in the symptomatic treatment of mild to moderate dementia. Using the two-electrode voltage clamp methodology, these ginkgolides were found to be moderately potent antagonists at recombinant human alpha(1)beta(2)gamma(2L) GABA(A) receptors expressed in Xenopus oocytes. Ginkgolides A, B, and C inhibited the direct action of gamma-aminobutyric acid (GABA) with K(i) values of 14.5+/-1.0, 12.7+/-1.7, and 16.3+/-2.4 microM respectively. Antagonism by these ginkgolides at alpha(1)beta(2)gamma(2L) GABA(A) receptors appears to be noncompetitive as indicated by the nonparallel right shift and reduced maximal GABA response in their GABA concentration-effect curves.

  9. A unified approach to ent-atisane diterpenes and related alkaloids: synthesis of (-)-methyl atisenoate, (-)-isoatisine, and the hetidine skeleton.

    PubMed

    Cherney, Emily C; Lopchuk, Justin M; Green, Jason C; Baran, Phil S

    2014-09-10

    A unified approach to ent-atisane diterpenes and related atisine and hetidine alkaloids has been developed from ent-kaurane (-)-steviol (1). The conversion of the ent-kaurane skeleton to the ent-atisane skeleton features a Mukaiyama peroxygenation with concomitant cleavage of the C13-C16 bond. Conversion to the atisine skeleton (9) features a C20-selective C-H activation using a Suárez modification of the Hofmann-Löffler-Freytag (HLF) reaction. A cascade sequence involving azomethine ylide isomerization followed by Mannich cyclization forms the C14-C20 bond in the hetidine skeleton (8). Finally, attempts to form the N-C6 bond of the hetisine skeleton (7) with a late-stage HLF reaction are discussed. The synthesis of these skeletons has enabled the completion of (-)-methyl atisenoate (3) and (-)-isoatisine (4).

  10. Chenopodolin: a phytotoxic unrearranged ent-pimaradiene diterpene produced by Phoma chenopodicola, a fungal pathogen for Chenopodium album biocontrol.

    PubMed

    Cimmino, Alessio; Andolfi, Anna; Zonno, Maria C; Avolio, Fabiana; Santini, Antonello; Tuzi, Angela; Berestetskyi, Alexander; Vurro, Maurizio; Evidente, Antonio

    2013-07-26

    A new phytotoxic unrearranged ent-pimaradiene diterpene, named chenopodolin, was isolated from the liquid culture of Phoma chenopodicola, a fungal pathogen proposed for the biological control of Chenopodium album, a common worldwide weed of arable crops such as sugar beet and maize. The structure of chenopodolin was established by spectroscopic, X-ray, and chemical methods as (1S,2S,3S,4S,5S,9R,10S,12S,13S)-1,12-acetoxy-2,3-hydroxy-6-oxopimara-7(8),15-dien-18-oic acid 2,18-lactone. At a concentration of 2 mg/mL, the toxin caused necrotic lesions on Mercurialis annua, Cirsium arvense, and Setaria viride. Five derivatives were prepared by chemical modification of chenopodolin functionalities, and some structure-activity relationships are discussed.

  11. SJ23B, a jatrophane diterpene activates classical PKCs and displays strong activity against HIV in vitro.

    PubMed

    Bedoya, Luis M; Márquez, Nieves; Martínez, Natalia; Gutiérrez-Eisman, Silvia; Alvarez, Amparo; Calzado, Marco A; Rojas, José M; Appendino, Giovanni; Muñoz, Eduardo; Alcamí, José

    2009-03-15

    Existence of virus reservoirs makes the eradication of HIV infection extremely difficult. Current drug therapies neither eliminate these viral reservoirs nor prevent their formation. Consequently, new strategies are needed to target these reservoirs with the aim of decreasing their size. We analysed a series of jatrophane diterpenes isolated from Euphorbia hyberna and we found that one of them, SJ23B, induces the internalization of the HIV-1 receptors CD4, CXCR4 and CCR5 and prevents R5 and X4 viral infection in human primary T cells at the nanomolar range. Moreover, SJ23B is a potent antagonist of HIV-1 latency. Using Jurkat-LAT-GFP cells, a model for HIV-1 latency, we found that prostratin and SJ23B activate HIV-1 gene expression, with SJ23B being at least 10-fold more potent than prostratin. SJ23B did not elicit transforming foci activity in NIH 3T3 cells but is a potent activator of PKCalpha and delta as measured by in vitro kinase assays and by cellular translocation experiments. By using isoform-specific PKC inhibitors we found that cPKCs are critical for SJ23B-induced HIV-1 reactivation. We also showed that both SJ23B-induced IkappaBalpha degradation and NF-kappaB activation were inhibited by the classical PKC inhibitor, Gö6976. Accordingly, SJ23B synergizes with ionomycin to translocate PKCalpha to the plasma membrane and to activate the NF-kappaB pathway. Moreover, SJ23B activates both NF-kappaB and Sp1-dependent transcriptional activities in primary T cells. We have shown that diterpene jatrophanes represent a new member of anti-AIDS agents that could be developed for mitigating HIV reactivation.

  12. Two residues determine the product profile of the class II diterpene synthases TPS14 and TPS21 of Tripterygium wilfordii.

    PubMed

    Hansen, Nikolaj L; Nissen, Jakob N; Hamberger, Björn

    2017-03-06

    The medicinal plant Tripterygium wilfordii (Celastraceae) contains a pair of class II diterpene synthases (diTPS) of specialized labdane-type metabolism that, despite remarkably close homology, form strikingly different products. TwTPS21 catalyzes bicyclization of the linear C20 precursor geranylgeranyl diphosphate to ent-copal-8-ol diphosphate, while TwTPS14 forms kolavenyl diphosphate. To determine the amino acid signature controlling the functional divergence of the homologues, we modeled their structures based on an existing crystal structure of the Arabidopsis ent-copalyl diphosphate synthase, archetypal of diTPSs in general metabolism of gibberellin phytohormones. Of the residues differing between TwTPS21 and TwTPS14 two located to the predicted active site, and we hypothesized that these are responsible for the functional differentiation of the enzymes. Using site-directed mutagenesis, we generated a panel of six variants, where one, or both positions were exchanged between the enzymes. In coupled heterologous assays with a corresponding class I diTPS, TwTPS2, complete product interchange was observed in variants with both reciprocal mutations, while substitutions of either residue gave mixed product profiles. Two mutants, TwTPS14:Y265H and TwTPS21:A325V, also produced ent-copalyl diphosphate, highlighting the evolutionary potential of enzymes of this family to drive rapid diversification of plant diterpene biosynthesis through neo-functionalization. Our study contributes to the understanding of structure-function relation in plant class II diTPSs and complements previous mutational studies of Arabidopsis ent-copalyl diphosphate synthase with additional examples from the specialized metabolism of T. wilfordii.

  13. Improving the sensory and oxidative stability of cooked and chill-stored lamb using dietary rosemary diterpenes.

    PubMed

    Serrano, Rafael; Ortuño, Jordi; Bañón, Sancho

    2014-09-01

    Two dietary rosemary extracts (DREs) containing diterpenes (carnosic acid and carnosol at 1:1 and 2:1 w:w) were tested in fattening lambs to stabilize the sensory quality of cooked and chill-stored patties. A total of 63 lambs were fed freely for 80 ± 5 d with a basal diet supplemented or not with DRE. Minced leg meat from each lamb was used to make patty batches. The patties were cooked at 72 ºC for 2 min, aerobically packed, kept at 2 ºC for up to 4 d and then reheated. Sensory traits (color, odor, flavor, and texture), CIELab color, and lipid oxidation (assessed as TBARS) were determined. In a first experiment, the lamb diet was supplemented with 600 mg of 1:1-DRE or 2:1-DRE kg(-1) feed. The 1:1-DRE diet delayed discoloration, flavor deterioration, and rancidity, while the 2:1-DRE diet was ineffective in this respect. In a second experiment, 4 supplementation levels of 1:1-DRE (0, 200, 400, and 600 mg kg(-1) feed) were compared. Flavor deterioration was delayed when the lamb diet was supplemented with at least 400 mg 1:1-DRE kg(-1) feed. The effects of the diet on the odor, flavor, and color were corroborated by differences in TBARS and CIELab. The results obtained suggest that rosemary diterpenes and/or their active secondary compounds deposited in muscle can act as endogenous antioxidants in cooked lamb. The carnosol intake seems crucial in the antioxidant actions achieved through DRE. The use of rosemary antioxidants in animal feeding would allow meat-based dishes to be preserved longer without adding preservatives.

  14. Influence of ionic interactions on essential oil and phenolic diterpene composition of Dalmatian sage (Salvia officinalis L.).

    PubMed

    Tounekti, Taieb; Munné-Bosch, Sergi; Vadel, A M; Chtara, Chaker; Khemira, Habib

    2010-01-01

    The potential of four essential cations (K(+), Ca(2+), Mg(2+) and Fe(2+)) to alleviate salt toxicity was studied in sage (Salvia officinalis L.) plants grown in pots. Two concentrations of the following chloride salts: KCl, CaCl₂, MgCl₂ and FeCl₃, were used together with 100mM NaCl to study the effects of these nutrients on plant growth, leaf essential oils (EOs) and phenolic diterpenes composition. The sage plants accumulated Na(+) in their leaves (includers); this has affected secondary metabolites' biosynthesis. Treatment with 100mM NaCl slightly decreased borneol and viridiflorol, while increased manool concentrations. Addition of KCl, CaCl₂ and MgCl₂ increased considerably in a dose-dependent manner the oxygen-containing monoterpenes (1.8-cineole, camphor, β-thujone and borneol) in 100mM NaCl-treated sage. Whereas, the contents of viridiflorol decreased further with the addition of KCl in 100mM NaCl-treated sage. Our results suggest that the changes in EOs composition were more related to K(+) and Ca(2+) availability than to Na(+) toxicity. Furthermore, treatment with NaCl decreased by 50% carnosic acid (CA), a potent antioxidant, content in the leaves. K(+) and Ca(2+) promoted the accumulation of CA and its methoxylated form (MCA) in the leaves. The concentration of CA was positively correlated with leaf K(+) (r=0.56, P=0.01) and Ca(2+) (r=0.44, P=0.05) contents. It appears that different salt applications in combination with NaCl treatments had a profound effect on EOs and phenolic diterpene composition in sage. Therefore, ionic interactions may be carefully considered in the cultivation of this species to get the desired concentrations of these secondary metabolites in leaf extracts.

  15. Endogenous diterpenes derived from ent-kaurene, a common gibberellin precursor, regulate protonema differentiation of the moss Physcomitrella patens.

    PubMed

    Hayashi, Ken-ichiro; Horie, Keisuke; Hiwatashi, Yuji; Kawaide, Hiroshi; Yamaguchi, Shinjiro; Hanada, Atsushi; Nakashima, Tamotsu; Nakajima, Masatoshi; Mander, Lewis N; Yamane, Hisakazu; Hasebe, Mitsuyasu; Nozaki, Hiroshi

    2010-07-01

    Gibberellins (GAs) are a group of diterpene-type plant hormones biosynthesized from ent-kaurene via ent-kaurenoic acid. GAs are ubiquitously present in seed plants. The GA signal is perceived and transduced by the GID1 GA receptor/DELLA repressor pathway. The lycopod Selaginella moellendorffii biosynthesizes GA and has functional GID1-DELLA signaling components. In contrast, no GAs or functionally orthologous GID1-DELLA components have been found in the moss Physcomitrella patens. However, P. patens produces ent-kaurene, a common precursor for GAs, and possesses a functional ent-kaurene synthase, PpCPS/KS. To assess the biological role of ent-kaurene in P. patens, we generated a PpCPS/KS disruption mutant that does not accumulate ent-kaurene. Phenotypic analysis demonstrates that the mutant has a defect in the protonemal differentiation of the chloronemata to caulonemata. Gas chromatography-mass spectrometry analysis shows that P. patens produces ent-kaurenoic acid, an ent-kaurene metabolite in the GA biosynthesis pathway. The phenotypic defect of the disruptant was recovered by the application of ent-kaurene or ent-kaurenoic acid, suggesting that ent-kaurenoic acid, or a downstream metabolite, is involved in protonemal differentiation. Treatment with uniconazole, an inhibitor of ent-kaurene oxidase in GA biosynthesis, mimics the protonemal phenotypes of the PpCPS/KS mutant, which were also restored by ent-kaurenoic acid treatment. Interestingly, the GA(9) methyl ester, a fern antheridiogen, rescued the protonemal defect of the disruption mutant, while GA(3) and GA(4), both of which are active GAs in angiosperms, did not. Our results suggest that the moss P. patens utilizes a diterpene metabolite from ent-kaurene as an endogenous developmental regulator and provide insights into the evolution of GA functions in land plants.

  16. Determination of steroidal glycosides in Yucca gloriosa flowers by LC/MS/MS.

    PubMed

    Montoro, Paola; Skhirtladze, Alexandre; Perrone, Angela; Benidze, Mariam; Kemertelidze, Ether; Piacente, Sonia

    2010-09-05

    An high-performance liquid chromatography (HPLC) coupled with tandem mass spectrometry (MS/MS) method, was developed for the quantitative analysis of the steroidal glycosides occurring in Yucca gloriosa flowers. The HPLC experiments were performed by means of an octadecyl-modified reversed-phase C-18 column and a binary mobile phase system under gradient elution conditions. The fragmentation patterns of steroidal saponins were analyzed by ESI-MS(n) in positive ion mode and a specific multiple reaction monitoring MS/MS detection was developed for their quantitative determination. The described method provides high sensitivity and specificity for quantitative determination of the steroidal glycosides in Y. gloriosa flowers. Quantification was performed against an external calibration line obtained using each pure steroidal glycoside. Short- and long-term repeatabilities of the methods were better than 3 and 6%, respectively. The method was validated according to EMEA guidelines and applied to real samples.

  17. Strategies to reduce end-product inhibition in family 48 glycoside hydrolases.

    PubMed

    Chen, Mo; Bu, Lintao; Alahuhta, Markus; Brunecky, Roman; Xu, Qi; Lunin, Vladimir V; Brady, John W; Crowley, Michael F; Himmel, Michael E; Bomble, Yannick J

    2016-03-01

    Family 48 cellobiohydrolases are some of the most abundant glycoside hydrolases in nature. They are able to degrade cellulosic biomass and therefore serve as good enzyme candidates for biofuel production. Family 48 cellulases hydrolyze cellulose chains via a processive mechanism, and produce end products composed primarily of cellobiose as well as other cellooligomers (dp ≤ 4). The challenge of utilizing cellulases in biofuel production lies in their extremely slow turnover rate. A factor contributing to the low enzyme activity is suggested to be product binding to enzyme and the resulting performance inhibition. In this study, we quantitatively evaluated the product inhibitory effect of four family 48 glycoside hydrolases using molecular dynamics simulations and product expulsion free-energy calculations. We also suggested a series of single mutants of the four family 48 glycoside hydrolases with theoretically reduced level of product inhibition. The theoretical calculations provide a guide for future experimental studies designed to produce mutant cellulases with enhanced activity.

  18. Occurrence of iridoid glycosides in in vitro cultures and intact plants of Scrophularia nodosa L.

    PubMed

    Sesterhenn, Katja; Distl, Melanie; Wink, Michael

    2007-03-01

    Shoot, root, and callus cultures of Scrophularia nodosa L. (Scrophulariaceae) were established and cultivated in vitro. Iridoid glycosides, such as harpagoside, aucubin, and catalpol were identified by LC-ESI-MS and their contents determined by HPLC. For comparison intact plants of S. nodosa were analysed. In shoot cultures slightly lower amounts of detectable iridoid glycosides (4.36% dry weight) were determined than in the field grown plants (4.88%). Concentration of harpagoside was highest in leaves of field plants (1.05%) and in flowers of in vitro plantlets (1.10%). For aucubin the highest amount was found in the leaves of in vitro plantlets (1.67%) whereas the levels of aucubin in the leaves of field plants were remarkably lower. Catalpol was produced as a trace compound in intact plants and shoot cultures. Callus and root cultures were apparently not able to synthesise iridoid glycosides.

  19. Two new quinochalcone C-glycosides from the florets of Carthamus tinctorius.

    PubMed

    Yue, Shijun; Tang, Yuping; Xu, Chengmei; Li, Shujiao; Zhu, Yue; Duan, Jin-Ao

    2014-09-22

    Two new quinochalcone C-glycosides, named hydroxysafflor yellow B (1) and hydroxysafflor yellow C (2), along with two known quinochalcone C-glycosides, safflomin C (3) and saffloquinoside C (4), and one known flavanone, (2R)-4',5-dihydroxyl-6, 7-di-O-β-d-glucopyranosyl flavanone (5), were isolated from the florets of Carthamus tinctorius. Their structures were determined by extensive spectroscopic (UV, IR, HR-ESI-MS, 1D and 2D NMR) analyses. In addition, these quinochalcone C-glycosides together with hydroxysafflor yellow A and anhydrosafflor yellow B were evaluated for their anti-oxidative effects against H2O2-induced cytotoxicity in cultured H9c2 cells. Among them, compound 2 exhibited significant anti-oxidative effects.

  20. Antinociceptive and anti-inflammatory activities of iridoid glycosides extract of Lamiophlomis rotata (Benth.) Kudo.

    PubMed

    Li, Maoxing; Shang, Xiaofei; Zhang, Ruxue; Jia, Zhengping; Fan, Pengcheng; Ying, Qiang; Wei, Lili

    2010-04-01

    Lamiophlomis rotata (Benth.) Kudo is a perennial herb (Labiatae) used as the Tibetan traditional medicine with the effects of alleviating pain, detumescence, hemostasis, promoting blood circulation to remove blood stasis and reinforcing marrow. In this study, we investigated the antinociceptive and anti-inflammatory activities of iridoid glycosides extract of L. rotata (IGLR) in mice. Our results showed that the iridoid glycosides extract could decrease acetic-acid-induced writhings times and formalin-induced lickings times, inhibit carrageenan-induced hind paw edema and xylene-induced ear swelling, and suppress peritoneal capillary permeability and leukocyte infiltration also induced by acetic acid in mice. All of these results suggested that the iridoid glycosides extract possesses the significant antinociceptive and anti-inflammatory activities.

  1. Strategies to reduce end-product inhibition in family 48 glycoside hydrolases

    SciTech Connect

    Chen, Mo; Bu, Lintao; Alahuhta, Markus; Brunecky, Roman; Xu, Qi; Lunin, Vladimir V.; Brady, John W.; Crowley, Michael F.; Himmel, Michael E.; Bomble, Yannick J.

    2016-02-01

    Family 48 cellobiohydrolases are some of the most abundant glycoside hydrolases in nature. They are able to degrade cellulosic biomass and therefore serve as good enzyme candidates for biofuel production. Family 48 cellulases hydrolyze cellulose chains via a processive mechanism, and produce end products composed primarily of cellobiose as well as other cellooligomers (dp ≤ 4). The challenge of utilizing cellulases in biofuel production lies in their extremely slow turnover rate. A factor contributing to the low enzyme activity is suggested to be product binding to enzyme and the resulting performance inhibition. In this study, we quantitatively evaluated the product inhibitory effect of four family 48 glycoside hydrolases using molecular dynamics simulations and product expulsion free-energy calculations. We also suggested a series of single mutants of the four family 48 glycoside hydrolases with theoretically reduced level of product inhibition. As a result, the theoretical calculations provide a guide for future experimental studies designed to produce mutant cellulases with enhanced activity.

  2. Two new cytotoxic glycosides isolated from the green walnut husks of Juglans mandshurica Maxim.

    PubMed

    Zhou, Yuan-Yuan; Liu, Quan-Yu; Yang, Bing-You; Jiang, Yan-Qiu; Liu, Yu-Xin; Wang, Ying; Guo, Shuang; Kuang, Haixue

    2017-06-01

    Two new glycosides including an alcohol glycoside and a phenolic glycoside: hexyl-1-O-α-d-arabinofuranosyl-(1 → 6)-β-d-glucopyranoside (1), 4-hydroxypropiophenone-4-O-β-d-glucopyranosyl(1 → 6)-β-d-glucopyranoside(2), along with six known naphthalenyl glucosides (3-8) were isolated from green walnut husks of Juglans mandshurica, and their structures were elucidated on the basis of spectroscopic studies. All compounds were evaluated for their inhibitory effects on tumour cells (BGC-823, HepG-2, MCF-7). The results showed that new compounds 1 and 2 had superior inhibitory activity in comparison with other naphthalenyl glucosides.

  3. N-Hexyl-4-aminobutyl glycosides for investigating structures and biological functions of carbohydrates.

    PubMed

    Suzuki, Katsuhiko; Tobe, Akifumi; Adachi, Shin; Daikoku, Shusaku; Hasegawa, Yasuko; Shioiri, Yuki; Kobayashi, Mariko; Kanie, Osamu

    2009-11-21

    The potential applications of N-hexyl-4-aminobutyl glycosides in the mass spectrometric investigation of glycan structure and in the investigation of glycan functions were studied. Under collision-induced dissociation (CID) conditions, sodiated glycosides carrying N-hexyl-4-aminobutyl groups effectively produced a hemiacetal species (C-ions), which is important in mass-spectrometry-based structural investigation. The usefulness of N-hexyl-4-aminobutyl glycosides in biological analysis was also confirmed by obtaining a binding constant for the binding of dipyrrometheneboron difluoride C3-labeled N-hexyl-4-aminobutyl beta-lactoside with an Erythrina cristagalli lectin, and by visualizing cellular organelles using a more hydrophobic BODIPY-labeled compound.

  4. Synthesis of phenylazonaphtol-β-D-O-glycosides, evaluation as substrates for beta-glycosidase activity and molecular studies

    PubMed Central

    2014-01-01

    Background Phenylazonaphtol-β-D-O-glycosides are alternative substrates for the detection of enzymatic activity of β-glycosidases which are involved in various important processes. These azoic compounds are currently exploited as prodrugs for colonic disease due the presence of β-glycosidase activity in the gut flora and therefore allowing the release of the drug at the specific site. Results Phenylazonaphtol-β-D-O-glucoside 3a and galactoside 3b were prepared via diazonium salt conditions under weak acidic conditions which do not compromise the O-glycosidic bond stability, by coupling reaction between 2-naphtol sodium salt with aminoglycosides 1a and 1b. The resulting phenylazonaphtol glycosides 2a and 2b were deprotected affording the phenylazonaphtol glycosides 3a and 3b in quantitative yield. The galactoside glycoside 3b was assayed as substrate for in vitro β-galactosidase enzymatic activity showing strong absorbance after releasing of the azoic chromophore. Also, docking studies were performed to determine the best pose as well as the interactions between the ligand and the residues located at the active site. Conclusions The methodology developed for synthesizing the phenylazonaphtol glycosides described proved to be convenient for generating azoic functionalities in the presence of glycosidic bonds and the glycosides suitable as alternative substrates and potentially useful prodrugs in the treatment of colonic diseases. PMID:24995152

  5. Temporary reduction of radiation does not permanently reduce flavonoid glycosides and phenolic acids in red lettuce.

    PubMed

    Becker, Christine; Kläring, Hans-Peter; Kroh, Lothar W; Krumbein, Angelika

    2013-11-01

    Applying transparent daytime screens in greenhouses in cool seasons reduces the amount of energy needed for heating, but also the solar radiation available for crops. This can reduce yield and product quality of leafy vegetables because of constrained photosynthesis and altered biosynthesis. To study this, we cultivated five-week old red leaf lettuce (Lactuca sativa L.) for four weeks in growth chambers under a photosynthetic photon flux density (PPFD) of 225 and 410 μmol m(-2) s(-1), respectively. Some plants were exchanged between radiation intensities after two weeks. We investigated the concentration of five flavonoid glycosides, three caffeic acid derivatives, reducing sugars as well as plant growth. Remarkably, no significant influence of radiation intensity on the concentration of phenolic acids or anthocyanin glycosides was observed. In contrast, quercetin and luteolin glycoside concentration was between 14 and 34% lower in plants growing under lower compared to higher PPFD. Already after two weeks of cultivation, plants grown under lower PPFD contained less quercetin and luteolin glycosides but they completely compensated if subsequently transferred to higher PPFD until harvest. Hence, marketable lettuce heads which experienced temporary shading followed by an unshaded phase did not contain lower concentrations of flavonoid glycosides or phenolic acids. Also, there was no reduction of head mass in this variant. Our results suggest that saving energy in early growth stages is feasible without losses in yield or health promoting phenolic substances. In addition, there was a close correlation between the concentration of reducing sugars and some flavonoid glycosides, indicating a close metabolic connection between their biosynthesis and the availability of carbohydrates.

  6. Megastigmane glycosides from leaves of Eucommia ulmoides Oliver with ACE inhibitory activity.

    PubMed

    Yan, Jian-Kun; Ding, Li-Qin; Shi, Xu-Liu; Donkor, Paul Owusu; Chen, Li-Xia; Qiu, Feng

    2017-01-01

    Four new megastigmane glycosides, eucomegastigsides A-D (2, 3, 5 and 7), together with three known megastigmane glycosides, (6R, 7E, 9R)-9-hydroxy-4, 7-megastigmadien-3-one-9-O-[α-l-arabinopyranosyl-(l→6)-β-d-glucopyranoside (1), foliasalacioside B1 (4) and eleganoside A (6), were isolated from the leaves of Eucommia ulmoides Oliver. Their anti-hypertensive effect was investigated in vitro based on the inhibition of Angiotensin Converting Enzyme (ACE) using HPLC. The results showed that the isolates (2, 3, 4, 5, 7) had moderate inhibitory effects on ACE in vitro compared with captopril.

  7. Phyto-glycosides as therapeutic target in the treatment of diabetes.

    PubMed

    Khan, Haroon; Khattak, Sumaira

    2016-09-09

    Diabetes is a chronic metabolic disorder characterized by increased level of glucose in the blood due to defects in insulin action, insulin secretion or both. The therapeutic agents in clinical practice are facing the challenge of patient compliance therefore, new effective therapies are most warrant. In this connection, the natural product could be the best option. This review encounters various plant glycosides with antidiabetic effects; mediated through different mechanism(s). Focusing glycosides as antidiabetic therapy could lead to the discovery of some new effective therapeutic agents.

  8. Phenylpropanoid and lignan glycosides from the aerial parts of Lespedeza cuneata.

    PubMed

    Zhou, Jian; Li, Chuang-Jun; Yang, Jing-Zhi; Ma, Jie; Wu, Lian-Qiu; Wang, Wen-Jie; Zhang, Dong-Ming

    2016-01-01

    Four phenylpropanoid glucosides (1-4) and five lignan glycosides (5-9) were isolated from the aerial parts of Lespedeza cuneata, together with three known lignan glycosides (10-12). Their structures were elucidated on the basis of spectroscopic analyses, and the absolute configurations of compounds 5-9 were determined from the CD spectra. In addition, the compounds were tested for their ability to activate the transcription effect on xbp1 promoter. Compounds 4, 5, 7, 9, 10, and 12 could activate the transcription of xbp1 to varying degrees, with EC50 values ranging from 0.18 to 0.64 μM.

  9. Electrospray ionization mass spectrometry of mixtures of triterpene glycosides with L-phenylalanine

    NASA Astrophysics Data System (ADS)

    Lekar, A. V.; Vetrova, E. V.; Borisenko, N. I.; Yakovishin, L. A.; Grishkovets, V. I.; Borisenko, S. N.

    2011-09-01

    Electrospray-ionization mass spectrometry (ESI-MS) was used to investigate for the first time the molecular complexation of L-phenylalanine with hederagenin 3-O- α- L-rhamnopyranosyl-(1 → 2)-O- α- L-arabinopyranoside ( α-hederin) and its 28-O- α- L-rhamnopyranosyl-(1 → 4)-O-β- D-glucopyranosyl-(1 → 6)-O-β- D-glucopyranosyl ester (hederasaponin C). The glycoside/ L-phenylalanine complexes with a 1:1 molar ratio turned out to be most stable. The structures of the glycosides and L-phenylalanine have been concluded to have an impact on the complexation process.

  10. Dietary flavonoid aglycones and their glycosides: Which show better biological significance?

    PubMed

    Xiao, Jianbo

    2017-06-13

    The dietary flavonoids, especially their glycosides, are the most vital phytochemicals in diets and are of great general interest due to their diverse bioactivity. The natural flavonoids almost all exist as their O-glycoside or C-glycoside forms in plants. In this review, we summarized the existing knowledge on the different biological benefits and pharmacokinetic behaviors between flavonoid aglycones and their glycosides. Due to various conclusions from different flavonoid types and health/disease conditions, it is very difficult to draw general or universally applicable comments regarding the impact of glycosylation on the biological benefits of flavonoids. It seems as though O-glycosylation generally reduces the bioactivity of these compounds - this has been observed for diverse properties including antioxidant activity, antidiabetes activity, anti-inflammation activity, antibacterial, antifungal activity, antitumor activity, anticoagulant activity, antiplatelet activity, antidegranulating activity, antitrypanosomal activity, influenza virus neuraminidase inhibition, aldehyde oxidase inhibition, immunomodulatory, and antitubercular activity. However, O-glycosylation can enhance certain types of biological benefits including anti-HIV activity, tyrosinase inhibition, antirotavirus activity, antistress activity, antiobesity activity, anticholinesterase potential, antiadipogenic activity, and antiallergic activity. However, there is a lack of data for most flavonoids, and their structures vary widely. There is also a profound lack of data on the impact of C-glycosylation on flavonoid biological benefits, although it has been demonstrated that in at least some cases C-glycosylation has positive effects on properties that may be useful in human healthcare such as antioxidant and antidiabetes activity. Furthermore, there is a lack of in vivo data that would make it possible to make broad generalizations concerning the influence of glycosylation on the benefits of

  11. Electrospray-ionization mass spectrometry of mixtures of triterpene glycosides with paracetamol

    NASA Astrophysics Data System (ADS)

    Lekar, A. V.; Vetrova, E. V.; Borisenko, N. I.; Yakovishin, L. A.; Grishkovets, V. I.

    2010-11-01

    Molecular complexation of paracetamol with hederagenin 3-O-α-L-rhamnopyranosyl-(1 → 2)-O-α-L-arabinopyranoside (α-hederin) and its 28-O-α-L-rhamnopyranosyl-(1 → 4)-O-β-D-glucopyranosyl-(1 → 6)-O-β-Dglucopyranosyl ether (hederasaponin C) was investigated for the first time using electrospray-ionization mass spectrometry (ESI-MS). The glycosides form complexes with paracetamol in a 1:1 molar ratio. The hederasaponin C complex is more stable. The structures of the glycosides and paracetamol are concluded to have an impact on the complexation process.

  12. Microcystbiopterins A-E, five O-methylated biopterin glycosides from two Microcystis spp. bloom biomasses.

    PubMed

    Lifshits, Marina; Kovalerchik, Dimitri; Carmeli, Shmuel

    2016-03-01

    Five previously undescribed biopterin glycosides, microcystbiopterin A-E, were isolated from the extracts of two bloom materials of Microcystis spp. collected from a fishpond (IL-337) and Lake Kinneret (IL-347), Israel. The structure of the pterins was established by interpretation of their UV, CD, 1D and 2D NMR spectra and HR mass measurements. Microcystbiopterin D is the first heptose containing pterin glycoside to be reported in the literature. Their antimicrobial and cytotoxic properties were evaluated but all were found not active in both assays.

  13. Sixteen novel C-21 steroidal glycosides from the roots of Cynanchum mooreanum.

    PubMed

    Cui, Bo; Wang, Xinhong; Yang, Yifu; Yang, Yang; Shi, Songshan; Guo, Fujiang; Li, Yiming

    2015-12-01

    Fourteen novel 14,15-diseco-18-nor-pregnane-type steroidal glycosides, mooreanoside A-C (1-3) and mooreanoside F-P (6-16) and two new 14,15-diseco-pregnane-type steroidal glycosides, mooreanoside D-E (4-5) were isolated from the roots of Cynanchum mooreanum Hemsl. Their structures were determined on the basis of spectroscopic and chemical analysis. Compounds 1-6, 8-10, 12-14 and 16 were tested for their immunological activities in vitro against Con-A induced proliferation of mice splenocytes.

  14. DPPH radical scavenging activity of two flavonol glycosides from Aconitum napellus sp. lusitanicum.

    PubMed

    Luis, J C; Valdés, F; Martín, R; Carmona, A J; Díaz, Jesús G

    2006-09-01

    The DPPH radical scavenging activity of two flavonol glycosides obtained from ethanolic extracts of Aconitum napellus sp. lusitanicum was studied. The results showed a high DPPH antiradical activity of compound 1 (quercetin 3-O-(6-trans-caffeoyl)-beta-glucopyranosyl-(1-->2)-beta-glucopyranosyl-7-O-alpha-rhamnopyranoside) when compared with compound 2 (quercetin-3-sophoroside-7-rhamnopyranoside), rutin and ascorbic acid. The relationship between the caffeoyl and rhamnopyranoside groups in the flavonol glycosides structures and the DPPH antiradical activity was also discussed.

  15. Eurycomaoside: a new quassinoid-type glycoside from the roots of Eurycoma longifolia.

    PubMed

    Bedir, Erdal; Abou-Gazar, Hassan; Ngwendson, Julius Ngunde; Khan, Ikhlas Ahmad

    2003-11-01

    A new C(19)-quassinoid-type glycoside has been isolated from the roots of Eurycoma longifolia. The structure elucidation of the compound was achieved by a combination of one- and two-dimensional NMR techniques, including (1)H-(1)H-correlation spectroscopy (COSY), (1)H-(13)C-heteronuclear correlation spectroscopy (HMQC), and (1)H-(13)C-heteronuclear multiple-bond correlation spectroscopy (HMBC), as well as high resolution electrospray ionization Fourier transformation mass spectrometry (HR-ESI-FT-MS) data. The C(1)-glycosidation site in the quassinoid framework is encountered for the first time.

  16. Synthesis and cosmetic whitening effect of glycosides derived from several phenylpropanoids.

    PubMed

    Tanimoto, Shinichi; Tominaga, Hitoshi; Okada, Yoshiharu; Nomura, Masato

    2006-03-01

    Plant-derived phenylpropanoid compounds (4-ethyl-2-methoxyphenol, 2,6-dimethoxyphenol, 2,3-dimethoxyphenol, 3,4-dimethoxyphenol, 3,5-dimethoxyphenol, 3,4-dihydroxycinnamic acid, 4-hydroxy-3-methoxycinnamic acid, and 3-hydroxy-4-methoxycinnamic acid) were glycosidated to form glycoside compounds. We evaluated the effects of these compounds on the inhibition of tyrosinase and melanin synthesis and their cytotoxicity from the viewpoint of their use as whitening agents in cosmetics. Some compounds had more potent tyrosinase-inhibiting activity than commercial arbutin, which was used as a control, and showed no cytotoxicity at low concentration ranges.

  17. A steryl glycoside fraction with hemolytic activity from tubers of Momordica cochinchinensis.

    PubMed

    Ng, T B; Li, W W; Yeung, H W

    1986-10-01

    A hemolytic fraction has been obtained from fresh tubers of Momordica cochinchinensis. The fraction was strongly adsorbed on DEAE-Sepharose CL6B. It did not stain with Coomassie brilliant blue in SDS-polyacrylamide gel electrophoresis and it gave no immunoprecipitin arcs in immunoelectrophoresis. The hemolytic activity of the fraction was resistant to heat and proteolytic enzymes. The behavior of the fraction in thin-layer chromatography and its positive reaction in Liebermann-Burchard test indicated that the hemolytic activity of the fraction can be attributed to a steryl glycoside(s).

  18. Synthesis of O- and C-glycosides derived from β-(1,3)-D-glucans.

    PubMed

    Marca, Eduardo; Valero-Gonzalez, Jessika; Delso, Ignacio; Tejero, Tomás; Hurtado-Guerrero, Ramon; Merino, Pedro

    2013-12-15

    A series of β-(1,3)-d-glucans have been synthesized incorporating structural variations specifically on the reducing end of the oligomers. Both O- and C-glucosides derived from di- and trisaccharides have been obtained in good overall yields and with complete selectivity. Whereas the O-glycosides were obtained via a classical Koenigs-Knorr glycosylation, the corresponding C-glycosides were obtained through allylation of the anomeric carbon and further cross-metathesis reaction. Finally, the compounds were evaluated against two glycosidases and two endo-glucanases and no inhibitory activity was observed.

  19. Colochirosides A₁, A₂, A₃, and D, Four Novel Sulfated Triterpene Glycosides from the Sea Cucumber Colochirus robustus (Cucumariidae, Dendrochirotida).

    PubMed

    Silchenko, Alexandra S; Kalinovsky, Anatoly I; Avilov, Sergey A; Andryjaschenko, Pelageya V; Dmitrenok, Pavel S; Kalinin, Vladimir I; Yurchenko, Ekaterina A; Dolmatov, Igor Yu

    2016-03-01

    Four new triterpene glycosides, colochirosides A₁ (1), A₂ (2), A₃ (3) and D (4), have been isolated from the sea cucumber Colochirus robustus (Cucumariidae, Dendrochirotida). Structures of the glycosides have been elucidated by 2D NMR spectroscopy and mass-spectrometry. Colochiroside D (4) has a new type of carbohydrate chain having the only sulfate group attached to C-6 of the third (glucose) monosaccharide residue. Cytotoxic activities of glycosides 1-4 against the ascite form of mouse Ehrlich carcinoma cells and hemolytic activity against mouse erythrocytes have been studied. Hemolytic activity of the glycosides was higher than cytotoxic. Glycosides 1, 3 and 4 demonstrated strong effects, whereas compound 2 showed only moderate activity.

  20. Jatrophane diterpenes as modulators of multidrug resistance. Advances of structure-activity relationships and discovery of the potent lead pepluanin A.

    PubMed

    Corea, Gabriella; Fattorusso, Ernesto; Lanzotti, Virginia; Motti, Riccardo; Simon, Pierre-Noël; Dumontet, Charles; Di Pietro, Attilio

    2004-02-12

    From the whole plant of Euphorbia peplus L., five new diterpenes based on a jatrophane skeleton (pepluanins A-E, 1-5) were isolated, together with two known analogues (6 and 7), which served to divulge in detail the structure-activity relationships within this class of P-glycoprotein inhibitors. The results revealed the importance of substitutions on the medium-sized ring (carbons 8, 9, 14, and 15). In particular, the activity is collapsed by the presence of a free hydroxyl at C-8, while it increases with a carbonyl at C-14, an acetoxyl at C-9, and a free hydroxyl at C-15. The most potent compound of the series, pepluanin A, showed a very high activity for a jatrophane diterpene, outperforming cyclosporin A by a factor of at least 2 in the inhibition of Pgp-mediated daunomycin transport.

  1. Synthetic studies of neoclerodane diterpenes from Salvia divinorum: semisynthesis of salvinicins A and B and other chemical transformations of salvinorin A.

    PubMed

    Harding, Wayne W; Schmidt, Matthew; Tidgewell, Kevin; Kannan, Pavitra; Holden, Kenneth G; Gilmour, Brian; Navarro, Hernan; Rothman, Richard B; Prisinzano, Thomas E

    2006-01-01

    Salvinorin A (1) is a hallucinogenic neoclerodane diterpene isolated from the widely available psychoactive plant Salvia divinorum and is the first example of a non-nitrogenous opioid receptor ligand. At present, there is little information available as to why this compound is selective for kappa opioid receptors. One approach to better understanding the mode of binding of 1 at kappa receptors is to systematically alter the structure of 1 and examine the effects on opioid receptor affinity and activity. Currently, there is a paucity of methods described for the preparation of analogues derived from 1. Here, we report the investigation of several chemical transformations of 1 isolated from S. divinorum. In particular, this work provides a semisynthesis of salvinicins A (2) and B (3) and has identified 10a as the first neoclerodane diterpene with delta opioid antagonist activity.

  2. Systematic screening and characterization of glycosides in tobacco leaves by liquid chromatography with atmospheric pressure chemical ionization tandem mass spectrometry using neutral loss scan and product ion scan.

    PubMed

    Ding, Li; Wang, Xiaoyu; Wang, Sheng; Yu, Jingjing; Qin, Yaqiong; Zhang, Xiaobing; Xie, Fuwei

    2015-12-01

    Glycosides in tobacco leaves are highly important aromatic precursors. It is necessary to reveal glycosides in tobacco leaves to improve tobacco planting and processing. This study describes a method for the systematic screening of glycosides in tobacco leaves by liquid chromatography with tandem mass spectrometry. Although glycosides contain numerous aglycones, the number of glycans is limited. Based on a screening table of glycans designed for neutral loss scan, glycosides with different aglycones were systematically screened out. Then, the MS(2) fragment spectra of scanned glycosides were further obtained using product ion scan. By comparison with the spectra in online tandem mass spectral databases, reported references, and verification by commercial standards, 64 glycosides were detected, including 39 glycosides linked with monosaccharides, 18 glycosides linked with disaccharides and 7 glycosides linked with trisaccharides. It is noteworthy that glycosides linked with trisaccharides have previously been rarely reported in tobacco. This method appears to be a useful tool for the systematic screening and characterization of glycosides in tobacco and can potentially be applied to other plants.

  3. Five new resin glycoside derivatives isolated from the convolvulin fraction of seeds of Quamoclit pennata after treatment with indium(III) chloride in methanol.

    PubMed

    Akiyama, Kousuke; Yamamoto, Kazutaka; Mineno, Tomoko; Okawa, Masafumi; Kinjo, Junei; Yoshimitsu, Hitoshi; Nohara, Toshihiro; Ono, Masateru

    2014-01-01

    Three new acylated methyl glycosides and two new acylated glycosidic acid methyl esters were isolated after treatment of the crude ether-insoluble resin glycoside (convolvulin) fraction from seeds of Quamoclit pennata BOJER (Convolvulaceae) with indium(III) chloride in methanol. Their structures were elucidated on the basis of spectroscopic data and chemical conversions.

  4. NaCl stress-induced changes in the essential oil quality and abietane diterpene yield and composition in common sage

    PubMed Central

    Tounekti, Taieb; Khemira, Habib

    2015-01-01

    Aim: The purpose of this study was to evaluate how increasing NaCl salinity in the medium can affects the essential oils (EOs) composition and phenolic diterpene content and yield in leaves of Salvia officinalis L. The protective role of such compounds against NaCl stress was also argued with regard to some physiological characteristics of the plant (water and ionic relations as well as the leaf gas exchanges). Materials and Methods: Potted plants were exposed to increasing NaCl concentrations (0, 50, 75, and 100 mM) for 4 weeks during July 2012. Replicates from each treatment were harvested after 0, 2, 3, and 4 weeks of adding salt to perform physiological measurements and biochemical analysis. Results: Sage EOs were rich in manool, viridiflorol, camphor, and borneol. Irrigation with a solution containing 100 mM NaCl for 4 weeks increased considerably 1.8-cineole, camphor and β-thujone concentrations, whereas lower concentrations (50 and 75 mM) had no effects. On the contrary, borneol and viridiflorol concentrations decreased significantly under the former treatment while manool and total fatty acid concentrations were not affected. Leaf extracts also contained several diterpenes such as carnosic acid (CA), carnosol, and 12-O-methoxy carnosic acid (MCA). The concentrations and total contents of CA and MCA increased after 3 weeks of irrigation with 75 or 100 mM NaCl. The 50 mM NaCl had no effect on these diterpenes. Our results suggest a protective role for CA against salinity stress. Conclusion: This study may provide ways to manipulate the concentration and yield of some phenolic diterpenes and EOs in sage. In fact, soil salinity may favor a directional production of particular components of interest. PMID:26401409

  5. Nigellamines A3, A4, A5, and C, new dolabellane-type diterpene alkaloids, with lipid metabolism-promoting activities from the Egyptian medicinal food black cumin.

    PubMed

    Morikawa, Toshio; Xu, Fengming; Ninomiya, Kiyofumi; Matsuda, Hisashi; Yoshikawa, Masayuki

    2004-04-01

    New dolabellane-type diterpene alkaloids, nigellamines A(3), A(4), A(5), and C, were isolated from the methanolic extract of an Egyptian medicinal food, black cumin (the seeds of Nigella sativa). Their absolute configurations were determined on the basis of chemical and physicochemical evidence. Nigellamines were found to lower triglyceride levels in primary cultured mouse hepatocytes, and in particular, the activity of nigellamine A(5) was equivalent to that of the hypolipidemic agent, clofibrate.

  6. Influence of the configurational pattern of sp(2)-iminosugar pseudo N-, S-, O- and C-glycosides on their glycoside inhibitory and antitumor properties.

    PubMed

    Sánchez-Fernández, Elena M; Gonçalves-Pereira, Rita; Rísquez-Cuadro, Rocío; Plata, Gabriela B; Padrón, José M; García Fernández, José M; Ortiz Mellet, Carmen

    2016-06-24

    The synthesis of a complete series of cyclic carbamate-type sp(2)-iminosugar N-, S-, O- and C-octyl pseudoglycosides related to nojirimycin, mannojirimycin and galactonojirimycin, all having the α-pseudoanomeric configuration, is reported. The gem-diamine-type N-pseudoglycosides can be accessed directly from the corresponding reducing sp(2)-imisosugar precursors by reaction with octylamine in methanol, whereas per-O-acetyl or 1-fluoro derivatives were used as pseudoglycosyl donors for the preparation of S-pseudoglycosides or O- and C-pseudoglycosides, respectively. Evaluation of their inhibitory properties against a panel of glycosidases evidenced selectivity profiles that strongly depend on the configurational pattern and the nature of the glycosidic linkage. On the contrary, the antiproliferative activity determined against a panel of tumor cell lines was largely independent of the relative orientation of the hydroxyl groups in the sp(2)-iminosugar moiety. Indeed, sp(2)-iminosugar representatives exhibiting significant growth inhibition potencies were identified in all three configurationally different types of compounds studied, namely α-d-gluco, α-d-manno and α-d-galacto glycoside analogs. Interestingly, none of the compounds affected viability and mortality of normal cells at the used concentrations. Altogether, the results strongly suggest that the anticancer activity of amphiphilic sp(2)-iminosugar glycosides might be unrelated, or not solely related, to their glycosidase inhibitory activity.

  7. Analysis of glycosidically bound aroma precursors in tea leaves. 1. Qualitative and quantitative analyses of glycosides with aglycons as aroma compounds.

    PubMed

    Wang, D; Yoshimura, T; Kubota, K; Kobayashi, A

    2000-11-01

    Twenty-six synthetic glycosides constituting aglycons of the main tea aroma compounds ((Z)-3-hexenol, benzyl alcohol, 2-phenylethanol, methyl salicylate, geraniol, linalool, and four isomers of linalool oxides) were synthesized in our laboratory as authentic compounds. Those compounds were used to carry out a direct qualitative and quantitative determination of the glycosides as aroma precursors in different tea cultivars by capillary gas chromatographic-mass spectrometric (GC-MS) analyses after trifluoroacetyl conversion of the tea glycosidic fractions. Eleven beta-D-glucopyranosides, 10 beta-primeverosides (6-O-beta-D-xylopyranosyl-beta-D-glucopyranoside) with aglycons as the above alcohols, and geranyl beta-vicianoside (6-O-alpha-L-arabinopyranosyl-beta-D-glucopyranoside) were identified (tentatively identified in the case of methyl salicylate beta-primeveroside) in fresh tea leaves and quantified on the basis of calibration curves that had been established by using the synthetic compounds. Primeverosides were more abundant than glucosides in each cultivar we investigated for making green tea, oolong tea, and black tea. Separation of the diastereoisomers of linalool and four isomers of linalool oxides by GC analyses is also discussed.

  8. Preparative isolation and purification of five flavonoid glycosides and one benzophenone galloyl glycoside from Psidium guajava by high-speed counter-current chromatography (HSCCC).

    PubMed

    Zhu, Yindi; Liu, Yue; Zhan, Ying; Liu, Lin; Xu, Yajuan; Xu, Tunhai; Liu, Tonghua

    2013-12-16

    Psidium guajava leaves have a diverse phytochemical composition including flavonoids, phenolics, meroterpenoids and triterpenes, responsible for the biological activities of the medicinal parts. In particular, flavonol glycosides show beneficial effects on type II diabetes mellitus. A simple and efficient HSCCC method has been developed for the preparative separation of five flavonoid glycosides and one diphenylmethane glycoside from P. guajava. A solvent system composed of n-hexane-ethyl acetate-methanol-water (0.7:4:0.8:4, v/v/v/v) was optimized for the separation. The upper phase was used as the stationary phase, and the lower phase was used as the mobile phase. Under the optimized conditions, hyperoside (15.3 mg), isoquercitrin (21.1 mg), reynoutrin (65.2 mg), quercetin-3-O-β-D-arabinopyranoside (71.7 mg), quercetin-3-O-α-L-arabinofuranoside (105.6 mg) and 2,4,6-trihydroxy-3,5-dimethylbenzophenone 4-O-(6''-O-galloyl)-β-D-glucopyranoside (98.4 mg) were separated from crude sample (19.8 g). The structures of all the isolates were identified by ESI-MS, 1H- and 13C-NMR analyses and their purities (>95%) were determined using HPLC.

  9. Lolitrem B and Indole Diterpene Alkaloids Produced by Endophytic Fungi of the Genus Epichloë and Their Toxic Effects in Livestock

    PubMed Central

    Philippe, Guerre

    2016-01-01

    Different group of alkaloids are produced during the symbiotic development of fungal endophytes of the genus Epichloë in grass. The structure and toxicity of the compounds vary considerably in mammalian herbivores and in crop pests. Alkaloids of the indole-diterpene group, of which lolitrem B is the most toxic, were first characterized in endophyte-infected perennial ryegrass, and are responsible for “ryegrass staggers.” Ergot alkaloids, of which ergovaline is the most abundant ergopeptide alkaloid produced, are also found in ryegrass, but generally at a lower rate than lolitrem B. Other alkaloids such as lolines and peramine are toxic for crop pests but have weak toxicological properties in mammals. The purpose of this review is to present indole-diterpene alkaloids produced in endophyte infected ryegrass from the first characterization of ryegrass staggers to the determination of the toxicokinetics of lolitrem B and of their mechanism of action in mammals, focusing on the different factors that could explain the worldwide distribution of the disease. Other indole diterpene alkaloids than lolitrem B that can be found in Epichloë infected ryegrass, and their tremorgenic properties, are presented in the last section of this review. PMID:26891327

  10. Insights on profiling of phorbol, deoxyphorbol, ingenol and jatrophane diterpene esters by high performance liquid chromatography coupled to multiple stage mass spectrometry.

    PubMed

    Nothias-Scaglia, Louis-Félix; Schmitz-Afonso, Isabelle; Renucci, Franck; Roussi, Fanny; Touboul, David; Costa, Jean; Litaudon, Marc; Paolini, Julien

    2015-11-27

    This paper reports our effort to develop a comprehensive HPLC-MS(n)-based dereplication strategy for phorbol ester (PE), deoxyphorbol ester (dPE) and ingenol ester (IE) profiling in plant extracts. This strategy is composed of two sequential analysis exploiting specific hybrid triple quadrupole/linear ion trap instrument modes. A first run was performed using a multiple reaction monitoring (MRM) mode targeting fragmentation of PE and dPE/IE coupled with the acquisition of MS(2) spectrum for the ions at m/z 311 and m/z 313, respectively. A second run was then completed based on precursor ion scan mode (PIS) and automatic MS(2) acquisition for each quasimolecular ion. The developed approach was used to investigate ten Euphorbia extracts showing bioactivity against chikungunya virus replication. Experiments allowed partial annotation of three dPE/IE but no PE was detected. Results suggested that other types of diterpene esters displayed PE- and dPE/IE-like fragmentations. The study of jatrophane ester (JE) standards by CID fragmentation using low and high resolution mass spectrometry confirmed this hypothesis, highlighting challenges and difficulties of diterpene esters profiling within plant extracts. Nonetheless, the present LC-MS(n) method can be easily adapted to profile other types of diterpene esters.

  11. Lolitrem B and Indole Diterpene Alkaloids Produced by Endophytic Fungi of the Genus Epichloë and Their Toxic Effects in Livestock.

    PubMed

    Philippe, Guerre

    2016-02-15

    Different group of alkaloids are produced during the symbiotic development of fungal endophytes of the genus Epichloë in grass. The structure and toxicity of the compounds vary considerably in mammalian herbivores and in crop pests. Alkaloids of the indole-diterpene group, of which lolitrem B is the most toxic, were first characterized in endophyte-infected perennial ryegrass, and are responsible for "ryegrass staggers." Ergot alkaloids, of which ergovaline is the most abundant ergopeptide alkaloid produced, are also found in ryegrass, but generally at a lower rate than lolitrem B. Other alkaloids such as lolines and peramine are toxic for crop pests but have weak toxicological properties in mammals. The purpose of this review is to present indole-diterpene alkaloids produced in endophyte infected ryegrass from the first characterization of ryegrass staggers to the determination of the toxicokinetics of lolitrem B and of their mechanism of action in mammals, focusing on the different factors that could explain the worldwide distribution of the disease. Other indole diterpene alkaloids than lolitrem B that can be found in Epichloë infected ryegrass, and their tremorgenic properties, are presented in the last section of this review.

  12. Seasonal variation on the contents of coumarin and kaurane-type diterpenes in Mikania laevigata and M. glomerata leaves under different shade levels.

    PubMed

    Bertolucci, Suzan Kelly V; Pereira, Ana Bárbara D; Pinto, José Eduardo B P; Oliveira, Alaíde B; Braga, Fernão C

    2013-02-01

    Coumarin (1) and kaurane-type diterpenes are considered the bioactive constituents of Mikania glomerata and M. laevigata, used in Brazil to treat respiratory affective disorders. The seasonal variation of 1, ortho-coumaric acid (2), benzoylgrandifloric acid (3), cinnamoylgrandifloric acid (4), and kaurenoic acid (5) in leaves of both species, cultivated in full sunlight and under shade levels of 40 and 80%, was quantified by HPLC. Compound 2 was detected solely in M. laevigata in concentrations below the limit of quantification. Coumarin was not found in M. glomerata, whereas its concentration reached 0.94±0.24% (w/w) in M. laevigata farmed in summer under 80% shading. Both Mikania species produced higher amounts of kaurane diterpenes when cultivated in plenty of sunlight. Hence, maximum contents of 1 are reached in M. laevigata cultivated under high shading, but with reduced concentrations of 3-5. Conversely, M. glomerata should be cultivated under full sunlight and harvested in winter for highest concentrations of kaurane-type diterpenes.

  13. Relevance of the carnosic acid/carnosol ratio for the level of rosemary diterpene transfer and for improving lamb meat antioxidant status.

    PubMed

    Jordán, María J; Castillo, Julián; Bañón, Sancho; Martínez-Conesa, Cristina; Sotomayor, José A

    2014-05-15

    The aim of the present work was to evaluate whether the relation between the concentrations of the two major diterpenes present in two typified rosemary extracts affects their levels of deposition and antioxidant capacity in different lamb tissues. The composition of the extracts expressed as percentage of weight/weight was 1:1 (14-16)% and 2:1 (25-11)% (carnosic acid-carnosol), respectively. Thirty weaned lambs were assigned randomly to three homogeneous groups. One group was fed a basal diet as a control and the diets of the other two were enriched with rosemary extracts 1:1 and 2:1, respectively. HPLC-ESI-MS/TOF identified a metabolite (C19H22O3) described for the first time in lamb tissues, along with carnosol, carnosic acid, rosmanol and carnosol-p-quinone. The results obtained corroborate the importance of the presence of carnosol in the dietary administration of rosemary extract as a way of improving the stability of the diterpene fraction during feed manufacturing and the level of deposition and antioxidant efficacy of diterpenes after ruminal fermentation.

  14. Potential anti-inflammatory phenolic glycosides from the medicinal plant Moringa oleifera fruits

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Bioassay-guided isolation and purification of the ethyl acetate extract of Moringa oleifera fruits yielded three new phenolic glycosides; 4-[(2'-O-acetyl-a-L-rhamnosyloxy) benzyl]isothiocyanate (1), 4-[(3'-O-acetyl-a-L-rhamnosyloxy)benzyl]isothiocyanate (2), and S-methyl-N-{4-[(a-L-rhamnosyloxy)benz...

  15. A new group of glycoside hydrolase family 13 α-amylases with an aberrant catalytic triad

    PubMed Central

    Sarian, Fean D.; Janeček, Štefan; Pijning, Tjaard; Ihsanawati; Nurachman, Zeily; Radjasa, Ocky K.; Dijkhuizen, Lubbert; Natalia, Dessy; van der Maarel, Marc J. E. C.

    2017-01-01

    α-Amylases are glycoside hydrolase enzymes that act on the α(1→4) glycosidic linkages in glycogen, starch, and related α-glucans, and are ubiquitously present in Nature. Most α-amylases have been classified in glycoside hydrolase family 13 with a typical (β/α)8-barrel containing two aspartic acid and one glutamic acid residue that play an essential role in catalysis. An atypical α-amylase (BmaN1) with only two of the three invariant catalytic residues present was isolated from Bacillus megaterium strain NL3, a bacterial isolate from a sea anemone of Kakaban landlocked marine lake, Derawan Island, Indonesia. In BmaN1 the third residue, the aspartic acid that acts as the transition state stabilizer, was replaced by a histidine. Three-dimensional structure modeling of the BmaN1 amino acid sequence confirmed the aberrant catalytic triad. Glucose and maltose were found as products of the action of the novel α-amylase on soluble starch, demonstrating that it is active in spite of the peculiar catalytic triad. This novel BmaN1 α-amylase is part of a group of α-amylases that all have this atypical catalytic triad, consisting of aspartic acid, glutamic acid and histidine. Phylogenetic analysis showed that this group of α-amylases comprises a new subfamily of the glycoside hydrolase family 13. PMID:28287181

  16. A new antifungal eudesmanolide glycoside isolated from Sphaeranthus indicus Linn. (Family Compositae).

    PubMed

    Mishra, Bhuwan B; Kishore, Navneet; Tiwari, Vinod K

    2016-03-08

    A new antifungal eudesmanolide glycoside 11,13-dihydro-3-O-(β-digitoxopyranose)-7α-hydroxy eudasman-6,12-olide (2) in addition to known compounds 1 and 3, has been isolated from Sphaeranthus indicus Linn. Its structure was determined by spectral analysis (UV, IR, 1D and 2D NMR and mass spectrum).

  17. Enhanced profiling of flavonol glycosides in the fruits of sea buckthorn (Hippophae rhamnoides).

    PubMed

    Fang, Rui; Veitch, Nigel C; Kite, Geoffrey C; Porter, Elaine A; Simmonds, Monique S J

    2013-04-24

    Use of enhanced LC-MS/MS methods to identify common glycosyl groups of flavonoid glycosides enabled better characterization of the flavonoids in fruits of sea buckthorn (Hippophae rhamnoides). The saccharide moieties of 48 flavonol O-glycosides detected in a methanol extract were identified by these methods. Several of the flavonol glycosides were acylated, two of which were isolated and found to be new compounds. Their structures were determined using spectroscopic and chemical methods as isorhamnetin 3-O-(6-O-E-sinapoyl-β-D-glucopyranosyl)-(1→2)-β-D-glucopyranoside-7-O-α-L-rhamnopyranoside (24) and isorhamnetin 3-O-(6-O-E-feruloyl-β-D-glucopyranosyl)-(1→2)-β-D-glucopyranoside-7-O-α-L-rhamnopyranoside (30). Analysis of the acylated glycosyl groups of 24 and 30 by serial mass spectrometry provided evidence to suggest the acylation position of 11 other minor flavonol glycosides acylated with hydroxycinnamic or hydroxybenzoic acids. The nitric oxide scavenging activities of 24 and 30 were compared with those of other flavonoids and with ascorbic acid and the potassium salt of 2-(4-carboxyphenyl)-4,5-dihydro-4,4,5,5-tetramethyl-1H-imidazolyl-1-oxy-3-oxide (carboxy-PTIO).

  18. Acetylated Triterpene Glycosides and Their Biological Activity from Holothuroidea Reported in the Past Six Decades

    PubMed Central

    Bahrami, Yadollah; Franco, Christopher M. M.

    2016-01-01

    Sea cucumbers have been valued for many centuries as a tonic and functional food, dietary delicacies and important ingredients of traditional medicine in many Asian countries. An assortment of bioactive compounds has been described in sea cucumbers. The most important and abundant secondary metabolites from sea cucumbers are triterpene glycosides (saponins). Due to the wide range of their potential biological activities, these natural compounds have gained attention and this has led to their emergence as high value compounds with extended application in nutraceutical, cosmeceutical, medicinal and pharmaceutical products. They are characterized by bearing a wide spectrum of structures, such as sulfated, non-sulfated and acetylated glycosides. Over 700 triterpene glycosides have been reported from the Holothuroidea in which more than 145 are decorated with an acetoxy group having 38 different aglycones. The majority of sea cucumber triterpene glycosides are of the holostane type containing a C18 (20) lactone group and either Δ7(8) or Δ9(11) double bond in their genins. The acetoxy group is mainly connected to the C-16, C-22, C-23 and/or C-25 of their aglycone. Apparently, the presence of an acetoxy group, particularly at C-16 of the aglycone, plays a significant role in the bioactivity; including induction of caspase, apoptosis, cytotoxicity, anticancer, antifungal and antibacterial activities of these compounds. This manuscript highlights the structure of acetylated saponins, their biological activity, and their structure-activity relationships. PMID:27527190

  19. Synthesis and structure-activity relationship of oleanolic mono- or di-glycosides against Magnaporthe oryzae.

    PubMed

    Huo, G; Liu, C; Hui, Y; Chen, X; Xiao, D

    2016-09-23

    Saponins are naturally-occurring units with broad diversity and are usually recognized as phytoanticipins. In order to develop new saponin chemical entities with high activity against Magnaporthe oryzae, we selected oleanolic acid (OA), which has wide natural distribution and rich content in plants. We used the ability of OA to act as an aglycone for glycosylation to obtain information on the structure-activity relationship (SAR) for rational molecular pesticide design. Oleanolic mono- or di-glycosides were synthesized at either the C3-hydroxy and/or C28-carboxyl position, using trichloroacetimidate or glycosyl bromide donors, respectively. Structures were confirmed by [(1)H]-,[(13)C]-NMR. Furthermore, the activity of the synthesized glycosides against M. oryzae was assessed in vitro, based on the mycelium growth rate. The twenty five oleanolic mono- or di-glycosides comprised fourteen saponins with 3-monosaccharide residue 1a-1n, six saponins with 28-monosaccharide residue 2a-2f, and five saponins with 3, 28-monosaccharide residue 3a-3e; all showed different activities against M. oryzae according to their different structures. We concluded that the optimal oleanolic mono- and di-glycoside structure for activity against M. oryzae is a C3 connection of a hexose such as mannose, galactose, or glucose, in combination with a C28 connection to a small group such as allyl or a C3 connection to a pentose accompanied by a larger group such as another pentose or heptenyl at C28.

  20. Dauricoside, a new glycosidal alkaloid having an inhibitory activity against blood-platelet aggregation.

    PubMed

    Hu, S M; Xu, S X; Yao, X S; Cui, C B; Tezuka, Y; Kikuchi, T

    1993-10-01

    Dauricoside (1), a new glycosidal alkaloid, was isolated from the rhizomes of Menispermum dauricum DC. along with dauricine (2), daurisoline (3), dauriporphine (4), menisporphine (5), and 6-O-demethylmenisporphine (6), and its structure was determined by means of spectroscopic methods. Compounds 1, 2, and 3 inhibited blood-platelet aggregation induced by adenosine 5'-diphosphate (ADP).

  1. Method validation of a survey of thevetia cardiac glycosides in serum samples.

    PubMed

    Kohls, Sarah; Scholz-Böttcher, Barbara; Rullkötter, Jürgen; Teske, Jörg

    2012-02-10

    A sensitive and specific liquid chromatography tandem mass spectrometry (HPLC-ESI(+)-MS/MS) procedure was developed and validated for the identification and quantification of thevetin B and further cardiac glycosides in human serum. The seeds of Yellow Oleander (Thevetia peruviana) contain cardiac glycosides that can cause serious intoxication. A mixture of six thevetia glycosides was extracted from these seeds and characterized. Thevetin B, isolated and efficiently purified from that mixture, is the main component and can be used as evidence. Solid phase extraction (SPE) proved to be an effective sample preparation method. Digoxin-d3 was used as the internal standard. Although ion suppression occurs, the limit of detection (LOD) is 0.27 ng/ml serum for thevetin B. Recovery is higher than 94%, and accuracy and precision were proficient. Method refinement was carried out with regard to developing a general screening method for cardiac glycosides. The assay is linear over the range of 0.5-8 ng/ml serum. Finally, the method was applied to a case of thevetia seed ingestion.

  2. Medicinal flowers. XXX. Eight new glycosides, everlastosides F-M, from the flowers of Helichrysum arenarium.

    PubMed

    Morikawa, Toshio; Wang, Li-Bo; Ninomiya, Kiyofumi; Nakamura, Seikou; Matsuda, Hisashi; Muraoka, Osamu; Wu, Li-Jun; Yoshikawa, Masayuki

    2009-08-01

    Eight new glycosides, everlastosides F (1), G (2), H (3), I (4), J (5), K (6), L (7), and M (8), were isolated from the methanolic extract of the flowers of Helichrysum arenarium. Their structures were elucidated on the basis of chemical and physicochemical evidence.

  3. Rehabilitation of faulty kinetic determinations and misassigned glycoside hydrolase family of retaining mechanism ß-xylosidases

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We obtained Cx1 from a commercial supplier, whose catalog listed it as a ß-xylosidase of glycoside hydrolase family 43. NMR experiments indicate retention of anomeric configuration in its reaction stereochemistry, opposing the assignment of GH43, which follows an inverting mechanism. Partial protein...

  4. A new group of glycoside hydrolase family 13 α-amylases with an aberrant catalytic triad.

    PubMed

    Sarian, Fean D; Janeček, Štefan; Pijning, Tjaard; Ihsanawati; Nurachman, Zeily; Radjasa, Ocky K; Dijkhuizen, Lubbert; Natalia, Dessy; van der Maarel, Marc J E C

    2017-03-13

    α-Amylases are glycoside hydrolase enzymes that act on the α(1→4) glycosidic linkages in glycogen, starch, and related α-glucans, and are ubiquitously present in Nature. Most α-amylases have been classified in glycoside hydrolase family 13 with a typical (β/α)8-barrel containing two aspartic acid and one glutamic acid residue that play an essential role in catalysis. An atypical α-amylase (BmaN1) with only two of the three invariant catalytic residues present was isolated from Bacillus megaterium strain NL3, a bacterial isolate from a sea anemone of Kakaban landlocked marine lake, Derawan Island, Indonesia. In BmaN1 the third residue, the aspartic acid that acts as the transition state stabilizer, was replaced by a histidine. Three-dimensional structure modeling of the BmaN1 amino acid sequence confirmed the aberrant catalytic triad. Glucose and maltose were found as products of the action of the novel α-amylase on soluble starch, demonstrating that it is active in spite of the peculiar catalytic triad. This novel BmaN1 α-amylase is part of a group of α-amylases that all have this atypical catalytic triad, consisting of aspartic acid, glutamic acid and histidine. Phylogenetic analysis showed that this group of α-amylases comprises a new subfamily of the glycoside hydrolase family 13.

  5. A Review on the pharmacology and toxicology of steviol glycosides extracted from Stevia rebaudiana.

    PubMed

    Momtazi-Borojeni, Amir Abbas; Esmaeili, Seyed-Alireza; Abdollahi, Elham; Sahebkar, Amirhossein

    2016-10-21

    Stevia rebaudiana Bertoni is a sweet and nutrient-rich plant belonging to the Asteraceae family. Stevia leaves contain steviol glycosides including stevioside, rebaudioside (A to F), steviolbioside, and isosteviol, which are responsible for the plant's sweet taste, and have commercial value all over the world as a sugar substitute in foods, beverages and medicines. Among the various steviol glycosides, stevioside, rebaudioside A and rebaudioside C are the major metabolites and these compounds are on average 250-300 times sweeter than sucrose. Steviol is the final product of Stevia metabolism. The metabolized components essentially leave the body and there is no accumulation. Beyond their value as sweeteners, Stevia and its glycosdies possess therapeutic effects against several diseases such as cancer, diabetes mellitus, hypertension, inflammation, cystic fibrosis, obesity and tooth decay. Studies have shown that steviol glycosides found in Stevia are not teratogenic, mutagenic or carcinogenic and cause no acute and subacute toxicity. The present review provides a summary on the biological and pharmacological properties of steviol glycosides that might be relevant for the treatment of human diseases.

  6. Enhancement of production of eugenol and its glycosides in transgenic aspen plants via genetic engineering.

    PubMed

    Koeduka, Takao; Suzuki, Shiro; Iijima, Yoko; Ohnishi, Toshiyuki; Suzuki, Hideyuki; Watanabe, Bunta; Shibata, Daisuke; Umezawa, Toshiaki; Pichersky, Eran; Hiratake, Jun

    2013-06-21

    Eugenol, a volatile phenylpropene found in many plant species, exhibits antibacterial and acaricidal activities. This study attempted to modify the production of eugenol and its glycosides by introducing petunia coniferyl alcohol acetyltransferase (PhCFAT) and eugenol synthase (PhEGS) into hybrid aspen. Gas chromatography analyses revealed that wild-type hybrid aspen produced small amount of eugenol in leaves. The heterologous overexpression of PhCFAT alone resulted in up to 7-fold higher eugenol levels and up to 22-fold eugenol glycoside levels in leaves of transgenic aspen plants. The overexpression of PhEGS alone resulted in a subtle increase in either eugenol or eugenol glycosides, and the overexpression of both PhCFAT and PhEGS resulted in significant increases in the levels of both eugenol and eugenol glycosides which were nonetheless lower than the increases seen with overexpression of PhCFAT alone. On the other hand, overexpression of PhCFAT in transgenic Arabidopsis and tobacco did not cause any synthesis of eugenol. These results indicate that aspen leaves, but not Arabidopsis and tobacco leaves, have a partially active pathway to eugenol that is limited by the level of CFAT activity and thus the flux of this pathway can be increased by the introduction of a single heterologous gene.

  7. Improvement of pseudojujubogenin glycosides production from regenerated Bacopa monnieri (L.) Wettst. and enhanced yield by elicitors.

    PubMed

    Kamonwannasit, Sirilak; Phrompittayarat, Watoo; Ingkaninan, Kornkanok; Tanaka, Hiroyuki; Putalun, Waraporn

    2008-01-01

    Bacopa monnieri (L.) Wettst. was studied for shoot induction and regeneration on Murashige and Skoog (MS) medium supplemented with different plant growth regulators. Stem explants cultured on medium containing 0.1 mg/l thidiazuron (TDZ) resulted in the highest number of shoots (117 shoots/explant). Regenerated plants from medium with 0.5 mg/l TDZ contained the highest level of pseudojujubogenin glycosides [(30.62 +/- 1.29) mg/g dry wt] which was 2-fold higher than that of in vitro grown plants of the same age [(16.96 +/- 1.49) mg/g dry wt]. Plantlets regenerated from 0.1 mg/l TDZ also showed a high level of pseudojujubogenin glycosides [(27.94 +/- 1.19) mg/g dry wt]. The effect of elicitor on pseudojujubogenin glycosides accumulation in B. monnieri whole plant cultures was investigated. Chitosan at 150 mg/l and yeast extract at 2 mg/ml increased the pseudojujubogenin glycosides production [(40.83 +/- 2.24) mg/g dry wt and (40.05 +/- 2.37) mg/g dry wt, respectively] after 7 days, which was 6-fold higher than in the control cultures.

  8. Two new sesquiterpene glycosides isolated from the fresh needles of Pinus massoniana Lamb.

    PubMed

    Xiao, Yun-Chuan; Ye, Liang; Zhao, Man-Xi; Yan, Cui-Qi; Wang, Wei; Huang, Quan-Shu; Liang, Kai; Meng, Bao-Hua; Ke, Xiao

    2017-02-01

    Two new sesquiterpene glycosides, namely massonside A (1) and massonside B (2), were isolated from the n-Bu extract of the fresh needles of Pinus massoniana Lamb. Their structures were established by 1D, 2D nuclear magnetic resonance and high-resolution mass spectrometry. Their biological activities were profiled by the anti-HBV and anti-HCV assays.

  9. Ruthenium catalyzed synthesis of 2,3-unsaturated C-glycosides from glycals.

    PubMed

    Srinivas, Batthula; Reddy, Thurpu Raghavender; Kashyap, Sudhir

    2015-04-10

    A highly efficient and convenient C-glycosylation method was developed using ruthenium(III) chloride for the synthesis of 2,3-unsaturated C-glycosides. Various nucleophiles such as allyl trimethylsilane, triethylsilane, trimethylsilyl cyanide, trimethylsilyl azide and heterocycles such as thiophene and furan reacted smoothly with glycals in the presence of catalytic amount of ruthenium trichloride under mild reaction conditions.

  10. Theoretical Calculation of Electronic Circular Dichroism of a Hexahydroxydiphenoyl-Containing Flavanone Glycoside

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Time-dependent density functional theory (TDDFT) was employed for theoretical calculation of electronic circular dichroism (ECD) of a hexahydroxydiphenoyl (HHDP)-containing flavanone glycoside, mattucinol-7-O-[4'',6''-O-(aS)-hexahydroxydiphenoyl]-ß-d-glucopyranoside (2). It identified the roles of t...

  11. Two new C21 steroidal glycosides from Marsdenia tenacissima (ROXB.) WIGHT et ARN.

    PubMed

    Wang, Shu; Lai, Yu-Han; Tian, Bao; Yang, Lin

    2006-05-01

    Two new C(21) steroidal glycosides, tenacissoside L (1), tenacissoside M (2), were isolated from the stems of Marsdenia tenacissima (ROXB.) WIGHT et ARN. Their structures were elucidated, respectively, by means of chemical and spectral data, including ESI-MS, HR-ESI-MS, 1D-NMR and 2D-NMR.

  12. Effect of different drying methods on the composition of steviol glycosides in Stevia rebaudiana Bertoni leaves

    NASA Astrophysics Data System (ADS)

    Aranda-González, Irma; Betancur-Ancona, David; Chel-Guerrero, Luis; Moguel-Ordóñez, Yolanda

    2017-01-01

    Drying techniques can modify the composition of certain plant compounds. Therefore, the aim of the study was to assess the effect of different drying methods on steviol glycosides in Stevia rebaudiana Bertoni leaves. Four different drying methods were applied to Stevia rebaudiana Bertoni leaves, which were then subjected to aqueous extraction. Radiation or convection drying was performed in stoves at 60°C, whereas shade or sun drying methods were applied at 29.7°C and 70% of relative humidity. Stevioside, rebaudioside A, rebaudioside B, rebaudioside C, rebaudioside D, dulcoside A, and steviolbioside were quantified by a validated HPLC method. Among steviol glycosides, the content (g 100 g-1 dry basis) of stevioside, rebaudioside A, rebaudioside B, and rebaudioside C varied according to the drying method. The total glycoside content was higher in sun-dried samples, with no significant differences compared to shade or convection drying, whereas radiation drying adversely affected the content of rebaudioside A and rebaudioside C (p <0.01) and was therefore a method lowering total glycoside content. The effect of the different drying methods was also reflected in the proportion of the sweetener profile. Convection drying could be suitable for modern food processing industries while shadow or sun drying may be a low-cost alternative for farmers.

  13. Utilisation of steviol glycosides from Stevia rebaudiana (Bertoni) by lactobacilli and bifidobacteria in in vitro conditions.

    PubMed

    Kunová, Gabriela; Rada, Vojtěch; Vidaillac, Adrien; Lisova, Ivana

    2014-05-01

    In the current study, eight strains of bifidobacteria and seven strains of lactobacilli were tested for their ability to grow in the presence of rebaudioside A and steviol glycosides from the sweetener Natusweet M001 originating from herb Stevia rebaudiana (Bertoni). Stevia is gaining popularity as a natural, non-caloric sugar substitute, and recently, it was allowed as a food additive by European Union too. Utilisation of steviol glycosides by intestinal microbiota suggests that they might have potential prebiotic effect. Based on the evaluation of bacterial density and pH values in our in vitro study, it was found that lactobacilli and bifidobacteria tested were able to utilise steviol glycosides as a carbon source only to a very limited extent. All strains tested showed significantly lower change in the absorbance A540 (P < 0.05) and pH decrease of the growth media as compared with the positive controls (medium containing glucose as a carbon source and de Man Rogosa Sharpe broth). We concluded that a suggested prebiotic effect was not confirmed either in the case of rebaudioside A or in the case of the sweetener Natusweet M001 containing a mixture of steviol glycosides.

  14. Carotenoid glycosides from cyanobacteria are teratogenic in the zebrafish (Danio rerio) embryo model.

    PubMed

    Jaja-Chimedza, Asha; Sanchez, Kristel; Gantar, Miroslav; Gibbs, Patrick; Schmale, Michael; Berry, John P

    2017-05-01

    Toxigenicity of cyanobacteria is widely associated with production of several well-described toxins that pose recognized threats to human and ecosystem health as part of both freshwater eutrophication, and episodic blooms in freshwater and coastal habitats. However, a preponderance of evidence indicates contribution of additional bioactive, and potentially toxic, metabolites. In the present study, the zebrafish (Danio rerio) embryo was used as a model of vertebrate development to identify, and subsequently isolate and characterize, teratogenic metabolites from two representative strains of C. raciborskii. Using this approach, three chemically related carotenoids - and specifically the xanthophyll glycosides, myxol 2'-glycoside (1), 4-ketomyxol 2'-glycoside (2) and 4-hydroxymyxol 2'-glycoside (3) - which are, otherwise, well known pigment molecules from cyanobacteria were isolated as potently teratogenic compounds. Carotenoids are recognized "pro-retinoids" with retinoic acid, as a metabolic product of the oxidative cleavage of carotenoids, established as both key mediator of embryo development and, consequently, a potent teratogen. Accordingly, a comparative toxicological study of chemically diverse carotenoids, as well as apocarotenoids and retinoids, was undertaken. Based on this, a working model of the developmental toxicity of carotenoids as pro-retinoids is proposed, and the teratogenicity of these widespread metabolites is discussed in relation to possible impacts on aquatic vertebrate populations.

  15. High-Throughput In Vitro Glycoside Hydrolase (HIGH) Screening for Enzyme Discovery

    SciTech Connect

    Kim, Tae-Wan; Chokhawala, Harshal A.; Hess, Matthias; Dana, Craig M.; Baer, Zachary; Sczyrba, Alexander; Rubin, Edward M.; Blanch, Harvey W.; Clark, Douglas S.

    2011-09-16

    A high-throughput protein-expression and screening method (HIGH method, see picture) provides a rapid approach to the discovery of active glycoside hydrolases in environmental samples. Finally, HIGH screening combines cloning, protein expression, and enzyme hydrolysis in one pot; thus, the entire process from gene expression to activity detection requires only three hours.

  16. DFT STUDY OF ALPHA-MALTOSE: INFLUENCE OF HYDROXYL ORIENTATIONS ON THE GLYCOSIDIC BOND

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The result of DFT geometry optimization of 68 unique alpha-maltose conformers at the B3LYP/6-311++G** level of theory is described. Particular attention is paid to the hydroxyl group rotational positions and their influence on the glycosidic bond dihedral angles. The orientation of lone pair elect...

  17. Anti-hepatitis B virus activities and absolute configurations of sesquiterpenoid glycosides from Phyllanthus emblica.

    PubMed

    Lv, Jun-Jiang; Wang, Ya-Feng; Zhang, Jing-Min; Yu, Shan; Wang, Dong; Zhu, Hong-Tao; Cheng, Rong-Rong; Yang, Chong-Ren; Xu, Min; Zhang, Ying-Jun

    2014-11-21

    During the process exploring anti-viral compounds from Phyllanthus species, eight new highly oxygenated bisabolane sesquiterpenoid glycoside phyllaemblicins G1–G8 (1–8) were isolated from Phyllanthus emblica, along with three known compounds, phyllaemblicin F (9), phyllaemblic acid (10) and glochicoccin D (11). Phyllaemblicin G2 (2), bearing a tricyclo [3.1.1.1] oxygen bridge ring system, is an unusual sesquiterpenoid glycoside, while phyllaemblicins G6–G8 (6–8) are dimeric sesquiterpenoid glycosides with two norbisabolane units connecting through a disaccharide. All the structures were elucidated by the extensive analysis of HRMS and NMR data. The relative configuration of phyllaemblicin G2 was constructed based on heteronuclear coupling constants measurement, and the absolute configurations for all new compounds were established by calculated electronic circular dichroism (ECD) using time dependent density functional theory. The sesquiterpenoid glycoside dimers 6–9 displayed potential anti-hepatitis B virus (HBV) activities, especially for the new compound 6 with IC50 of 8.53 ± 0.97 and 5.68 ± 1.75 μM towards the HBV surface antigen (HBsAg) and HBV excreted antigen (HBeAg) secretion, respectively.

  18. Differential El Ion Fragmentation Pathways for Peracetylated C-Glycoside Ketals

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Aqueous-based Knoevenagel condensation of sugars with beta-diketones is a useful method for preparing beta-C-glycoside ketones. A mechanism has been proposed in which C-C bond formation between the anomeric sugar carbon and the bridged methylene of the diketone is followed by beta-elimination of wa...

  19. Triterpene glycosides from the sea cucumber Cladolabes schmeltzii. II. Structure and biological action of cladolosides A1-A6 .

    PubMed

    Silchenko, Alexandra S; Kalinovsky, Anatoly I; Avilov, Sergey A; Andryjaschenko, Pelageya V; Dmitrenok, Pavel S; Yurchenko, Ekaterina A; Dolmatov, Igor Yu; Savchenko, Alexander M; Kalinin, Vladimir I

    2014-10-01

    Six new triterpene glycosides, cladolosides Al-A6 (1-6), have been isolated from the Vietnamese sea cucumber Cladolabes schmeltzii (Cladolabinae, Sclerodactylidae, Dendrochirotida). Structures of the glycosides were elucidated by 2D NMR spectroscopy and MS. All the glycosides have nonsulfated tetrasaccharide linear carbohydrate moieties. Glycoside 6 has a glucose residue as the third monosaccharide unit, while the rest of the compounds comprise a xylose in this postion of the carbohydrate chain. Glycosides 1-6 differ from each other in the structures of their holostane aglycones. Cytotoxic activities of glycosides 1-6 were studied against mouse spleenocytes, along with hemolytic activities against mouse erythrocytes. All the compounds, except cladoloside A5 (5) posessing a hydroxy-group in the aglycone side chain, demonstrated rather strong cytotoxic and hemolytic effects. The most active glycosides were cladolosides A1 (1) and A2 (2) having two O-acetic groups and the xylose residue in the third position of the sugar chain.

  20. Neuraminidase-resistant hemagglutination inhibitors: acrylamide copolymers containing a C-glycoside of N-acetylneuraminic acid.

    PubMed

    Sparks, M A; Williams, K W; Whitesides, G M

    1993-03-19

    Copolymers consisting of a polyacrylamide backbone with side chains terminated in C-glycosidic analogs of N-acetylneuraminic acid were synthesized by free radical copolymerization of alpha-2-C-[3-[[2-(N-acryloylamino)ethyl]thio]propyl]-N- acetylneuraminic acid (5) with acrylamide. Unlike natural and synthetic polyvalent materials that contain N-acetylneuraminic acid in O-glycosidic form, these C-glycosidic copolymers resist neuraminidase-catalyzed cleavage of the neuraminic acid residue from the copolymer backbone. Examination of these C-glycosidic copolymers in a hemagglutination inhibition assay indicated that they are as effective in vitro as polyvalent O-glycosidic copolymers in inhibiting agglutination of erythrocytes by influenza virus. The minimum value of the inhibition constant, calculated on the basis of the concentration of Neu5Ac groups in solution, is Ki(HAI) approximately 10(-7) M for both copolymers. The inhibitory potency of the C-glycoside-based copolymers becomes more significant at lower concentrations of Neu5Ac moieties in solution than does the inhibitory potency of the O-glycoside-based copolymer.