RESUMO
Two new dihydroisochromenes, named seimisochromenes A and B (1 and 2), were isolated from an endophytic fungus, Seimatosporium sp. The structures of seimisochromenes A and B have been determined from 1D ((1)H and (13)C NMR spectra) and 2D (COSY, HMQC, HMBC, and NOESY) NMR experiments.
Assuntos
Benzopiranos/isolamento & purificação , Xylariales/química , Benzopiranos/química , Estrutura Molecular , Ressonância Magnética Nuclear BiomolecularRESUMO
Phytochemical investigation of the endophytic fungus Coniothyrium sp. resulted in the isolation of a new phenoxyphenyl ether, named coniothyren (1), and two known compounds, coniol (2) and (+)-epoxydon (3). The structure of the new compound was elucidated by detailed spectroscopic analysis, namely, (1)H NMR, (13)C NMR, COSY, HMQC, HMBC, and HR-EI-MS. Preliminary studies demonstrated that (+)-epoxydon (3) displayed good antibacterial and antialgal activities toward Bacillus megaterium and Chlorella fusca, respectively.
Assuntos
Antibacterianos/isolamento & purificação , Ascomicetos/química , Éteres/isolamento & purificação , Éteres Fenílicos/isolamento & purificação , Antibacterianos/química , Antibacterianos/farmacologia , Éteres/química , Éteres/farmacologia , Estrutura Molecular , Ressonância Magnética Nuclear Biomolecular , Éteres Fenílicos/química , Éteres Fenílicos/farmacologiaRESUMO
Four known hydroxyanthraquinones (1-4) together with four new derivatives having a tetralone moiety, namely coniothyrinones A-D (5-8), were isolated from the culture of Coniothyrium sp., an endophytic fungus isolated from Salsola oppostifolia from Gomera in the Canary Islands. The structures of the new compounds were elucidated by detailed spectroscopic analysis and comparison with reported data. The absolute configurations of coniothyrinones A (5), B (6), and D (8) were determined by TDDFT calculations of CD spectra, allowing the determination of the absolute configuration of coniothyrinone C (7) as well. Coniothyrinones A (5), B (6), and D (8) could be used as ECD reference compounds in the determination of absolute configuration for related tetralone derivatives. This is the first report of anthraquinones and derivatives from an isolate of the genus Coniothyrium sp. These compounds showed inhibitory effects against the fungus Microbotryum violaceum, the alga Chlorella fusca, and the bacteria Escherichia coli and Bacillus megaterium.
Assuntos
Antraquinonas/química , Antibacterianos/química , Antifúngicos/química , Ascomicetos/química , Endófitos/química , Antraquinonas/farmacologia , Antibacterianos/farmacologia , Antifúngicos/farmacologia , Chlorella/efeitos dos fármacos , Modelos Moleculares , Conformação Molecular , EstereoisomerismoRESUMO
Two polyketides, cryptosporiopsin A (1) and hydroxypropan-2',3'-diol orsellinate (3), and a natural cyclic pentapeptide (4), together with two known compounds were isolated from the culture of Cryptosporiopsis sp., an endophytic fungus from leaves and branches of Zanthoxylum leprieurii (Rutaceae). The structures of these metabolites were elucidated on the basis of their spectroscopic and spectrometric data. Cryptosporiopsin A and the other metabolites exhibited motility inhibitory and lytic activities against zoospores of the grapevine downy mildew pathogen Plasmopara viticola at 10-25µg/mL. In addition, the isolated compounds displayed potent inhibitory activity against mycelial growth of two other peronosporomycete phytopathogens, Pythium ultimum, Aphanomyces cochlioides and a basidiomycetous fungus Rhizoctonia solani. Weak cytotoxic activity on brine shrimp larvae was observed.
Assuntos
Aphanomyces/efeitos dos fármacos , Artemia/efeitos dos fármacos , Ascomicetos/química , Peptídeos Cíclicos/farmacologia , Policetídeos/farmacologia , Pythium/efeitos dos fármacos , Zanthoxylum/química , Animais , Aphanomyces/crescimento & desenvolvimento , Ascomicetos/metabolismo , Conformação Molecular , Peptídeos Cíclicos/química , Peptídeos Cíclicos/metabolismo , Folhas de Planta/química , Folhas de Planta/metabolismo , Policetídeos/química , Policetídeos/metabolismo , Pythium/crescimento & desenvolvimento , Relação Estrutura-Atividade , Zanthoxylum/metabolismoRESUMO
Two new acaranoic acids, named seimatoporic acid A and B (1, and 2), together with six known compounds, R-(-)-mellein (3), cis-4-hydroxymellein (4), trans-4-hydroxymellein (5), 4R-hydroxy-5-methylmellein (6), (-)-5-hydroxymethylmellein (7), and ergosterol (8) were isolated from an endophytic fungus, Seimatosporium sp, by a bioassay-guided procedure. The structures of the new compounds have been assigned from analysis of the 1H and 13C NMR spectra, DEPT, and by 2D COSY, HMQC, HMBC and NOESY experiments. A mixture of compounds 1 and 2 showed strong antifungal activity against Botrytis cinerea, Septoria tritici, and Pyricularia oryzae.
Assuntos
Anti-Infecciosos/isolamento & purificação , Isocumarinas/química , Isocumarinas/isolamento & purificação , Xylariales/química , Endófitos/química , Endófitos/metabolismo , Epilobium/microbiologia , Testes de Sensibilidade Microbiana , Xylariales/metabolismoRESUMO
Four new pyrenocines, named pyrenocines J-M (1-4), were isolated from an endophytic fungus, Phomopsis sp, by a bioassay-guided method. The structures of the new compound have been assigned from ¹H and ¹³C NMR spectra, DEPT, and by 2D COSY, HMQC, and HMBC experiments. Preliminary studied showed that compounds 1, 2 and 4 showed good antifungal, antibacterial, and algicidal properties, while compound 3 had good antibacterial and algicidal properties.
Assuntos
Acroleína/farmacologia , Anti-Infecciosos/farmacologia , Ascomicetos/química , Produtos Biológicos/farmacologia , Pironas/farmacologia , Acroleína/análogos & derivados , Acroleína/química , Acroleína/isolamento & purificação , Anti-Infecciosos/química , Anti-Infecciosos/isolamento & purificação , Produtos Biológicos/química , Endófitos/química , Estrutura Molecular , Pironas/química , Pironas/isolamento & purificaçãoRESUMO
Chromatographic purification of the extract of an endophytic fungal culture yielded depsitinuside (1), a new phenolic ester together with ergosterol (2) and (22E,24S)-24-methyl-5-α-cholesta-7,22-diene-3ß,5,6ß-triol (3). The structure of 1 was elucidated based on 1D, 2D NMR spectroscopy and high-resolution mass spectrometry, whereas the known compounds (2 and 3) were identified by (1)H NMR, mass spectrometry, and in comparison with the literature values. Compound 1 was evaluated for its enzyme inhibitory potential against acetylcholinesterase, butyrylcholinesterase and lipoxygenase, and was found inactive (10%-40% inhibition at a concentration of 2 mg/ml).
Assuntos
Ascomicetos/química , Depsídeos/isolamento & purificação , Galactosídeos/isolamento & purificação , Depsídeos/química , Galactosídeos/química , Estrutura Molecular , Ressonância Magnética Nuclear Biomolecular , Paquistão , Viburnum/microbiologiaRESUMO
Cytospolides F-Q (6-17) and decytospolides A and B (18 and 19), 14 unusual nonanolide derivatives, were isolated from Cytospora sp., an endophytic fungus from Ilex canariensis. The structures were elucidated by means of detailed spectroscopic analysis, chemical interconversion, and X-ray single crystal diffraction. The solution- and solid-state conformers were compared by the combination of experimental methods (X-ray, NMR) supported by DFT calculations of the conformers. Absolute configurations were assigned using the modified Mosher's method and solution- and solid-state TDDFT ECD calculations. In an in vitro cytotoxicity assay toward the tumor cell lines of A549, HCT116, QGY, A375, and U973, the γ-lactone 17 demonstrated a potent growth inhibitory activity toward the cell line A-549, while nonanolide 16 with (2S) configuration showed the strongest activity against cell lines A-549, QGY, and U973. A cell cycle analysis indicated that compound 16 can significantly mediate G1 arrest in A549 tumor cells, confirming the important role of the C-2 methyl in the growth inhibition toward the tumor line. The discovery of an array of new nonanolides demonstrates the productivity of the fungus, and it is an example of chemical diversity, extending the nonanolide family by derivatives formed by ring cleavage, oxidation, esterification, and Michael addition.
Assuntos
Ascomicetos/química , Lactonas/química , Cristalografia por Raios X , Modelos Moleculares , Conformação Molecular , EstereoisomerismoRESUMO
Massarigenin A (1) and papyracillic acids A (2) and B (3) were isolated from the endophytic fungus Microsphaeropsis sp. Their structures were elucidated by multidimensional nuclear magnetic resonance spectroscopy; the structure of massarigenin A (1) was also confirmed by X-ray crystallography. The absolute configuration of massarigenin A (1) was established by means of circular dichroism (CD) spectroscopy and time-dependent density functional theory (TDDFT) calculations. The impact of intermolecular hydrogen bonds detected in the crystal packing of 1 on CD spectra measured in the solid state was also investigated.
Assuntos
Dicroísmo Circular/métodos , Fungos/química , Fungos/metabolismo , Lactonas/química , Compostos de Espiro/química , Cristalografia por Raios X , Ligação de Hidrogênio , Lactonas/isolamento & purificação , Espectroscopia de Ressonância Magnética , Estrutura Molecular , Compostos de Espiro/isolamento & purificaçãoRESUMO
Two new benzyl gamma-butyrolactone analogues, (R)-5-((S)-hydroxy(phenyl)-methyl)dihydrofuran-2(3H)-one (1) and its 6-acetate (2), and a new naphthalenone derivative (8), together with eight additional known aromatic derivatives, (S)-5-((S)-hydroxy(phenyl)-methyl)dihydrofuran-2(3H)-one (3), (S)-5-benzyl-dihydrofuran-2(3H)-one (4), 5-phenyl-4-oxopentanoic acid (5), gamma-oxo-benzenepentanoic acid methyl ester (6), 3-(2,5-dihydro-4-hydroxy-5-oxo-3-phenyl-2-furyl)propionic acid (7), (3R)-5-methylmellein (9), integracins A (10) and B (11) were isolated from Cytospora sp., an endophytic fungus isolated from Ilex canariensis from Gomera. The structures of these compounds were elucidated by detailed spectroscopic analysis, comparison with reported data, and chemical interconversion. The absolute configurations of the new compounds (1, 2, 8) were established on the basis of optical rotation or CD spectra analysis. Preliminary studies showed antimicrobial activity of these compounds against the fungi Microbotryum violaceum, Botrytis cinerea and Septoria tritici, the alga Chlorella fusca, and the bacterium Bacillus megaterium.
Assuntos
Anti-Infecciosos/análise , Ascomicetos/química , Furanos/isolamento & purificação , Furanos/química , Ilex/microbiologia , Testes de Sensibilidade Microbiana , Estrutura MolecularRESUMO
Chemical investigation of the fungal strain Microdiplodia sp. isolated from the shrub Lycium intricatum led to the isolation of four new compounds: a hexahydroxanthone (2), a 2,3-dihydrochroman-4-one (3), a 7-oxoxanthone derivative (4), and a 1,4-oxazepan-7-one (5). The relative configurations of the new compounds were determined by intensive NMR investigations, notably NOESY experiments at different temperatures. The absolute configurations of the well-known fungal metabolite diversonol (1) and of other xanthone derivatives (3, 4) were established by means of TDDFT ECD calculations. Most of the metabolites were biologically active, with antibacterial activity against Legionella pneumophila and/or antifungal activity against Microbotryum violaceum.
Assuntos
Antibacterianos/isolamento & purificação , Antifúngicos/isolamento & purificação , Ascomicetos/química , Xantonas/isolamento & purificação , Antibacterianos/química , Antibacterianos/farmacologia , Antifúngicos/química , Antifúngicos/farmacologia , Bacillus megaterium/efeitos dos fármacos , Basidiomycota/efeitos dos fármacos , Cristalografia por Raios X , Escherichia coli/efeitos dos fármacos , Legionella pneumophila/efeitos dos fármacos , Lycium/microbiologia , Testes de Sensibilidade Microbiana , Estrutura Molecular , Espanha , Xantonas/química , Xantonas/farmacologiaRESUMO
Phomosine K (1), a new phomosine derivative, has been isolated from Phomopsis sp., in addition to six known compounds: phomosine A (2), phenylalanine amide (3), 2-hydroxymethyl-4beta,5alpha,6beta-trihydroxycyclohex-2-en (4), (-)-phyllostine (5), (+)-epiepoxydon (6), and (+)-epoxydon monoacetate (7). Preliminary studies showed that compound 1 had strong antibacterial activity, while compounds 4-7 showed good antifungal, antibacterial, and algicidal properties, except compounds 4 and 6, which lacked antifungal activity.
Assuntos
Anti-Infecciosos/isolamento & purificação , Ascomicetos/metabolismo , Anti-Infecciosos/química , Anti-Infecciosos/farmacologiaRESUMO
From the endophytic fungus Phomosis sp., four known phomosines A-D (1-4) and three new phomosines H-J (5-7) have been isolated. The structures of the new compounds were determined on the basis of their spectroscopic data analysis (1H, 13C, 1H-1H COSY, HMQC, and HMBC NMR, as well as mass spectrometry). The structures of phomosine H (5) and J (7) were also confirmed by semisynthesis from phomosine A (1). The remaining four known compounds [phomosines A-D (1-4)] were identified by comparing their spectroscopic data with those reported in the literature. The four known metabolites were biologically active. Of the novel metabolites, only 6 was antifungal and antibacterial.
Assuntos
Anti-Infecciosos/isolamento & purificação , Ascomicetos/metabolismo , Éteres/isolamento & purificação , Ligustrum/microbiologia , Anti-Infecciosos/farmacologia , Éteres/química , Éteres/farmacologiaRESUMO
The new (22E,24R)-3-acetoxy-19(10-->6)-abeo-ergosta-5,7,9,22-tetraen-3beta-ol (1) and the known (22E,24R)-19(10-->6)-abeo-ergosta-5,7,9,22-tetraen-3beta-ol (2), two interesting ergosteroids with rare aromatized ring B, together with seven known derivatives, namely (22E,24R)-ergosta-5,7,22-trien-3beta-ol (3), (22E,24R)-ergosta-4,7,22-trien-3-one (4), (22E,24R)-ergosta-4,6,8(14),22-tetraen-3-one (5), (22E,24R)-5alpha,8alpha-epidioxyergosta-6,22-dien-3beta-ol (6), (22E,24R)-ergosta-7,22-dien-3beta,5alpha,6beta-triol (7), (22E,24R)-6-acetoxy-ergosta-7,22-dien-3beta,5alpha,6beta-triol (8), and (22E,24R)-3,6-diacetoxy-ergosta-7,22-dien-3beta,5alpha,6beta-triol (9), were isolated from Colletotrichum sp., an endophytic fungus isolated from Ilex canariensis from Gomera. The structures of these compounds were elucidated by detailed spectroscopic analysis, comparison with reported data, and chemical interconversion. The isolation of these metabolites not only displays a beautiful array of chemical diversity, but also gives insight into the biosynthetic interconnections. Preliminary studies showed antimicrobial activity of these compounds against the fungus Microbotryum violaceum, the alga Chlorella fusca, and the bacteria Escherichia coli and Bacillus megaterium.
Assuntos
Colletotrichum/química , Esteroides/química , Acetilação , Antibacterianos/biossíntese , Antibacterianos/química , Antibacterianos/farmacologia , Bactérias/efeitos dos fármacos , Cromatografia em Camada Fina , Meios de Cultura , Eucariotos/efeitos dos fármacos , Fungos/efeitos dos fármacos , Ilex/microbiologia , Espectroscopia de Ressonância Magnética , Testes de Sensibilidade Microbiana , Esteroides/biossíntese , Esteroides/farmacologiaRESUMO
Seven new drimane sesquiterpenoids (1-3, 6-9), along with the known compounds deoxyuvidin B (4), strobilactone B (5), and RES-1149-2 (10), were obtained from cultures of the fungus Aspergillus ustus, which was isolated from the marine sponge Suberites domuncula. Their structures were established by means of spectroscopic analyses including one- and two-dimensional NMR spectroscopy and high-resolution MS. Compounds 6, 7, and 10 showed cytotoxic activity against a panel of tumor cell lines, including L5178Y, HeLa, and PC12 cells, with 7 being the most active (EC(50) against L5178Y cell line: 0.6 microg/mL).
Assuntos
Antineoplásicos/isolamento & purificação , Aspergillus/química , Sesquiterpenos/isolamento & purificação , Animais , Antineoplásicos/química , Antineoplásicos/farmacologia , Ensaios de Seleção de Medicamentos Antitumorais , Células HeLa , Humanos , Biologia Marinha , Estrutura Molecular , Sesquiterpenos Policíclicos , Sesquiterpenos/química , Sesquiterpenos/farmacologia , Suberites/microbiologiaRESUMO
Three new metabolites, microsphaeropsones A-C (1-3) with a unique oxepino[2,3-b]chromen-6-one (ring-enlarged xanthone) skeleton, were isolated from the endophytic fungus Microsphaeropsis species, co-occurring with their putative biogenetic anthraquinoide precursors citreorosein (4) and emodin (5). From another Microsphaeropsis species, large amounts of fusidienol A (8 a), smaller amounts of emodin (5), the known aromatic xanthones 9 a and 9 b, the new 3,4-dihydrofusidienol A (8 b), and the new aromatic xanthone 9 c were isolated. The endophyte Seimatosporium species produced a new aromatic xanthone, seimatoxanthone A (10), and 3,4-dihydroglobosuxanthone A (12), closely related to alpha-diversolonic ester (13) from Microdiplodia sp.. The structures were determined mainly by extensive 1D and 2D NMR experiments and supported by X-ray single-crystal analysis of 1 and the oxidation product 7. The absolute configurations of the microsphaeropsones A-C (1-3) were established by comparison of the electronic and vibrational circular dichroism (ECD and VCD) spectra of 1 with time-dependent DFT (TDDFT) and DFT calculations by using either the solid-state structures or DFT-optimized geometries as inputs. Preliminary studies indicated that 1, 2, and enone 7 showed antibacterial, fungicidal, and algicidal properties.
Assuntos
Cromonas/química , Cromonas/isolamento & purificação , Fungos/química , Oxepinas/química , Xantonas/química , Xantonas/isolamento & purificação , Bactérias/efeitos dos fármacos , Produtos Biológicos/química , Produtos Biológicos/isolamento & purificação , Produtos Biológicos/farmacologia , Chlorella/efeitos dos fármacos , Cromonas/farmacologia , Dicroísmo Circular , Hidrogenação , Espectroscopia de Ressonância Magnética , Xantonas/farmacologiaRESUMO
Three new isocoumarin derivatives ( 2- 4) were isolated together with monocerin ( 1) from Microdochium bolleyi, an endophytic fungus from Fagonia cretica, a herbaceous plant of the semiarid coastal regions of Gomera. Compounds 2 and 3 are both 12-oxo epimers of 1, and 4 is a ring-opened derivative of 1. The structures were elucidated by detailed spectroscopic analysis and comparison with reported data. The absolute configurations were determined by a modified Mosher's method. Compounds 1, 3, and 4 showed good antifungal, antibacterial, and antialgal activities against Microbotryum violaceum, Escherichia coli, Bacillus megaterium, and Chlorella fusca. Compound 2 was moderately antifungal and antialgal.
Assuntos
Antibacterianos/isolamento & purificação , Antibacterianos/farmacologia , Antifúngicos/isolamento & purificação , Antifúngicos/farmacologia , Isocumarinas/isolamento & purificação , Isocumarinas/farmacologia , Xylariales/química , Antibacterianos/química , Antifúngicos/química , Isocumarinas/química , Testes de Sensibilidade Microbiana , Estrutura Molecular , EspanhaRESUMO
Blennolides A-G (2-8), seven unusual chromanones, were isolated together with secalonic acid B (1) from Blennoria sp., an endophytic fungus from Carpobrotus edulis. This is the first reported isolation of the blennolides 2 and 3 (hemisecalonic acids B and E), the existence of which as the monomeric units of the dimeric secalonic acids had long been postulated. A compound of the proposed structure 4 (beta-diversonolic ester) will need to be revised, as its reported data do not fit those of the established structure of blennolide C (4). Other monomers, the blennolides D-F (5-7) seem to be derived from blennolides A (2) and B (3) by rearrangement of the hydroaromatic ring. The heterodimer 8, composed of the monomeric blennolide A (2) and the rearranged 11-dehydroxy derivative of blennolide E (6), extends the ergochrome family with an ergoxanthin type of skeleton. The structures of the new compounds were elucidated by detailed spectroscopic analysis and further confirmed by an X-ray diffraction study of a single crystal of 2. The absolute configurations were determined by TDDFT calculations of CD spectra, including the solid-state CD/TDDFT approach. Preliminary studies showed strong antifungal and antibacterial activities of these compounds against Microbotryum violaceum and Bacillus megaterium, respectively. They were also active against the alga Chlorella fusca and the bacterium Escherichia coli.
Assuntos
Fungos/química , Xantonas/isolamento & purificação , Dicroísmo Circular , Dimerização , Modelos Moleculares , Análise Espectral/métodos , Xantonas/químicaRESUMO
The filamentous fungi associated with healthy and decaying Fucus serratus thalli were studied over a 1-year period using isolation methods and molecular techniques such as 28S rRNA gene PCR-denaturing gradient gel electrophoresis (DGGE) and phylogenetic and real-time PCR analyses. The predominant DGGE bands obtained from healthy algal thalli belonged to the Lindra, Lulworthia, Engyodontium, Sigmoidea/Corollospora complex, and Emericellopsis/Acremonium-like ribotypes. In the culture-based analysis the incidence of recovery was highest for Sigmoidea marina isolates. In general, the environmental sequences retrieved could be matched unambiguously to isolates recovered from the seaweed except for the Emericellopsis/Acremonium-like ribotype, which showed 99% homology with the sequences of four different isolates, including that of Acremonium fuci. To estimate the extent of colonization of A. fuci, we used a TaqMan real-time quantitative PCR assay for intron 3 of the beta-tubulin gene, the probe for which proved to be species specific even when it was used in amplifications with high background concentrations of other eukaryotic DNAs. The A. fuci sequence was detected with both healthy and decaying thalli, but the signal was stronger for the latter. Additional sequence types, representing members from the Dothideomycetes, were recovered from the decaying thallus DNA, which suggested that a change in fungal community structure had occurred. Phylogenetic analysis of these environmental sequences and the sequences of isolates and type species indicated that the environmental sequences were novel in the Dothideomycetes.
Assuntos
Fucus/microbiologia , Fungos/genética , Filogenia , Sequência de Bases , Clonagem Molecular , Primers do DNA/genética , Alemanha , Funções Verossimilhança , Modelos Genéticos , Dados de Sequência Molecular , RNA Ribossômico 28S/genética , Reação em Cadeia da Polimerase Via Transcriptase Reversa , Análise de Sequência de DNA , Especificidade da Espécie , Tubulina (Proteína)/genéticaRESUMO
Three new massarilactones E-G (1-3) and the massarilactone acetonide (4) were isolated from the ethyl acetate extract of the endophytic fungus Coniothyrium sp., associated with the plant Artimisia maritima. Their structures were determined by analysis of the 1D and 2D NMR and mass spectroscopic data. The structure of massarilactones E (1) was confirmed by X-ray diffraction analysis, and its absolute configuration determined by the solid-state CD/TDDFT method.