RESUMO
Two new steroidal saponins, timosaponin X (1) and timosaponin Y (2), and one new pregnane glycoside, timopregnane B (3), were isolated from the rhizomes of Anemarrhena asphodeloides, as well as three known compounds 25S-timosaponin BII (4), protodesgalactotigonin (5), and timosaponin BII-a (6) isolated from this plant for the first time. By the detailed analysis of 1D, 2D NMR, MS spectra, and chemical evidences, the structures of new compounds were elucidated as 26-O-ß-d-glucopyranosyl-(25S)-5ß-22-methoxy-furost-3ß,26-diol 3-O-ß-d-glucopyranosyl-(1 â 2)-α-l-arabinopyranoside (1), 5ß-pseudo-spirost-3ß,15α,23α-triol 3-O-ß-d-glucopyranosyl-(1 â 2)-ß-d-galactopyranoside (2), (5ß,17α)-Δ((16)(17))-20-one-pregn-2ß,3ß-diol 3-O-ß-d-glucopyranosyl-(1 â 2)-ß-d-galactopyranoside (3).
Assuntos
Anemarrhena/química , Glicosídeos/isolamento & purificação , Pregnanos/isolamento & purificação , Saponinas/isolamento & purificação , Esteroides/isolamento & purificação , Medicamentos de Ervas Chinesas/química , Glicosídeos/química , Estrutura Molecular , Ressonância Magnética Nuclear Biomolecular , Pregnanos/química , Rizoma/química , Saponinas/química , Esteroides/químicaRESUMO
Three new oleanane-type triterpenoid saponins named celosins H, I, and J were isolated from the seeds of Celosia argentea L. Their structures were characterized as 3-O-ß-D-xylopyranosyl-(1 â 3)-ß-D-glucuronopyranosyl-polygalagenin 28-O-ß-D-glucopyranosyl ester, 3-O-ß-D-glucuronopyranosyl-medicagenic acid 28-O-ß-D-xylcopyranosyl-(1 â 4)-α-L-rhamnopyranosyl-(1 â 2)-ß-D-fucopyranosyl ester, and 3-O-ß-D-glucuronopyranosyl-medicagenic acid 28-O-α-L-arabinopyranosyl-(1 â 3)-[ß-D-xylcopyranosyl-(1 â 4)]-α-L-rhamnopyranosyl-(1 â 2)-ß-D-fucopyranosyl ester by NMR, MS, and chemical evidences, respectively. In our opinion, celosins H-J could be used as chemical markers for the quality control of C. argentea seeds.
Assuntos
Celosia/química , Medicamentos de Ervas Chinesas/isolamento & purificação , Ácido Oleanólico/análogos & derivados , Saponinas/isolamento & purificação , Medicamentos de Ervas Chinesas/química , Estrutura Molecular , Ressonância Magnética Nuclear Biomolecular , Ácido Oleanólico/química , Ácido Oleanólico/isolamento & purificação , Saponinas/química , Sementes/química , EstereoisomerismoRESUMO
Two new furostanol saponins (1 and 2), along with one known saponin (3), were obtained from the rhizomes of Aspidistra typica Baill. Their structures were elucidated as (25R)-26-O-ß-d-glucopyranosyl-furost-5-ene-12-one-3ß,22α,26-triol-3-O-ß-d-glucopyranosyl-(1 â 2)-[ß-d-xylopyranosyl-(1 â 3)]-ß-d-glucopyranosyl-(1 â 4)-ß-d-galactopyranoside (1, typaspidoside A), (25S)-26-O-ß-d-glucopyranosyl-furost-5-ene-12-one-3ß,22α,26-triol-3-O-ß-d-glucopyranosyl-(1 â 2)-[ß-d-xylopyranosyl-(1 â 3)]-ß-d-glucopyranosyl-(1 â 4)-ß-d-galactopyranoside (2, 25S-typaspidoside A), and timosaponin H1 (3), based on the integrative spectroscopic analysis of 1D- and 2D-NMR experiments, ESI-MS data and chemical evidence. The investigation on the chemical components of this plant is reported for the first time.
Assuntos
Medicamentos de Ervas Chinesas/isolamento & purificação , Liliaceae/química , Saponinas/isolamento & purificação , Esteroides/isolamento & purificação , Medicamentos de Ervas Chinesas/química , Espectroscopia de Ressonância de Spin Eletrônica , Estrutura Molecular , Rizoma/química , Saponinas/química , Estereoisomerismo , Esteroides/químicaRESUMO
Phytochemical investigation of the fresh tubers of Ophiopogon japonicus led to the isolation of two new furostanol saponins (1 and 2) together with two known steroidal saponins (3 and 4). Comprehensive spectroscopic analysis allowed the chemical structures of two new compounds to be elucidated as (25R)-26-O-[ß-d-glucopyranosyl-(1 â 2)-ß-d-glucopyranosyl]-5-ene-furost-1ß,3ß,22α,26-tetraol-3-O-α-l-rhamnopyranosyl-(1 â 2)-[ß-d-xylopyranosyl-(1 â 4)]-ß-d-glucopyranoside (1, ophiopogonin P) and (25R)-26-O-[ß-d-glucopyranosyl-(1 â 6)-ß-d-glucopyranosyl]-5-ene-furost-1ß,3ß,22α,26-tetraol-3-O-α-l-rhamnopyranosyl-(1 â 2)-[ß-d-xylopyranosyl-(1 â 4)]-ß-d-glucopyranoside (2, ophiopogonin Q). Furostanol saponins with the disaccharide chain linked at C-26 hydroxy group of the aglycone have been rarely reported from natural sources.
Assuntos
Medicamentos de Ervas Chinesas/isolamento & purificação , Ophiopogon/química , Saponinas/isolamento & purificação , Esteróis/isolamento & purificação , Medicamentos de Ervas Chinesas/química , Estrutura Molecular , Ressonância Magnética Nuclear Biomolecular , Tubérculos/química , Saponinas/química , Estereoisomerismo , Esteróis/químicaRESUMO
Three new steroidal saponins, parisyunnanosides G-I (1-3), one new C(21) steroidal glycoside, parisyunnanoside J (4), and three known compounds, padelaoside B (5), pinnatasterone (6), and 20-hydroxyecdyson (7), were isolated from the rhizomes of Paris polyphylla Smith var. yunnanensis. Compounds 1 and 3 have unique trisdesmoside structures that include a C-21 ß-d-galactopyranose moiety. All compounds were evaluated for their cytotoxicity against human CCRF leukemia cells.
Assuntos
Antineoplásicos Fitogênicos/isolamento & purificação , Medicamentos de Ervas Chinesas/isolamento & purificação , Liliaceae/química , Saponinas/isolamento & purificação , Esteroides/isolamento & purificação , Antineoplásicos Fitogênicos/química , Antineoplásicos Fitogênicos/farmacologia , Ensaios de Seleção de Medicamentos Antitumorais , Medicamentos de Ervas Chinesas/química , Medicamentos de Ervas Chinesas/farmacologia , Humanos , Estrutura Molecular , Rizoma/química , Saponinas/química , Saponinas/farmacologia , Esteroides/química , Esteroides/farmacologiaRESUMO
Nine spirostanol saponins (1-9) and seven mixtures of 25 R and 25 S spirostanol saponin isomers (10-16) were obtained from the seeds of Trigonella foenum-graecum after enzymatic hydrolysis of the furostanol saponin fraction by ß-glucosidase. Their structures were determined by NMR and MS spectroscopy. Among them, 1- 4, 6, 8, and 9 were new compounds and five, 11B, 12A, 13B, 14A, and 14B, were new structures observed from seven mixtures. In addition, the inhibitory effects of all saponins on rat platelet aggregation were evaluated.
Assuntos
Agregação Plaquetária/efeitos dos fármacos , Saponinas/farmacologia , Espirostanos/farmacologia , Trigonella/química , beta-Glucosidase/química , Animais , Medicamentos de Ervas Chinesas/farmacologia , Hidrólise , Masculino , Estrutura Molecular , Extratos Vegetais/farmacologia , Ratos , Ratos Wistar , Saponinas/química , Saponinas/isolamento & purificação , Sementes/química , Espirostanos/química , Espirostanos/isolamento & purificação , beta-Glucosidase/metabolismoRESUMO
Five new steroidal glycosides, timosaponin J ( 1), timosaponin K ( 2), (25 S)-karatavioside C ( 5), timosaponin L ( 6), and (25 S)-officinalisnin-I ( 8), together with eight known steroidal saponins, timosaponin E (1) ( 3), purpureagitosid ( 4), timosaponin BII ( 7), timosaponin B III ( 9), anemarrhenasaponin I ( 10), anemarrhenasaponin III ( 11), anemarrhenasaponin A (2) ( 12), and timosaponin A III ( 13), were isolated from the rhizomes of Anemarrhena asphodeloides. Their structures were elucidated on the basis of spectroscopic and chemical evidence. The aglycones of compounds 1 and 2 are new aglycones. Compounds 1- 13 were evaluated for their platelet aggregation activities, and compound 13 exhibited the strongest inhibitory effect on adenosine diphosphate (ADP)-induced platelet aggregation.
Assuntos
Anemarrhena/química , Glicosídeos/farmacologia , Inibidores da Agregação Plaquetária/farmacologia , Agregação Plaquetária/efeitos dos fármacos , Esteroides/farmacologia , Difosfato de Adenosina/farmacologia , Animais , Medicamentos de Ervas Chinesas/química , Medicamentos de Ervas Chinesas/isolamento & purificação , Glicosídeos/química , Glicosídeos/isolamento & purificação , Espectroscopia de Ressonância Magnética , Masculino , Estrutura Molecular , Plantas Medicinais/química , Ratos , Ratos Wistar , Rizoma/química , Saponinas/química , Saponinas/isolamento & purificação , Saponinas/farmacologia , Esteroides/química , Esteroides/isolamento & purificaçãoRESUMO
Five new glucosylated steroidal glycosides, cantalasaponin I-B(1) (1), I-B(2) (2), I-B(3) (3), I-B(4) (4) and I-B(5) (5), were isolated and purified from the transformed product of the cantalasaponin I by using Toruzyme 3.0 l as biocatalyst. Their structures were elucidated on the basis of high-resolution electrospray ionization mass spectrometry, one-dimensional ((1) H and (13) C NMR) and two-dimensional [COSY, heteronuclear single-quantum correlation (HSQC), HMBC and HSQC-TOCSY] NMR spectral analyses and chemical evidence.
Assuntos
Saponinas/química , Biocatálise , Glucosiltransferases/química , Glucosiltransferases/metabolismo , Glicosilação , Espectroscopia de Ressonância Magnética/normas , Estrutura Molecular , Padrões de Referência , Saponinas/isolamento & purificação , Saponinas/metabolismoRESUMO
In order to clarify the chemical constituents in Qiliqiangxin capsule, a rapid ultra-performance liquid chromatography/orthogonal acceleration time-of-flight mass spectrometry (UPLC-Q-TOF/MS(E)) method was established. Forty peaks were identified on line using this method. The herbal sources of these peaks were assigned. The results implied that triterpenoid saponins, flavonoid glycosides, C21-steroids and phenolic acids were included in the main components of Qiliqiangxin capsule. The method is simple and rapid for elucidation of the constituents of Qiliqiangxin capsule and the results are useful for the quality control of Qiliqiangxin capsule.
Assuntos
Medicamentos de Ervas Chinesas/química , Saponinas/análise , Triterpenos/análise , Cápsulas , Cromatografia Líquida de Alta Pressão , Flavonas/análise , Ginsenosídeos/análise , Glicosídeos/análise , Hidroxibenzoatos/análise , Plantas Medicinais/química , Controle de Qualidade , Espectrometria de Massas por Ionização por Electrospray , Esteroides/análise , Espectrometria de Massas em TandemRESUMO
Two new spirostanol saponins, named kingianoside H (1) and kingianoside I (2), were isolated from the processed rhizomes of Polygonatum kingianum, along with a known triterpenoid saponin ginsenoside-Rc (3), four known spirostanol saponins Tg (4), (5), polygonatoside C(1) (6) and ophiopogonin C' (7). The structures of the new compounds were elucidated by detailed spectroscopic analyses, including 1D and 2D NMR techniques and chemical methods. Compounds 3 and 5 were first reported from the genus Polygonatum. Compounds 4, 6 and 7 are reported for the first time from the processed Polygonatum kingianum.
Assuntos
Polygonatum/química , Saponinas/química , Espirostanos/química , Espectroscopia de Ressonância Magnética , Rizoma/química , Saponinas/síntese química , Espirostanos/isolamento & purificaçãoRESUMO
Four triterpenoid saponins were isolated from Albizziae cortex, and a complete assignment of their (1)H and (13)C NMR spectra was carried out using 1D and 2D NMR ((1)H-(1)H COSY, HSQC, HMBC, and HSQC-TOCSY) methods. Their (1)H NMR assignments were reported for the first time and some of their (13)C NMR spectral data reported in literature were corrected.
Assuntos
Albizzia/química , Espectroscopia de Ressonância Magnética/métodos , Saponinas/química , Terpenos/química , Isótopos de Carbono , Prótons , Xilema/químicaRESUMO
AIM: To investigate the chemical constituents of the rhizomes of Anemarrhena asphodeloides Bunge. METHODS: The compounds were separated by means of solvent extraction, chromatography on absorbent resin SP825 and silica gel C18 repeatedly, and their structures were elucidated on the basis of chemical methods and spectral analyses (FAB-MS, 1H NMR, 13C NMR, 1H-1H COSY). RESULTS: Six steroidal saponins were isolated from the rhizomes of Anemarrhena asphodeloides Bunge. They were identified as (25S)-26-O-beta-D-glucopyranosyl-22-hydroxy-5beta-furostane-2beta, 3beta, 26-triol-3-O-beta-D-glucopyranosyl-(1 --> 2)-beta-D-galactopyranoside (timosaponin N, 1), timosaponin E1 (2), (25S)-26-O-beta-D-glucopyranosyl-22-methoxy-5beta-furostane-2beta, 3beta, 26-triol-3-O-beta-D-glucopyranosyl-(1 --> 2)-beta-D-galactopyranoside (timosaponin O, 3) , timosaponin E2 (4), (25R) -26-O-beta-D-glucopyranosyl-22-hydroxy-5alpha-furostane-2alpha, 3beta, 26-triol-3-O-beta-D-glucopyranosyl-(1 --> 2)-[beta-D-xylpyranosyl-(1 --> 3)]-beta-D-glucopyranosyl-(1 --> 4)-beta-D-galactopyranoside (purpureagitosid, 5) and marcogenin-3-O-beta-D-glucopyranosyl-(1 --> 2)-beta-D-galactopyranoside (6). CONCLUSION: Compound 1 and compound 3 are new compounds, and compound 5 was isolated from the rhizomes of Anemarrhena asphodeloides Bunge for the first time.
Assuntos
Anemarrhena/química , Plantas Medicinais/química , Saponinas/isolamento & purificação , Conformação Molecular , Estrutura Molecular , Rizoma/química , Saponinas/químicaRESUMO
In this study seven strains of the genus Arthrobacter were screened by biotransformation to discover glycosylating patterns on steroid saponins. A strain of Arthrobacter nitroguajacolicus (CPCC 203516) was found to have the ability of fructosylation. Crude enzyme of the strain was extracted for the further study of conversion characteristics and patterns. Sucrose was used as a non-activated sugar donor, and fifteen steroidal saponins were involved. Nine furostan saponins of the substrates were converted, and ten products were isolated and identified. Based on the HR-ESI-MS, 1D, and 2D NMR spectral data, one fructosyl was added to furostan saponins at C6-OH of 26-O-ß-D-glucopyranosyl by A. nitroguajacolicus for all nine products. One product was distinguished by an additional fructosyl at the position of C6-OH on the first added fructosyl. Spirostan saponins of the substrates could not be converted. Steroidal saponins embracing a fructosyl are quite rare according to other reports based on similar studies. This study successfully converted furostan saponins into new compounds.
Assuntos
Arthrobacter/metabolismo , Saponinas/química , Saponinas/metabolismo , Esteroides/química , Biotransformação , Frutose/metabolismo , Glicosilação , Especificidade por SubstratoRESUMO
Five new steroidal saponins (1-5) were isolated from the fermentation broth of total furostanol glycosides from tubers of Dioscorea zingiberensis C.H. Wright incubated with a fungal, Absidia coerulea AS 3.3389, along with known saponins, zingiberensis new saponin (6), deltonin (7), prosapogenin A of dioscin (8), and protobioside (9), and their structures were established by NMR spectroscopy and mass spectrometry as well as by comparison with previously reported spectral data in the literatures. The induced effects in vitro on rat platelet aggregation of all compounds were evaluated.
Assuntos
Absidia/metabolismo , Dioscorea/química , Glicosídeos/metabolismo , Saponinas/química , Saponinas/metabolismo , Esteroides/química , Esteróis/metabolismo , Animais , Biotransformação , Fermentação , Masculino , Estruturas Vegetais/química , Agregação Plaquetária/efeitos dos fármacos , Ratos , Ratos Wistar , Saponinas/isolamento & purificação , Saponinas/farmacologia , Amido/metabolismoRESUMO
For the first time, a systematic phytochemical study was performed on the roots of Marsdenia tenacissima. Finally, sixteen new polyoxypregnane glycosides, marstenacissides A1-A7 (1-7) and marstenacissides B1-B9 (8-16), were isolated from M. tenacissima roots. The structures of these new compounds were established by various spectroscopic techniques, including 1D and 2D NMR spectroscopy and mass spectrometry.
Assuntos
Marsdenia/química , Extratos Vegetais/química , Raízes de Plantas/química , Pregnanos/química , Saponinas/química , Espectroscopia de Ressonância Magnética , Conformação Molecular , Extratos Vegetais/isolamento & purificação , Pregnanos/isolamento & purificação , Saponinas/isolamento & purificação , Espectrometria de Massas por Ionização por ElectrosprayRESUMO
Sixteen steroidal saponins, including seven previously unreported compounds, were isolated from Tribulus terrestris. The structures of the saponins were established using 1D and 2D NMR spectroscopy, mass spectrometry, and chemical methods. They were identified as: 26-O-ß-d-glucopyranosyl-(25R)-furost-4-en-2α,3ß,22α,26-tetrol-12-one (terrestrinin C), 26-O-ß-d-glucopyranosyl-(25R)-furost-4-en-22α,26-diol-3,12-dione (terrestrinin D), 26-O-ß-d-glucopyranosyl-(25S)-furost-4-en-22α,26-diol-3,6,12-trione (terrestrinin E), 26-O-ß-d-glucopyranosyl-(25R)-5α-furostan-3ß,22α,26-triol-12-one (terrestrinin F), 26-O-ß-d-glucopyranosyl-(25R)-furost-4-en-12ß,22α,26-triol-3-one (terrestrinin G), 26-O-ß-d-glucopyranosyl-(1â6)-ß-d-glucopyranosyl-(25R)-furost-4-en-22α,26-diol-3,12-dione (terrestrinin H), and 24-O-ß-d-glucopyranosyl-(25S)-5α-spirostan-3ß,24ß-diol-12-one-3-O-ß-d-glucopyranosyl-(1â4)-ß-d-galactopyranoside (terrestrinin I). The isolated compounds were evaluated for their platelet aggregation activities. Three of the known saponins exhibited strong effects on the induction of platelet aggregation.
Assuntos
Medicamentos de Ervas Chinesas/isolamento & purificação , Fitosteróis/isolamento & purificação , Fator de Ativação de Plaquetas/isolamento & purificação , Saponinas/isolamento & purificação , Tribulus/química , Medicamentos de Ervas Chinesas/química , Medicamentos de Ervas Chinesas/farmacologia , Estrutura Molecular , Ressonância Magnética Nuclear Biomolecular , Fitosteróis/química , Fitosteróis/farmacologia , Fator de Ativação de Plaquetas/química , Fator de Ativação de Plaquetas/farmacologia , Saponinas/química , EstereoisomerismoRESUMO
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-ß- D-glucopyranosyl kaur-5, 16-dien-3ß, 6, 13ß-trihydroxy-7-oxo-18-oic acid methyl ester and 3-O-ß-neohesperidosyl kaur-5, 16-dien-3ß, 6, 13ß-trihydroxy-7-oxo-18-oic acid methyl ester, respectively. The kaurene diterpenoid glycosides were first isolated and identified from fenugreek seeds.
Assuntos
Diterpenos/química , Glicosídeos/química , Sementes/química , Trigonella/química , Estrutura MolecularRESUMO
Ultra high-performance liquid chromatography (UHPLC) coupled with hybrid quadrupole time-of-flight mass spectrometry (Qtof MS(E)) was used to rapidly separate and identify steroidal saponins from the crude extract of the seeds of Trigonella foenum-graecum (TFG). By using the UHPLC/Qtof MS(E) data acquisition strategy, both intact precursor and fragment ion information were obtained from a single injection. Fragmentation rules for five major groups of saponins from TFG are summarized, and possible fragmentation pathways are proposed. Accurate mass measurements of molecular ions and fragment ions as well as retention times permitted the identification or tentative identification of a total of ninety-five saponins based on comparison with reference standards. This included twenty-two pairs of isomers. Thirty of these saponins were identified for the first time.
Assuntos
Fitosteróis/análise , Extratos Vegetais/análise , Saponinas/análise , Sementes , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz/métodos , Espectrometria de Massas em Tandem/métodos , Trigonella , Cromatografia Líquida de Alta Pressão/métodos , Fitosteróis/química , Extratos Vegetais/química , Saponinas/química , Sementes/química , Trigonella/químicaRESUMO
Twelve flavonoid glycosides were involved in the biotransformation of the glycosyl moieties by Curvularia lunata 3.4381, and the products were analyzed by UPLC/PDA-Q-TOF-MS(E). Curvularia lunata displayed hydrolyzing activities on the terminal Rha or Glc units of some flavonoid glycosides. Terminal Rha with a 1 â 2 linkage of isorhamnetin-3-O-neohesperidoside and typhaneoside could be hydrolyzed by Curvularia lunata, but terminal Rha with a 1 â 6 linkage of rutin, typhaneoside, and quercetin-3-O-apiosyl-(1 â 2)-[rhamnosyl-(1 â 6)]-glucoside could not be hydrolyzed. Curvularia lunata could also hydrolyze the Glc of icariin, floramanoside B, and naringin. This is the first report of the hydrolysis of glycosyl units of flavonoid glycosides by Curvularia lunata. A new way to convert naringin to naringenin was found in this research.
Assuntos
Ascomicetos/química , Flavonoides/química , Glucosídeos/química , Hidrólise , Espectrometria de Massas , Estrutura MolecularRESUMO
Eight novel steroidal saponins, ophiopogonins H-O (1-8), along with seven known steroidal saponins (9-15) were isolated from the tubers of Ophiopogon japonicus. The structures of these new compounds were determined by detailed spectroscopic analysis, including extensive 1D and 2D NMR data, and the analysis of hydrolytic reaction products. For the first time, rare furostanol saponins with disaccharide moiety linked at position C-26 of the aglycone were reported to be isolated from a natural source.