RESUMO
Alkaline hydrolysis of crude resin glycoside fraction of the seeds of Ipomoea muricata (L.) Jacq. (Convolvulaceae) yielded a new glycosidic acid, muricatic acid D; three known glycosidic acids, namely, muricatic acids A, B, and C; and three known organic acids, namely, isobutyric, 2S-methylbutyric, and 2S-methyl-3S-hydroxybutyric acid. Two new genuine resin glycosides with macrolactone structures (jalapins), muricatins X and XI, were also isolated from the fraction. Their structures were determined using spectroscopic data and chemical evidence.
Assuntos
Glicosídeos/química , Ipomoea/química , Extratos Vegetais/química , Resinas Vegetais/química , Sementes/química , Butiratos/química , Cromatografia Líquida , Convolvulaceae/química , Hidrólise , Espectroscopia de Ressonância Magnética , Estrutura Molecular , Solventes/químicaRESUMO
Two new triterpene glycosides, 24-deoxyoxytrogenin 3-O-α-L-rhamnopyranosyl (1â2)[ß-D-glucopyranosyl]-ß-D-galactopyranosyl (1â2)-ß-D-glucuronopyranoside and sophoradiol 3-O-α-L-rhamnopyranosyl (1â2)-ß-D-glucuronopyranosyl (1â2)-ß-D-glucuronopyranoside with four known glycosides were isolated from a Chinese natural medicine, the roots of Uraria crinita (L.) DESV. Their structures were determined by chemical and spectral methods.
Assuntos
Fabaceae/química , Glicosídeos/isolamento & purificação , Glicosídeos/análise , Medicina Tradicional Chinesa , Raízes de Plantas/químicaRESUMO
We examined the sulfides in onion (Allium cepa L.), Welsh onion (A. fistulosum L.), and garlic (A. sativum L.), and obtained three new thiolane-type sulfides (onionins A1-A3) from onion; two new thiabicyclic-type sulfides (welsonins A1, A2), together with onionins A1-A3, from Welsh onion; and six new acyclic-type sulfides (garlicnins L-1-L-4, E, and F), ten new thiolane-type sulfides (garlicnins A, B1-B4, C1-C3, K1, and K2), and three new atypical cyclic-type sulfides (garlicnins G, I, and J) from garlic. Acetone extracts showed the potential of these sulfides in inhibiting the polarization of M2 activated macrophages that are capable of suppressing tumor-cell proliferation. The effect of the thiolane-type sulfide of a major component, onionin A1, on tumor progression and metastasis in both osteosarcoma and ovarian cancer-bearing mouse models was then examined. Tumor proliferation was depressed, and tumor metastasis was controlled by regulating macrophage activation. These results showed that onionin A1 is an effective agent for controlling tumors in both in vitro and in vivo models, and that the antitumor effects observed in vivo are likely caused by reversing the antitumor immune system. Activation of the antitumor immune system by onionin A1 might be an effective adjuvant therapy for patients with osteosarcoma, ovarian cancer and other malignant tumors. Based on these findings, pharmacological investigations will be conducted in the future to develop natural and healthy foods and anti-cancer agents that can prevent or combat disease.
Assuntos
Allium/química , Antineoplásicos Fitogênicos/farmacologia , Neoplasias/tratamento farmacológico , Neoplasias/patologia , Cebolas/química , Sulfetos/farmacologia , Animais , Antineoplásicos Fitogênicos/química , Antineoplásicos Fitogênicos/isolamento & purificação , Proliferação de Células/efeitos dos fármacos , Humanos , Neoplasias/imunologia , Sulfetos/química , Sulfetos/isolamento & purificaçãoRESUMO
Newly characterized, atypical sulfides, garlicnins G (1), I (2), and J (3), were isolated from the acetone extracts of garlic bulbs, Allium sativum. Their production pathways are regarded as different from those of cyclic sulfoxides, 3,4-dimethyltetrahydrothiophene-S-oxide derivatives such as onionins A1-A3, garlicnins B1-B4 and C1-C3.
Assuntos
Alho/química , Sulfetos/isolamento & purificação , Tiofenos/isolamento & purificação , Estrutura Molecular , Sulfetos/química , Tiofenos/químicaRESUMO
Four hexaglycosides of methyl 3S,12S-dihydroxyhexadecanoate (1-4) were provided after treatment of the crude convolvulin fraction from Rhizoma Jalapae Braziliensis (the root of Ipomoea operculata (GOMES) MART., Convolvulaceae) with indium(III) chloride in methanol. The structures of 1-4 were elucidated on the basis of spectroscopic and chemical methods. Their sugar moieties were partially acylated with organic acids including (3S,9R)-3,6:6,9-diepoxydecanoic (exogonic) acid, (E)-2-methylbut-2-enoic (tiglic) acid, and isovaleric acid.
Assuntos
Ácidos/síntese química , Glicosídeos/síntese química , Índio/química , Metanol/química , Éteres Metílicos/síntese química , Resinas Vegetais/química , Ácidos/química , Acilação , Convolvulaceae/química , Glicosídeos/química , Éteres Metílicos/química , Estrutura Molecular , Raízes de Plantas/químicaRESUMO
A new resin glycoside, named muricatin IX (1), was isolated from the seeds of Ipomoea muricata (L.) JACQ. (Convolvulaceae). The structure of 1 was determined on the basis of spectroscopic data as well as chemical evidence. Compound 1 is the first representative of resin glycosides in which an organic acid connects the sugar moiety and the aglycone moiety to form macrocyclic ester ring.
Assuntos
Glicosídeos/isolamento & purificação , Ipomoea/química , Resinas Vegetais/isolamento & purificação , Sementes/química , Glicosídeos/química , Conformação Molecular , Resinas Vegetais/químicaRESUMO
Four new resin glycosides, named calysolins XIV (1), XV (2), XVI (3), and XVII (4) were isolated from the leaves, stems, and roots of Calystegia soldanella ROEM.. et SCHULT. (Convolvulaceae). Their structures were determined based on spectroscopic and chemical evidence, and consisted of two different types: those (1) with a macrolactone structure and those (2-4) with a non-macrolactone structure. Their sugar moieties were partially acylated by specific organic acids, including tiglic, 2S-methylbutyric, and 2S,3S-nilic acids. Additionally, evaluation of the antiviral activity of 1-4 revealed effects against the herpes simplex virus type 1.
Assuntos
Antivirais/química , Antivirais/farmacologia , Calystegia/química , Glicosídeos/química , Glicosídeos/farmacologia , Herpesvirus Humano 1/efeitos dos fármacos , Antivirais/isolamento & purificação , Glicosídeos/isolamento & purificação , Herpes Simples/tratamento farmacológico , HumanosRESUMO
It has been shown that commercial tomato juice packaged in 900 g plastic bottles contains rare, naturally occurring steroidal solanocapsine-type tomato glycosides in which the saponins consist of esculeosides B-1 (2) and B-2 (3) in 0.041% as major components lacking esculeoside A. We suggest that these saponins are derived from esculeoside A (1) when the juice in plastic bottles is prepared by treatment with boiling water, similar to the process used in preparing canned tomatoes. Herein, the obtained tomato saponins (2) and (3) provided sapogenols esculeogenin B1 (4) and B2 (5), respectively, by acid hydrolysis. The former was identical to esculeogenin B previously reported, and the latter was a new sapogenol characterized to be (5α,22S,23S,25S)-22,26-epimino-16ß,23-epoxy-3ß,23,27-trihydroxycholestane.
Assuntos
Sucos de Frutas e Vegetais/análise , Sapogeninas/análise , Saponinas/análise , Solanum lycopersicum/química , Hidrólise , Espectroscopia de Ressonância MagnéticaRESUMO
Newly identified cyclic sulfoxides-garlicnins K1 (1), K2 (2), and H1 (3)-were isolated from the acetone extracts of the bulbs of garlic, Allium sativum. Garlicnin H1 (3) demonstrated potential to suppress tumor cell proliferation by regulating macrophage activation. The structures of garlicnins K1 and K2, 3,4-dimethyl-5-allyl-tetrahydrothiophen-2-one-S-oxides, and the structure of garlicnin H1, 3-carboxy-3-hydroxy-4-methyl-5-allylsulfoxide-tetrahydrothiophen-2-(ethane-1,2-diol)-S-oxide were characterized by spectroscopic analysis.
Assuntos
Alho/química , Sulfóxidos/química , Antígenos CD/análise , Antígenos CD/metabolismo , Antígenos de Diferenciação Mielomonocítica/análise , Antígenos de Diferenciação Mielomonocítica/metabolismo , Linhagem Celular , Ensaio de Imunoadsorção Enzimática , Alho/metabolismo , Humanos , Macrófagos/citologia , Macrófagos/efeitos dos fármacos , Macrófagos/metabolismo , Espectroscopia de Ressonância Magnética , Conformação Molecular , Extratos Vegetais/química , Raízes de Plantas/química , Raízes de Plantas/metabolismo , Receptores de Superfície Celular/análise , Receptores de Superfície Celular/metabolismo , Sulfóxidos/isolamento & purificação , Sulfóxidos/farmacologiaRESUMO
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.
Assuntos
Glicosídeos/química , Índio/química , Metanol/química , Resinas Vegetais/química , Sementes/química , Acilação , Éter/químicaRESUMO
In this study, the new stable sulfur-containing compounds onionins A2 (1) and A3 (2) were isolated from the acetone extracts of the bulbs of Allium cepa L. and identified as the stereoisomers of onionin A1 discovered in our previous study. Their chemical structures, 3,4-dimethyl-5-(1E-propenyl)-tetrahydrothiophene-2-sulfenic acid-S-oxides, were characterized using various spectroscopic techniques. In addition, 1 and 2 together with onionin A1 were successfully isolated from the leaves of the Welsh onion, Allium fistulosum L. The onion-extracted fractions showed good potential to inhibit the polarization of M2 activated macrophages, indicating their possible ability to inhibit tumor cell proliferation.
Assuntos
Fatores Imunológicos/química , Macrófagos/efeitos dos fármacos , Cebolas/química , Ácidos Sulfênicos/química , Tiofenos/química , Antígenos CD/análise , Antígenos CD/imunologia , Antígenos de Diferenciação Mielomonocítica/análise , Antígenos de Diferenciação Mielomonocítica/imunologia , Antineoplásicos Fitogênicos/química , Antineoplásicos Fitogênicos/isolamento & purificação , Antineoplásicos Fitogênicos/farmacologia , Células Cultivadas , Humanos , Fatores Imunológicos/isolamento & purificação , Fatores Imunológicos/farmacologia , Macrófagos/imunologia , Raízes de Plantas/química , Receptores de Superfície Celular/análise , Receptores de Superfície Celular/imunologia , Ácidos Sulfênicos/isolamento & purificação , Ácidos Sulfênicos/farmacologia , Tiofenos/isolamento & purificação , Tiofenos/farmacologiaRESUMO
Four new acylated glycosidic acid methyl esters were isolated after treatment of the crude ether-insoluble resin glycoside (convolvulin) fraction obtained from the 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.
Assuntos
Ácidos/isolamento & purificação , Convolvulaceae/química , Glicosídeos/química , Resinas Vegetais/química , Sementes/química , Ácidos/química , Acilação , Cloretos/química , Ésteres , Índio/química , Metanol/química , MetilaçãoRESUMO
Four new resin glycosides having macrolactone structures (jalapins), named calysolins X (1)-XIII (4), were isolated from the leaves, stems, and roots of Calystegia soldanella ROEM. et SCHULT. (Convolvulaceae). Their structures were determined on the basis of spectroscopic data as well as chemical evidence. The sugar moieties of 1-4 were partially acylated by some organic acids, including tiglic acid, 2S-methylbutyric acid, and 2S,3S-nilic acid. Additionally, the antiviral activity of 1-4 toward herpes simplex virus type 1 was evaluated. All the compounds showed antiviral activity.
Assuntos
Antivirais/química , Calystegia/química , Glicosídeos/química , Herpesvirus Humano 1/efeitos dos fármacos , Lactonas/química , Resinas Vegetais/química , Antivirais/isolamento & purificação , Antivirais/farmacologia , Glicosídeos/isolamento & purificação , Glicosídeos/farmacologia , Herpes Simples/tratamento farmacológico , Humanos , Lactonas/isolamento & purificação , Lactonas/farmacologiaRESUMO
Five new resin glycosides having macrolactone structures (jalapins), named calysolins V-IX (1-5), were isolated from the leaves, stems, and roots of Calystegia soldanella ROEM. et SCHULT. (Convolvulaceae). Their structures were determined on the basis of spectroscopic data as well as chemical evidence. The isolated compounds could be classified into two macrolactone types-one having a 22-membered ring (1-4) and the other with a 27-membered ring (5). The sugar moieties of 1-5 were found to exist in partially acylated forms comprising 2S-methylbutyric acid and tiglic acid. Compounds 4 and 5 are the first representatives of the calysolic acid C as the component glycosidic acid. Additionally, the antiviral activity of 1-5, together with calysolins I-IV and soldanelline B, which are previously isolated jalapins from this plant, toward herpes simplex virus type 1 was evaluated. All the compounds showed antiviral activity.
Assuntos
Antivirais/química , Antivirais/farmacologia , Calystegia/química , Glicosídeos/química , Glicosídeos/farmacologia , Herpesvirus Humano 1/efeitos dos fármacos , Lactonas/química , Lactonas/farmacologia , Resinas Vegetais/química , Resinas Vegetais/farmacologiaRESUMO
Six novel acyclic sulfides, named garlicnins L-1-L-4 (1-4), E (5), and F (6), were isolated from the acetone extracts, with the ability to suppress M2 macrophage activation, of the bulbs of garlic (Allium sativum L.), and their chemical structures were characterized.
Assuntos
Alho/química , Macrófagos/efeitos dos fármacos , Sulfetos/farmacologia , Tiofenos/farmacologia , Humanos , Estrutura Molecular , Relação Estrutura-Atividade , Sulfetos/química , Sulfetos/isolamento & purificação , Tiofenos/química , Tiofenos/isolamento & purificaçãoRESUMO
Here reports new conversions methods of tomato saponins, esculeoside A (1) and a mixture of esculeosides B-1 (2) and B-2 (3), (the latter two were obtained from tomato cans) into pregnane derivative (5) by an alkal treatment followed by acid treatment. Compound 1 or a mixture of 2 and 3 were each refluxed with 1 N KOH to afford a characteristic pyridine steroidal glycoside (4), which was then treated with 2 N HCl-MeOH to afford a pregnane derivative, 3ß-hydroxy-5α-pregn-16-en-20-one (5). The results of the above two reactions indicated that tomato saponins are chemically closely related to pregnane hormones. We assume that the assimilated tomato saponins via the small intestine are metabolized into pregnane derivatives, demonstrating various bioactivities such as anti-cancer, anti-osteoporosis, and anti-menopausal disorder activities.
Assuntos
Pregnanos/síntese química , Saponinas/química , Solanum lycopersicum/química , Conformação Molecular , Pregnanos/químicaRESUMO
Dendritic cells (DCs) can initiate immune response through the presenting antigens to naïve T lymphocytes. Esculeoside A (EsA), a spirosolane glycoside, is reported as a major component in the ripe fruit of tomato. Little is known about the effect of tomato saponin on mice bone marrow-derived DCs. This study revealed that EsA and its aglycon, esculeogenin A (Esg-A), attenuated the phenotypic and functional maturation of murine DCs stimulated by lipopolysaccharide (LPS). We found that EsA/Esg-A down-regulated the expression of major histocompatibility complex type II molecules and costimulatory molecule CD86 after LPS stimulation. It was also determined that EsA-/Esg-A-treated DCs were poor stimulators of allogeneic T-cell proliferation and exhibited impaired interleukin-12 and TNF-α production. Additionally, EsA/Esg-A was able to inhibit TLR4-related and p-NFκB signaling pathways. This study shows new insights into the immunopharmacology of EsA/Esg-A, and represents a novel approach to controlling DCs for therapeutic application.
Assuntos
Células Dendríticas , Saponinas , Transdução de Sinais , Solanum lycopersicum , Receptor 4 Toll-Like , Animais , Células Dendríticas/efeitos dos fármacos , Células Dendríticas/metabolismo , Células Dendríticas/imunologia , Receptor 4 Toll-Like/metabolismo , Transdução de Sinais/efeitos dos fármacos , Saponinas/farmacologia , Camundongos , NF-kappa B/metabolismo , Lipopolissacarídeos/farmacologia , Camundongos Endogâmicos C57BL , Interleucina-12/metabolismo , Proliferação de Células/efeitos dos fármacos , Camundongos Endogâmicos BALB C , Linfócitos T/efeitos dos fármacos , Linfócitos T/metabolismo , Linfócitos T/imunologia , Fator de Necrose Tumoral alfa/metabolismo , Frutas/química , Antígeno B7-2/metabolismo , SapogeninasRESUMO
Several novel sulfides, called garlicnins B2 (1), B3 (2), B4 (3), C2 (4), and C3 (5), were isolated from acetone extracts of garlic, Allium sativum L. and characterized. These garlicnins are capable of suppressing M2 macrophage activation and they have a novel skeleton of cyclic sulfoxide. The structures of the former 3 and latter of 2 were deduced to be 2-(sulfenic acid)-5-(allyl)-3,4-dimethyltetrahydrothiophene-S-oxides and 2-(allyldithiine)-5-(propenylsulfoxide)-3,4-dimethyltetrahydrothiophene-S-oxides, respectively. The mechanism of the proposed production of these compounds is discussed. The identification of these novel sulfoxides from garlic accumulates a great deal of new chemistry in the Allium sulfide field, and future pharmacological investigations of these compounds will aid the development of natural, healthy foods and anti-cancer agents that may prevent or combat disease.
Assuntos
Compostos Alílicos/química , Dissulfetos/química , Alho/química , Sulfóxidos/química , Acetona/química , Compostos Alílicos/isolamento & purificação , Compostos Alílicos/farmacologia , Antígenos CD/metabolismo , Antígenos de Diferenciação Mielomonocítica/metabolismo , Linhagem Celular , Dissulfetos/isolamento & purificação , Dissulfetos/farmacologia , Humanos , Macrófagos/efeitos dos fármacos , Espectroscopia de Ressonância Magnética , Conformação Molecular , Receptores de Superfície Celular/metabolismo , Sulfóxidos/isolamento & purificação , Sulfóxidos/farmacologiaRESUMO
Treatment of the ether-insoluble resin glycoside (convolvulin) fraction from seeds of Quamoclit pennata (Convolvulaceae) with indium(III) chloride in methanol provided three oligoglycosides of hydroxy fatty acid (glycosidic acid) methyl esters and two methyl glycosides, which were partially acylated by a glycosidic acid, 7S-hydroxydecanoic acid 7-O-ß-D-quinovopyranoside (quamoclinic acid B) and/or two organic acids, (E)-2-methylbut-2-enoic (tiglic) acid and/or 3R-hydroxy-2R-methylbutyric (nilic) acid. Their structures were elucidated on the basis of spectroscopic data and chemical conversions.
Assuntos
Convolvulaceae/química , Glicosídeos/química , Éteres Metílicos/química , Resinas Vegetais/química , Sementes/química , Acilação , Glicosídeos/isolamento & purificação , Índio/química , Metanol/química , Éteres Metílicos/isolamento & purificação , Resinas Vegetais/isolamento & purificaçãoRESUMO
Italian canned tomatoes contain the tomato glycosides esculeosides B-1 (1, 0.0052%) and B-2 (2, 0.0068%) without esculeoside A. Herein, the structure of esculeoside B-1 (1) is characterized to be 3-O-ß-lycotetraosyl (5S,22R,23S,25S)-22,26-epimino-16ß,23-epoxy-3ß,23,27-trihydroxycholestane 27-O-ß-D-glucopyranoside. We hypothesized that these substances might be derived from esculeoside A when the cans are prepared with treatment in boiling water. To confirm that hypothesis, we refluxed esculeoside A with water for 6.5 h, providing esculeosides B-1 (1) and B-2 (2) in yields of 25.8% and 31.0%, respectively.