ABSTRACT
This is a comparative study on the intraspecific chemical variability of Aristolochia cordigera species, collected in two different regions of Brazil, Biome Cerrado (semiarid) and Biome Amazônia (coastal). The use of GC-MS and statistical methods led to the identification of 56 compounds. A higher percentage of palmitone and germacrene-D in the hexanes extracts of the leaves of plants from these respective biomes was observed. Phytochemical studies on the extracts led to the isolation and identification of 19 known compounds, including lignans, neolignans, aristolochic acids, indole-ß-carboline, and indole alkaloids. In addition, two new indole alkaloids, 3,4-dihydro-hyrtiosulawesine and 6-O-(ß-glucopyranosyl)hyrtiosulawesine, were isolated and a new neolignan, cis-eupomatenoid-7, was obtained in a mixture with its known isomer eupomatenoid-7. Their structures were determined by spectroscopic methods, mainly by 1D- and 2D-NMR. The occurrence of indole alkaloids is being described for the first time in the Aristolochiaceae family. Moreover, the in vitro susceptibility of intracellular amastigote and promastigote forms of Leishmania amazonensis to the alkaloids and eupomatenoid-7 were evaluated. This neolignan exhibited low activity against promastigotes (IC50 = 46 µM), while the alkaloids did not show inhibitory activity. The new alkaloid 6-O-(ß-glucopyranosyl)hyrtiosulawesine exhibited activity in the low micromolar range against Plasmodium falciparum, with an IC50 value of 5 µM and a selectivity index higher than 50.
Subject(s)
Antiprotozoal Agents/pharmacology , Aristolochia/chemistry , Cytotoxins/pharmacology , Indole Alkaloids/pharmacology , Lignans/pharmacology , Plant Extracts/pharmacology , Antiprotozoal Agents/chemistry , Antiprotozoal Agents/isolation & purification , Brazil , Cell Line, Tumor , Cytotoxins/chemistry , Cytotoxins/isolation & purification , Gas Chromatography-Mass Spectrometry , Humans , Indole Alkaloids/chemistry , Indole Alkaloids/isolation & purification , Leishmania/drug effects , Lignans/chemistry , Lignans/isolation & purification , Molecular Structure , Plant Extracts/chemistry , Plant Extracts/isolation & purification , Plasmodium falciparum/drug effectsABSTRACT
Root extracts of Holostylis reniformis (Aristolochiaceae) yielded three new natural sesquiterpenes, a sesquiterpene with an unusual carbon skeleton, 4,5-seco-guaiane (7-epi-11-hydroxychabrolidione A, 1), a nine-membered lactone with new carbon skeleton (holostylactone, 2), and a new megastigmane [(6S,7E)-6,9-dihydroxy-10-(2'-hydroxy-ethoxy)-4,7-megastigmadien-3-one, 3], together with bulnesol and sitosterol-3-O-β-D-glucopyranoside. The structures of these compounds were determined by spectroscopic analyses and B3LYP/STO-3G** theoretical studies.
Subject(s)
Aristolochiaceae/chemistry , Lactones , Sesquiterpenes, Guaiane/chemistry , Sesquiterpenes , Lactones/chemistry , Lactones/isolation & purification , Magnetic Resonance Spectroscopy , Molecular Structure , Plant Extracts/chemistry , Plant Roots/chemistry , Sesquiterpenes/chemistry , Sesquiterpenes/isolation & purification , Sesquiterpenes, Guaiane/isolation & purificationABSTRACT
A new aristolactam, aristolactam 9-O-ß-D-glucopyranosyl-(1â2)-ß-D-glucoside, and two alkamides, N-cis- and N-trans-p-coumaroyl-3-O-methyldopamine, were isolated from stems of Aristolochia gigantea, together with the known compounds allantoin, E-nerolidol, ß-sitosterol, (+)-kobusin, (+)-eudesmin, trans-N-feruloyltyramine, trans-N-coumaroyltyramine, trans-N-feruloyl-3-O-methyldopamine, aristolactam Ia-N-ß-D-glucoside, aristolactam Ia 8-ß-D-glucoside, aristolactam IIIa, and magnoflorine. Their structures were determined by spectroscopic analyses.
Subject(s)
Aristolochia/chemistry , Lactams/chemistry , Polyunsaturated Alkamides/chemistry , Lactams/isolation & purification , Molecular Structure , Polyunsaturated Alkamides/isolation & purificationABSTRACT
Microbiological transformation of the aryltetralone lignan (-)-8'-epi-aristoligone (1) with Cunninghamella echinulata ATCC 10028B afforded two known natural lignans, (-)-holostyligone (3) and (-)-arisantetralone (4). Incubation of the aryltetralin lignan (-)-isogalbulin (2), obtained by chemical transformation of 1, with C. echinulata ATCC 10028B afforded the known lignan aryltetralol (5) and seven new metabolites, (-)-8-hydroxyisogalbulin (6), (-)-7-methoxyisogalbulin (7), (-)-4'-O-demethyl-8-hydroxyisogalbulin (8), (-)-7-methoxy-8-hydroxyisogalbulin (9), (-)-4'-O-demethyl-7-methoxyisogalbulin (10), (-)-4',5-O-didemethylcyclogalgravin (11), and (-)-4'-O-demethylcyclogalgravin (12). When 2 was subjected to biotransformation with Beauveria bassiana ATCC 7159, (-)-8-hydroxyisogalbulin (6) was the only isolable product. The structures of all new compounds were established by detailed analysis of their spectroscopic data.
Subject(s)
Beauveria/metabolism , Cunninghamella/metabolism , Lignans/metabolism , Biotransformation , Lignans/chemistry , Lignans/isolation & purification , Molecular Structure , Nuclear Magnetic Resonance, Biomolecular , StereoisomerismABSTRACT
Corydines, isocorydines, and analogous aporphine alkaloids were isolated from the leaves of Aristolochia lagesiana var. intermedia, together with three bisaporphine salts (lagesianines B-D). Their structures were determined by chemical derivatizations and spectroscopic analyses. Lagesianines B and C are the first examples of N-CH(2)-N' and C-2-O-C-1' linked dimeric aporphine alkaloids, respectively, while the monomeric units of lagesianine D, which has a carbon skeleton, are linked through C-7-C-5'via an ethane-1,2-diol group (C-7-CHOHCHOH-C-5').
Subject(s)
Aporphines/chemistry , Aporphines/isolation & purification , Aristolochia/chemistry , Magnetic Resonance SpectroscopyABSTRACT
Holostylis reniformis biosynthesizes 8-8' linked lignans without 9,9'-oxygenation. To elucidate the biosynthetic pathways to these lignans, the reputed precursors [U-(14)C]phenylalanine, [9-(3)H(1)]coniferyl alcohol, and [9-(3)H(1)]isoeugenol were administered to roots of the plant, which led to the incorporation of (3)H and (14)C into ten 2,7' linked-lignans (aryltetralone lignans) and two 7,7'-epoxylignans (furan lignans). These administration experiments demonstrated that the lignans were propenylphenol-derived and that H. reniformis can exhibit regioselective control over radical-radical coupling (via isoeugenol radicals). Regiospecific control over propenylphenol-derived lignan biosynthesis was observed, together with diastereoselective control of C2-C7' bond formation for the aryltetralone lignans (7'R). These experiments provide evidence that isoeugenol is a biosynthetic intermediate to the aryltetralone and furan lignans.
Subject(s)
Antimalarials/metabolism , Aristolochiaceae/metabolism , Lignans/biosynthesis , Chromatography, High Pressure Liquid , Magnetic Resonance Spectroscopy , Spectrometry, Mass, Electrospray Ionization , Spectrophotometry, UltravioletABSTRACT
Biflavones, a chalcone-flavone, and a tetraflavonoid with a new carbon skeleton were isolated from the leaves of Aristolochia ridicula. Their structures were determined by chemical derivatizations and spectrometric analyses.
Subject(s)
Aristolochia/chemistry , Flavonoids/chemistry , Flavonoids/metabolism , Aristolochia/metabolism , Molecular Structure , Plant Leaves/chemistryABSTRACT
The insecticidal activity of hexane extracts from the roots and leaves of Aristolochia malmeana was evaluated against Anticarsia gemmatalis larvae by topical application. Extract from the roots was the most active and caused 50% mortality in larvae at 308.4 microg/microL. From this extract, a clerodane diterpene, (-)-kolavenic acid, and three lignans, (-)-kusunokinin, (-)-hinokinin, and (8 S,8' R,9 S)-cubebin, were isolated by chromatography and partition procedures and then evaluated for their insecticidal activities either individually or in pairs. (-)-Kusunokinin showed higher activity against A. gemmatalis (LD10=9.3, LD50=230.1 microg/microL) than the crude extract, and its activity was dose-dependent, whereas the other constituents did not exhibit any significant activity. Together with (-)-kusunokinin and (-)-hinokinin, (-)-copalic acid, (-)-2-oxokolavenic acid, (-)- ent-6-beta-hydroxy-copalic acid, (8 R,8' R,9 R)- and (8 R,8' R,9 S)-cubebins, (-)-fargesin, and (-)-phillygenin were isolated from the hexane extract of the leaves. The compounds were identified on the basis of spectroscopic analysis.
Subject(s)
Aristolochia/chemistry , Diterpenes/administration & dosage , Insecticides , Lepidoptera , Lignans/administration & dosage , Animals , Dose-Response Relationship, Drug , Larva , Plant Extracts/administration & dosage , Plant Extracts/chemistry , Plant Leaves/chemistry , Plant Roots/chemistryABSTRACT
In the two, almost identical, mol-ecules in the asymmetric unit of the title compound [systematic name: (E)-3-methyl-5-(1,2,4a,5-tetra-methyl-1,2,3,4,4a,7,8,8a-octa-hydro-naphthalen-1-yl)pent-2-enoic acid], C(20)H(32)O(2), the rings are trans fused. The cyclo-hexane ring has a chair conformation and the cyclo-hexene ring a distorted half-boat conformation. The two independent mol-ecules are connected into a dimer via O-Hâ¯O hydrogen bonds. The dimers are associated into supra-molecular chains along c via C-Hâ¯O contacts.
ABSTRACT
Essential oils were obtained from roots of 10 Aristolochia species by hydrodistillation and analysed by GC-MS. A total of 75 compounds were identified in the analysed oils. Multivariate analyses of the chemical constituents of the roots enabled classification of the species into four morphological groups. These forms of analysis represent an aid in identification of further specimens belonging to these species.
Subject(s)
Aristolochia/chemistry , Aristolochia/classification , Gas Chromatography-Mass Spectrometry , Oils, Volatile/analysis , Oils, Volatile/chemistry , Plant Roots/chemistry , Principal Component AnalysisABSTRACT
Aryltetralol and aryltetralone lignans were isolated from the hexane extracts of the roots of Holostylis reniformis. Their structures were determined by spectroscopic methods and chemical transformations.
Subject(s)
Aristolochiaceae/chemistry , Lignans/chemistry , Plant Roots/chemistry , Tetralones/chemistry , Magnetic Resonance Spectroscopy , Molecular Conformation , Molecular StructureABSTRACT
(8S,8'R,9S)-, (8R,8'R,9R)-, and (8R,8'R,9S)-cubebins, together with (8R,8'R,8''R,8'''R,9R,9''S)-bicubebin, were isolated from Aristolochia lagesiana and Aristolochia pubescens. Their structures were determined by spectroscopic methods, including 1H and 13C NMR spectroscopy at low temperatures, and by chemical transformations.
Subject(s)
Aristolochia/chemistry , Lignans/chemistry , Plant Extracts/chemistry , Plants, Medicinal , 4-Butyrolactone/chemistry , 4-Butyrolactone/pharmacology , Circular Dichroism , Lignans/isolation & purification , Lignans/pharmacology , Magnetic Resonance Spectroscopy , Molecular ConformationABSTRACT
Biflavones and a chalcone-flavone tetramer were isolated from the leaves of Aristolochia ridicula, together with proto-quercitol. Their structures were determined by spectroscopic methods.
Subject(s)
Aristolochia/chemistry , Chalcone/analogs & derivatives , Chalcone/isolation & purification , Flavones/isolation & purification , Inositol/analogs & derivatives , Chalcones , Inositol/isolation & purification , Molecular Structure , Plant Leaves/chemistryABSTRACT
Acetone and ethanol extracts of the tubercula and several compounds isolated from Aristolochia pubescens (Willd) were bioassayed on velvetbean caterpillars, Anticarsia gemmatalis (Hübner), for evaluation of the insecticidal activities. Of the extracts subjected to bioassay, the acetone extract showed the highest activity. (-)-Cubebin did not show activity against soybean caterpillars, whereas aristolochic acid and ent-kaur-15-en-17-ol increased the larval period. These compounds, and (+)-eudesmin and (+)-sesamin, reduced the viability of this period, giving rise to malformed adults. These extracts and compounds are therefore potential botanical insecticide agents for the control of velvetbean caterpillars in soybean crops.
Subject(s)
Aristolochia/chemistry , Insecticides/toxicity , Larva/drug effects , Lepidoptera/drug effects , Plant Extracts/toxicity , Animals , Aristolochic Acids/toxicity , Biological Assay , Dioxoles/toxicity , Diterpenes/toxicity , Furans/toxicity , Lignans/toxicityABSTRACT
Aryltetralone lignans and two 7,8-seco-lignans were isolated from the acetone and hexane extracts of the roots of Holostylis reniformis, together with (-)-galbacin. Their structures were determined by spectroscopic methods.
Subject(s)
Aristolochiaceae/chemistry , Lignans/chemistry , Tetralones/chemistry , Circular Dichroism , Molecular Structure , Nuclear Magnetic Resonance, Biomolecular , Plant Extracts/chemistry , Plant Roots/chemistryABSTRACT
From the acetone and ethanol extracts of the tubercula of Aristolochia pubescens, two diterpene esters of aristolochic acids were isolated, together with 23 known compounds. The structures of the compounds were determined on the basis of spectroscopic analysis.
Subject(s)
Aristolochia/chemistry , Aristolochic Acids/chemistry , Diterpenes/chemistry , Esters/chemistry , Esters/isolation & purification , Magnetic Resonance Spectroscopy , Plants, Medicinal/chemistryABSTRACT
2-Deoxyribonolactones and four tetrahydroisoquinoline alkaloids were isolated from the acetone extract of the leaves of Aristolochia arcuata Mast., together with pinitol, sequoyitol, glycerol, fructose, sucrose, eupomatenoid-7, salsolinol, and 6,7-dihydroxy-1,1-dimethyl-1,2,3,4-tetrahydroisoquinoline. Their structures were determined on the basis of spectroscopic methods, mainly using 1H, 13C, 15N, and 31P NMR.