ABSTRACT
INTRODUCTION: Tetrapterys mucronata Cav. (Malpighiaceae) is a plant used in some regions of Brazil in the preparation of ayahuasca. OBJECTIVE: To determine the content of the main tryptamine alkaloids in the stem bark of T. mucronata Cav. and assess their possible toxic and hallucinogenic properties based on the doses found in a water decoction that mimics the ayahuasca preparation. METHODS: Four alkaloids previously described for their toxic and hallucinogenic properties were quantitated by multiple reaction monitoring HPLC combined with electrospray ionisation and tandem MS (HPLC-ESI/MS/MS) in the water decoction and ethanolic extracts from the bark of T. mucronata. RESULTS: Exhaustive extraction of the stem barks with ethanol revealed the following alkaloid levels: bufotenine (1) 3.26 ± 0.31 mg/g, 5-methoxy-N-methyltryptamine (2) 0.88 ± 0.08 mg/g, 5-methoxy-bufotenine (3) 3.07 ± 0.22 mg/g and 2-methyl-6-methoxy-1,2,3,4-tetrahydro-ß-carboline (4) 0.14 ± 0.004 mg/g. The water decoction presented slightly lower levels, ranging between 2.32 ± 0.14, 0.50 ± 0.04, 1.53 ± 0.09 and 0.10 ± 0.01 mg/g for (1), (2), (3) and (4) respectively. CONCLUSIONS: The HPLC-ESI/MS/MS quantitation revealed significant alkaloid levels, in particular for bufotenine and 5-methoxy-bufotenine. As such compounds are known for their toxic and hallucinogenic properties, these results indicate that the consumption of this plant as an ingredient in ayahuasca preparations may present a risk to consumers.
Subject(s)
Alkaloids/analysis , Chromatography, High Pressure Liquid/methods , Malpighiaceae/chemistry , Spectrometry, Mass, Electrospray Ionization/methods , Tandem Mass Spectrometry/methods , Alkaloids/chemistry , Brazil , Bufotenin/analogs & derivatives , Bufotenin/analysis , Carbolines/analysis , Hallucinogens/chemistry , Plant Bark/chemistry , Serotonin/analogs & derivatives , Serotonin/analysisABSTRACT
ETHNOPHARMACOLOGICAL RELEVANCE: Diospyros bipindensis (Gürke) stem bark is used in Cameroon by Baka Pygmies for the treatment of respiratory disorders. AIM OF THE STUDY: To assess the anti-inflammatory, antibacterial and antioxidant properties of constituents from the bark extracts through bioassay-guided fractionation. MATERIALS AND METHODS: The anti-inflammatory activity of extracts, fractions and pure compounds was assessed through the inhibition of the pro-inflammatory mediator nuclear factor-kappa B (NF-κB) transcriptional activity and nitric oxide (NO) production. DPPH, ABTS and ORAC assays were used for determining the antioxidant properties. The activity against Streptococcus pneumoniae, Staphylococcus aureus, Streptococcus pyogenes, Escherichia coli and Klebsiella pneumoniae, was evaluated on the basis of the minimum inhibitory concentration (MIC) and the minimum bactericidal concentration (MBC) by the macrodilution method. RESULTS: The water extract showed antimicrobial activity against S. pneumoniae (MIC: 300 µg/ml) and S. pyogenes (MIC: 300 µg/ml). The dichloromethane extract efficiently inhibited NF-κB transcriptional activity and NO production and exhibited significant antioxidant activity in the ORAC assay. An interesting activity was also found against S. pneumoniae (MIC: 200 µg/ml), S. aureus (MIC: 400 µg/ml) and S. pyogenes (MIC: 200 µg/ml). The phytochemical investigation of the dichloromethane extract afforded plumbagin, canaliculatin, ismailin, betulinic acid and 4-hydroxy-5-methyl-coumarin as the main constituents. Plumbagin and ismailin were found to be responsible for the main biological activities observed. CONCLUSIONS: These results may provide a rational support for the traditional use of Diospyros bipindensis stem bark in the treatment of respiratory disorders, since the anti-inflammatory, antimicrobial and antioxidant compounds isolated from the dichloromethane extract were also present in the traditional water extract.
Subject(s)
Anti-Bacterial Agents/pharmacology , Anti-Inflammatory Agents/pharmacology , Antioxidants/pharmacology , Diospyros , Animals , Anti-Bacterial Agents/isolation & purification , Anti-Inflammatory Agents/isolation & purification , Antioxidants/isolation & purification , Bacteria/drug effects , Biphenyl Compounds/metabolism , Cell Line , HEK293 Cells , Humans , Mice , Microbial Sensitivity Tests , NF-kappa B/metabolism , Naphthoquinones/isolation & purification , Naphthoquinones/pharmacology , Nitric Oxide/metabolism , Pentacyclic Triterpenes , Picrates/metabolism , Plant Bark , Plant Extracts/chemistry , Triterpenes/isolation & purification , Triterpenes/pharmacology , Tumor Necrosis Factor-alpha , Betulinic AcidABSTRACT
A new prenylated salicylic acid derivative, 3-farnesyl-2-hydroxy benzoic acid (1), was isolated from the leaves of Piper multiplinervium C. DC. (Piperaceae). It showed anti-Helicobacter pylori activity (MIC 37.5 microg/ml) and antimicrobial activity at MICs between 2.5 and 5 microg/ml against Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Mycobacterium smegmatis, Pseudomonas aeruginosa and Candida albicans. Its structure was elucidated by means of MS, 1H and 13C NMR. The ethnomedical claim of Piper multiplinervium to treat stomach aches by the Kuna Indians of Panama may be justified by anti-Helicobacter pylori activity of its MeOH extract.
Subject(s)
Anti-Infective Agents/pharmacology , Farnesol/analogs & derivatives , Helicobacter pylori/drug effects , Hydroxybenzoates/pharmacology , Piper/chemistry , Anti-Infective Agents/isolation & purification , Escherichia coli/drug effects , Escherichia coli/growth & development , Farnesol/pharmacology , Helicobacter pylori/growth & development , Microbial Sensitivity Tests , Molecular Structure , Panama , Plant Leaves , Staphylococcus aureus/drug effects , Staphylococcus aureus/growth & developmentABSTRACT
HPLC-UV-MS analysis of the methanol extract of Jamesbrittenia fodina (Wild) O. M. Hilliard (Scrophulariaceae) revealed the presence of different iridoid cinnamic esters; however, isolation of these constituents was prevented by instability problems. HPLC-UV-MS and HPLC-NMR analysis of the mixtures obtained after a tentative isolation indicated that, in the first instance, instability was due to a light-induced cis/trans isomerisation of the cinnamic moieties. Further investigation of related compounds showed an additional instability problem linked to other chemical transformations. A detailed HPLC-NMR-MS study of these fractions demonstrated that the modifications occurred on the rhamnose moiety of these iridoids. It could be concluded that the second type of instability was attributable to transesterification of the cinnamic moiety on the rhamnose unit. The recording of stop-flow HPLC-NMR spectra for specific HPLC peaks permitted the direct monitoring of these transformations. Based on these on-line data, six new unstable aucubin derivatives were efficiently characterised.
Subject(s)
Iridoids/analysis , Iridoids/chemistry , Scrophulariaceae/chemistry , Chromatography, High Pressure Liquid , Magnetic Resonance Spectroscopy , Mass Spectrometry , Molecular Structure , Online SystemsABSTRACT
The dichloromethane extract of the aerial parts of Blumea gariepina (Asteraceae) was shown to be active against the phytopathogenic fungus Cladosporium cucumerinum and to inhibit acetylcholinesterase. In order rapidly to identify the active principles, the crude extract was analysed by on-flow HPLC-1H-NMR. HPLC-micro-fractionation was performed and all peaks collected were submitted to assays against C. cucumerinum and acetylcholinesterase. By this means, the biological activities could be efficiently associated with selected HPLC peaks. Complementary on-line structural data for all peaks of interest in the crude extract were obtained from HPLC-MS and from HPLC-UV with post-column addition of UV shift reagents. This chemical screening strategy with integrated bioassays permitted the on-line identification of a number of constituents and gave useful information for an efficient isolation procedure.
Subject(s)
Asteraceae/chemistry , Flavonols/isolation & purification , Thymol/analogs & derivatives , Antifungal Agents/isolation & purification , Antifungal Agents/pharmacology , Cholinesterase Inhibitors/isolation & purification , Cholinesterase Inhibitors/pharmacology , Chromatography, High Pressure Liquid , Chromatography, Thin Layer , Flavonols/pharmacology , Molecular Structure , Nuclear Magnetic Resonance, Biomolecular , Plant Extracts/chemistry , Plant Extracts/isolation & purification , Plant Extracts/pharmacology , Spectrometry, Mass, Electrospray Ionization , Spectrophotometry, Ultraviolet , Thymol/isolation & purification , Thymol/pharmacologyABSTRACT
The bark of catuaba (Erythroxylum vacciniifolium Martius, Erythroxylaceae), a tree native to the northern part of Brazil, was investigated for its alkaloid content. With the aim of obtaining preliminary structure information on-line, the alkaloid extract was analysed by high-performance liquid chromatography coupled to diode array UV detection, to mass spectrometry and to nuclear magnetic resonance. Interpretation of on-line spectroscopic data obtained from this extract led to structural elucidation of six new alkaloids and partial identification of 18 potentially original alkaloids bearing the same tropane skeleton esterified in positions 3 and 6 by 1-methyl-1H-pyrrol-2-carboxylic acid and/or 4-hydroxy-3,5-dimethoxybenzoic acid.
Subject(s)
Alkaloids/analysis , Chromatography, High Pressure Liquid/methods , Erythroxylaceae/chemistry , Magnetic Resonance Spectroscopy/methods , Mass Spectrometry/methods , Spectrophotometry, Ultraviolet/methods , Alkaloids/chemistry , Molecular Structure , Tropanes/chemistryABSTRACT
Heliotropamide (1), a new alkaloid with a novel oxopyrrolidine-3-carboxamide central moiety, has been isolated as the major product of the dicholoromethane extract of Heliotropium ovalifolium aerial parts. Its structure was elucidated by spectrometric methods including ESI-HR, EI, D/CI mass spectrometry, (1)H, (13)C, and 2D NMR experiments, and chemical derivatization. Neither heliotropamide nor its acetylated derivative (1a) showed any antifungal activity against Cladosporium cucumerinum and Candida albicans, antibacterial activity against Bacillus subtilis, radical-scavenging properties in the DPPH test, or inhibitory potential toward acetylcholinesterase.
Subject(s)
Alkaloids/isolation & purification , Anti-Bacterial Agents/isolation & purification , Antifungal Agents/isolation & purification , Cholinesterase Inhibitors/isolation & purification , Free Radical Scavengers/isolation & purification , Heliotropium/chemistry , Plants, Medicinal/chemistry , Pyrrolidines/isolation & purification , Alkaloids/chemistry , Alkaloids/pharmacology , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/pharmacology , Antifungal Agents/chemistry , Antifungal Agents/pharmacology , Bacillus subtilis/drug effects , Candida albicans/drug effects , Cholinesterase Inhibitors/chemistry , Cholinesterase Inhibitors/pharmacology , Cladosporium/drug effects , Free Radical Scavengers/chemistry , Free Radical Scavengers/pharmacology , Microbial Sensitivity Tests , Molecular Structure , Nuclear Magnetic Resonance, Biomolecular , Pyrrolidines/chemistry , Pyrrolidines/pharmacology , ZimbabweABSTRACT
LC-UV-MS analysis of the methanol extract of Jamesbrittenia fodina O. M. Hilliard (Scrophulariaceae) revealed the presence of cinnamic ester derivatives. Two isomeric pairs of these constituents were detected, but could not be isolated. In order to identify these unstable compounds, LC-1H-NMR spectra were obtained for each individual isomer and standard NMR measurements were performed in-mixture. The spectra clearly demonstrated that the fractions consisted of mixtures of cis and trans cinnamoyl catalpol glycoside esters.
Subject(s)
Chromatography, Liquid/methods , Glucosides/analysis , Glucosides/chemistry , Iridoids/analysis , Iridoids/chemistry , Magnetic Resonance Spectroscopy/methods , Mass Spectrometry/methods , Scrophulariaceae/chemistry , Glucosides/metabolism , Iridoid Glucosides , Iridoids/metabolism , Molecular Structure , Plant Components, Aerial/chemistryABSTRACT
The absolute configuration of asymmetric centres of two alpha-pyrones isolated from Ravensara crassifolia was determined using the Mosher method. The conventional analysis of the purified ester derivatives by 1H-NMR was replaced by a rapid and sensitive method in which the alpha-pyrones were analysed under isocratic reversed-phase LC-NMR conditions prior to and after derivatisation reactions. Comparison of the LC-1H-NMR spectra of the actual alpha-pyrones with those of the corresponding Mosher's esters recorded in the acetonitrile:deuterated water solvent system exhibited shifts comparable with those obtained using conventional deuterated solvents. Based on the shifts recorded, determination of the absolute configuration was possible by application of Mosher rules. The use of LC-NMR has permitted a direct analysis of crude reaction mixtures containing less than 50 microg of the starting material. Completion of the reaction was checked by LC-MS and the crude reaction mixture was analysed by stop-flow LC-NMR. This methodology seems very promising for the determination at the micro-scale level of the absolute configuration of natural products which are available only in very small amounts.
Subject(s)
Lauraceae/chemistry , Pyrones/chemistry , Pyrones/isolation & purification , Alkylation , Chromatography, Liquid , Magnetic Resonance Spectroscopy , Molecular StructureABSTRACT
In our continuing search for new antifungal agents of plant origin, the investigation of Erythrina vogelii Hook. f. (Leguminosae), a plant used in the traditional medicine of Ivory Coast to treat various infectious ailments, was undertaken. In order to rapidly identify the active principles, the crude extract was analysed by low-flow LC-1H nuclear magnetic resonance spectrometry (NMR) which gave a sensitive detection of all the main peaks. LC microfractionation was performed just after LC-NMR detection and all peaks collected were submitted to antifungal bioautography assays against Cladosporium cucumerinum. By this means, the antifungal activity could be efficiently linked to three of the LC peaks. In order to obtain complementary on-line structural information for all peaks of interest, high-resolution LC-MS-MS together with LC-UV with post-column addition of UV shifts reagents was undertaken on the crude extract. This chemical screening strategy with integrated antifungal bioassays has permitted the on-line identification of numerous constituents and has given useful information for an efficient peak-guided isolation procedure.
Subject(s)
Antifungal Agents/isolation & purification , Chromatography, Liquid/methods , Fabaceae/chemistry , Magnetic Resonance Spectroscopy/methods , Mass Spectrometry/methods , Spectrophotometry, Ultraviolet/methods , Chromatography, Thin LayerABSTRACT
Phytochemical investigation of the CH2Cl2 extract of Erythrina vogelii led to the isolation of five isoflavonoids. Three prenylated isoflavonoids are new natural compounds. The isolation of the antifungal compounds was monitored by inhibition of the growth of Cladosporium cucumerinum in a direct TLC bioautographic assay. The structures of these compounds were elucidated by spectroscopic techniques.
Subject(s)
Antifungal Agents/pharmacology , Cladosporium/drug effects , Erythrina , Flavonoids/isolation & purification , Isoflavones/isolation & purification , Plant Extracts/isolation & purification , Flavonoids/chemistry , Flavonoids/pharmacology , Isoflavones/chemistry , Isoflavones/pharmacology , Magnetic Resonance Spectroscopy , Molecular Structure , Plant Bark/chemistry , Plant Extracts/chemistry , Plant Extracts/pharmacology , Plant Roots/chemistry , Protein PrenylationABSTRACT
Two new benzoquinones, heliotropinones A and B, have been isolated from the aerial parts of Heliotropium ovalifolium. Their structures were elucidated by spectrometric methods including high resolution electrospray ionization (ESI-HR), EI mass spectrometry, 1H, 13C and 2D NMR experiments. The two quinones demonstrated antifungal activities against Cladosporium cucumerinum and Candida albicans as well as antibacterial activity against Bacillus subtilis.
Subject(s)
Anti-Infective Agents/isolation & purification , Benzoquinones/isolation & purification , Boraginaceae/chemistry , Anti-Bacterial Agents , Anti-Infective Agents/chemistry , Anti-Infective Agents/pharmacology , Bacillus subtilis/drug effects , Benzoquinones/chemistry , Benzoquinones/pharmacology , Candida albicans/drug effects , Cladosporium/drug effects , Microbial Sensitivity Tests , Spectrum AnalysisABSTRACT
Several glycosyl derivatives of squamocin (1) have been synthesized by glycosylation under Lewis acid catalysis with two different 1-O-acetyl sugars. Separation of these compounds has been achieved by HPLC and centrifugal partition chromatography (CPC). A detailed NMR, ESIMS, and LSIMS study allowed complete structural elucidations. The cytotoxic activity of the glycosyl derivatives was investigated and compared with that of squamocin and dihydrosquamocin against human epidermoid carcinoma cells (KB), African green monkey (Cercopithecus aethiops) kidney epithelial cells (VERO), and mouse lymphocytic leukemia cells (L1210). The antiproliferative effects of some derivatives were studied on cell cycles in mouse lymphocytic leukemia cells (L1210).
Subject(s)
Antineoplastic Agents/chemical synthesis , Furans/chemical synthesis , Lactones/chemical synthesis , Animals , Antineoplastic Agents/chemistry , Antineoplastic Agents/pharmacology , Cell Cycle/drug effects , Chlorocebus aethiops , Drug Screening Assays, Antitumor , Furans/chemistry , Furans/pharmacology , Glycosylation , Humans , Lactones/chemistry , Lactones/pharmacology , Magnetic Resonance Spectroscopy , Mass Spectrometry , Mice , Tumor Cells, Cultured , Vero CellsABSTRACT
A new bistetrahydrofuran acetogenin, salzmanin (1), was isolated from the MeOH extract of Annona salzmanii, in addition to the known compounds, squamocin, almunequin, bullatalicin, and annonacin. The structure of 1 was elucidated by spectroscopic methods, including LSIMS-MS technique, and confirmed by a chemical transformation. The cytotoxic activity of 1 and squamocin was investigated.
Subject(s)
4-Butyrolactone/analogs & derivatives , Antineoplastic Agents, Phytogenic/isolation & purification , Magnoliopsida/chemistry , 4-Butyrolactone/chemistry , 4-Butyrolactone/isolation & purification , 4-Butyrolactone/pharmacology , Antineoplastic Agents, Phytogenic/chemistry , Antineoplastic Agents, Phytogenic/pharmacology , Drug Screening Assays, Antitumor , Furans/chemistry , Furans/isolation & purification , Furans/pharmacology , Humans , Lactones/chemistry , Lactones/isolation & purification , Lactones/pharmacology , Magnetic Resonance Spectroscopy , Mass Spectrometry , Molecular Conformation , Plant Roots/chemistry , Spectrophotometry, Ultraviolet , Tumor Cells, CulturedABSTRACT
Three new bistetrahydrofuran acetogenins, carolins A-C (1-3), were isolated from the MeOH extract of Annona spinescens in addition to the known compound, squamocin (4). The structures of 1, 2, and 3 were elucidated by spectroscopic methods including LSIMS/MS technique and confirmed by a chemical transformation, The cytotoxic activity of the new compounds 1-3 is reported and discussed in comparison with 4 and the previously isolated spinencin (5).
Subject(s)
4-Butyrolactone/analogs & derivatives , Antineoplastic Agents, Phytogenic/isolation & purification , Fatty Alcohols/isolation & purification , Plants, Medicinal/chemistry , 4-Butyrolactone/isolation & purification , 4-Butyrolactone/pharmacology , Animals , Antineoplastic Agents, Phytogenic/pharmacology , Chlorocebus aethiops , Drug Screening Assays, Antitumor , Fatty Alcohols/pharmacology , Humans , Magnetic Resonance Spectroscopy , Molecular Conformation , Seeds/chemistry , Spectrophotometry, Ultraviolet , Tumor Cells, Cultured , Vero CellsABSTRACT
The trunk bark and roots of Annona spinescens have been investigated for their alkaloid content. Two new berbine alkaloids, pessoine (1) and spinosine (2), have been isolated from the bark, and their structures were elucidated by spectroscopic methods. Eight known isoquinoline alkaloids were also obtained. The trypanocidal and antileishmanial activities of these isolated compounds have been investigated.
Subject(s)
Antiprotozoal Agents/isolation & purification , Berberine Alkaloids/isolation & purification , Leishmania/drug effects , Plants, Medicinal/chemistry , Animals , Antiprotozoal Agents/pharmacology , Berberine Alkaloids/pharmacology , Magnetic Resonance Spectroscopy , Spectrophotometry, Ultraviolet , Trypanocidal Agents/isolation & purification , Trypanocidal Agents/pharmacology , Trypanosoma cruzi/drug effectsABSTRACT
Mean serum zinc (1.14 micrograms/ml) and copper (2.35 micrograms/ml) in 24 women taking oral contraceptive agents were compared against mean serum zinc (1.25 micrograms/ml) and copper (1.98 micrograms/ml) of 20 women of the same age range who served as controls. Serum zinc was significantly lower while serum copper was significantly higher for women taking the oral contraceptive agents. There was no significant correlation between the serum zinc and copper levels either in the control group (r = 0.04) or in the group taking the contraceptives (r = 0.36).
PIP: Mean serum zinc (1.14 mcg/ml) and copper (2.35 mcg/ml) in 24 women taking oral contraceptives (OCs) were compared against mean serum zinc (1.29 mcg/ml) and copper (1.98 mcg/ml) of 20 same-aged women who served as controls. Serum zinc was significantly lower while serum copper was significantly higher for women taking the OCs. There was no significant correlation between the serum zinc and copper levels either in the control group (r=0.04) or in the group taking the contraceptive (r=0.36). (author's modified)
Subject(s)
Contraceptives, Oral, Hormonal/adverse effects , Contraceptives, Oral/adverse effects , Copper/blood , Estrogens/adverse effects , Progestins/adverse effects , Zinc/blood , Adult , Female , Humans , Zinc/deficiencyABSTRACT
Niveis sericos medios de zinco (1.14 micrograma/ml) e cobre 2.35 micrograma/ml), em 24 mulheres em uso de anovulatorios orais, foram comparados com niveis sericos medios de zinco (1.29 micrograma/ml) e cobre (1.98 micrograma/ml) de 20 mulheres da mesma faixa etaria que serviram como controles. Os valores encontrados no grupo em uso de anovulatorios foram significantemente mais baixos para o zinco e significantemente mais elevados para o cobre, quando comparados com os valores observados no grupo controle. Nao houve correlacao significativa entre zinco e cobre sericos no grupo controle (r = 0.04) e tampouco no grupo em uso de anovulatorios (r = 0.36)