Recognition of antioxidants and photosensitizers in Dyssodia pinnata by EPR spectroscopy.

INTRODUCTION: Previous studies report the isolation mainly of terthiophene derivatives and flavonoids from Dyssodia species. Terthiophenes are known as photosensitizers by their capacity to generate singlet oxygen (1 O2 ), and flavonoid antioxidant activity is recognized. These opposite properties could represent interesting options in photodynamic therapy. OBJECTIVE: To determine the antioxidant and photosensitizer activities of extracts and isolates of Dyssodia pinnata by electron paramagnetic resonance (EPR). METHODOLOGY: Extracts and isolates were evaluated as antioxidants by the interactions with copper ion (Cu2+ ) observed in EPR, and by the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH) and the thiobarbituric reactive substances (TBARS) methods. Their abilities as 1 O2 producers were also estimated by EPR. RESULTS: Terthiophenes were obtained from hexane (DPH) and acetone (DPA) extracts, and flavonoids from DPA and methanol (DPM) extracts. The interaction with Cu2+ of extracts and isolated compounds of Dyssodia pinnata showed two effects in EPR: reduction and chelation; flavonoids exhibited both effects, while terthiophenes showed only reduction. DPA, DPM, and flavonoids were active in DPPH and TBARS assays. Quercetagetin-7-O-ß-glucoside showed the highest antioxidant and chelating activities, 3-glycosidated flavonoids were less active. Upon irradiation extracts and terthiophenes induced 1 O2 formation. CONCLUSION: Flavonoid reducing activity on Cu2+ and free radical scavenging capacity were related to the number of hydroxy groups and to the conjugation between the B and C rings. All tested flavonols showed a major complex with Cu2+ , with the most probable site of chelation between the 5-hydroxy and 4-oxo groups. Extracts and terthiophene derivatives showed photosensitizer activity. Thus, EPR is useful to evaluate free radical scavenging and pro-oxidant properties.

Chemical Composition and Antimicrobial Activity of Ageratina deltoidea.

The chemical study of Ageratina deltoidea afforded grandiflorenic acid (1), ent-kaurenoic acid (2), and eight benzylbenzoates (3 - 10), two of them, 3,5-dimethoxybenzyl 2,3,6-trimethoxybenzoate (5) and 4-(ß-d-glucopyranosyloxy)-3-hydroxybenzyl 2,6-dimethoxybenzoate (9), described for the first time. In addition, the new sesquiterpene lactone deltoidin C (13), together with the known 11 and 12, the phenolic compounds: ayanin, 2,6-dimethoxybenzoic acid, methyl 3,4-dihydroxycinnamate, chlorogenic acid, and 3,5-dicaffeoylquinic acid were also isolated. The structures of these compounds were determined by spectroscopic methods and chemical reactions. The antibacterial and antifungal activities of compounds 1 - 12 were evaluated on Staphylococcus aureus, Escherichia coli, and Candida albicans. Deltoidin A (11) was the most active antibacterial agent (MIC 16.0 µg ml-1 ) against E. coli, and the ent-kaurenoid derivatives (1 - 2) showed activity (MIC 31.0 µg ml-1 ) against S. aureus.

Terpenoids from Melampodium perfoliatum.

The phytochemical study of the aerial parts of Melampodium perfoliatum afforded six melampolides (1, 3, 5-8), a eudesmanolide (9), two diterpene lactones (10, 11), and two ent-kaurane derivatives (12, 13), together with the known melampodin (2) and polymatin A (4). The structures of the compounds were elucidated by physical data analysis and chemical reactions. Compounds 2, 4, 5, and 10 exhibited dose-dependent anti-inflammatory activity on the 12-O-tetradecanoylphorbol-13-acetate-induced ear edema model, with ID50 values of 1.14, 0.56, 1.15, and 1.49 µmol/ear, respectively, compared to the reference compound indomethacin (0.24 µmol/ear).

Sesquiterpenoids from Pittocaulon filare.

The phytochemical study of Pittocaulon filare afforded three oplopanes (1-3), a eudesmane (6), and three oplopane glucosides (7-9), one of them reported as its acetyl derivative (7a), together with several known compounds. The structures of the compounds were elucidated by spectroscopic analysis and chemical reactions. The anti-inflammatory activity of compounds 1-5 was determined using the 12-O-tetradecanoylphorbol-13-acetate (TPA)-induced ear edema model, and the effect of compounds 1-4 on the recruitment of neutrophils was evaluated using the myeloperoxidase test. Compounds 1 and 2 were the more active anti-inflammatory agents, with lower ID50 values (0.17 and 0.18 µmol/ear, respectively) than indomethacin (0.24 µmol/ear), but they had a lesser effect on the inhibition of neutrophil infiltration than both indomethacin and compound 3, indicating that the tested compounds do not have the same ability to inhibit edema and to prevent cell infiltration.

Antihyperglycemic effect and genotoxicity of Psittacanthus calyculatus extract in streptozotocin-induced diabetic rats / Efecto antihiperglicemico y genotoxico de extractos de Psittacanthus calyculatus en ratas diabeticas inducidas con streptozotocina

Psittacanthus calyculatus (DC.) G. Don (Lorantaceae) is known as “ingerto”. The aerial parts are used in the treatment of diabetes and hypertension. Methanolic extract was tested with streptozotocin-induced diabetic rats. Dose of 200 mg/Kg body weight for acute experiments, as well as 200 and 400 mg/Kg for semi-chronic bioassay were used. In both experiments extract produced significant hypoglycemic activity in streptozotocin-induced rats when compared with diabetic control (p 0.05). To study possible clastogenic effects of methanolic extract a mouse micronucleus test was performed (as part of the genetic toxicology trial). CD-1 white mice were administered with 200 and 400 mg/Kg of methanolic extract of P. calyculatus dissolved in water by intraperitoneal injection. The cytotoxic activity polychromatic erythrocytes/normochromatic erythrocytes (PCE/NCE) and the induction of micronuclei in peripheral blood erythrocytes (MNPCE) was recorded with sampling times of 24, 48 and 72, h after an exposure without killing of mice. The frequency of MNPCE in the circulating blood obtained from the tail of the mouse was statistically not significant compared with its negative control animals (time zero) and the PCE/NCE ratio showed evidences of light cytotoxic activity compared with its negative control animals (time zero). Thus, in this test, the methanolic extract of Psittacanthus calyculatus dissolved in water did not induce chromosomal damage resulting in micronucleus formation in peripheral blood erythrocytes and showed light cytotoxic activity.

En la zona del bajío mexicano la planta Psittacanthus calyculatus (DC.) G. Don (Lorantaceae) es conocida popularmente como “ingerto”. Las partes aéreas de este vegetal se utilizan para tratar enfermedades como la diabetes y la hipertensión. Se realizaron experimentos agudos y semi-crónicos en ratas diabéticas inducidas con estreptozotocina. El efecto hipoglucemiante del extracto metanólico se evaluó a dosis de 200 y 400 mg/Kg de peso. En ambos experimentos, el extracto redujo significativamente (p < 0.05) la glucemia en las ratas diabéticas. Para determinar los posibles efectos clastogénicos del extracto metanólico se administraron por vía intraperitoneal a ratones cepa CD-1 las dosis que mostraron actividad hipoglucemiante disueltas en agua y se llevó a cabo el bioensayo de micronúcleos en sangre periférica de ratón. La actividad citotóxica se determinó mediante el cálculo de la relación entre los eritrocitos policromáticos y los eritrocitos normocromáticos (PCE/NCE). La inducción de micronúcleos en eritrocitos de sangre periférica (MNPCE) fue el indicador de gentotoxicidad los cuales se midieron a las 24, 48 y 72 horas después de la administración del extracto. La frecuencia de micronúcleos en eritrocitos policromáticos no fue estadísticamente significativa con relación al control negativo (al tiempo 0) por lo tanto, el extracto no induce daño cromosómico. Asimismo la relación PCE/NCE mostró que el extracto metanólico fue ligeramente citotóxico a la dosis de 400 mg/Kg y a las 48 h posteriores a la administración.

Chemical constituents of Roldana lineolata.

The new eremophilanolide 1, the known eremophilane derivatives 2 and 3, already described as part of mixtures, the known compounds hyperin, 2''-acetylhyperin and two calenduladiol esters were isolated from Roldana lineolata. Their structures were determined by spectroscopic methods. Compounds 1 and 2 as well as their acetylated and oxidized derivatives were tested against several fungi strains. Eremophilanolide 1 showed a mild activity against Trichophyton mentagrophytes.

Cacalol derivatives from Roldana angulifolia.

Four new modified eremophilanes, angulifolide (1) and angulifolins A-C (2-4), and two new triacetylglucosides (7 and 8) were isolated from Roldana angulifolia, together with several known compounds. The structures of the new compounds were elucidated by spectroscopic analysis and chemical reactions. The absolute configuration of compounds 2 and 3 was established by Mosher ester methodology. Cytotoxicity against selected human cancer cell lines was determined for the more abundant isolated metabolites.

Eremophilanes from Senecio mairetianus and some reaction products.

Eight new eremophilanolides (1, 2, 4-7, 9, and 10), a new eremophilane (13), and several known compounds were isolated from the roots and aerial parts of Senecio mairetianus. The chemical structures were proposed taking into consideration spectroscopic analyses and chemical transformations. X-ray diffraction analysis of 2, 4, and 9 confirmed their structures. The stereochemistry of 1,10-epoxy-8alpha-methoxyermophilanolide (3) was determined. Compounds 4-7, 9, and 10 are possible artifacts obtained by preparation of the alkaloidal extract.

Insect growth inhibition by tocotrienols and hydroquinones from Roldana barba-johannis.

The methanol extract from the aerial parts of Roldana barba-johannis (Asteraceae) afforded sargachromenol, sargahydroquinoic acid, and sargaquinoic acid. These natural products and their corresponding acetylated and methylated derivatives showed insecticidal and insect growth regulatory activities against the Fall Armyworm [Spodoptera frugiperda J.E. Smith, (Lepidoptera: Noctuidae)], an important insect pest of corn. The most active compounds were sargachromenol and its acetylated derivative; sargahydroquinoic acid and its acetylated derivative; and a mixture of sargachromenol, sargahydroquinoic acid, and sargaquinoic acid (6:3:1) and the acetylated form of this mixture. All these compounds and mixtures had significant inhibitory effects between 5.0 and 20.0 ppm in diets. Most compounds were insecticidal to larvae, with lethal doses between 20 and 35 ppm. In addition, these substances also demonstrated scavenging properties toward 2,2-diphenyl-1-picrylhydrazyl radical in TLC autographic and spectrophotometric assays. These compounds appear to have selective effects on the pre-emergence metabolism of the insect. The results from these compounds were fully comparable in activity to those known natural insect growth inhibitors such as gedunin and methanol extracts of Cedrela salvadorensis and Yucca periculosa. These substances may be useful as natural insecticidal agents.

Antioxidant and insect growth regulatory activities of stilbenes and extracts from Yucca periculosa.

The methanol extract from the bark of Yucca periculosa F. Baker afforded 4,4'-dihydroxstilbene, resveratrol and 3,3',5,5'-tetrahydroxy-4-methoxystilbene and had growth regulatory activity against the Fall Army worm (Spodoptera frugiperda J.E. Smith, Lepidoptera:Noctuidae) an insect pest of corn. The most active compound was 3,3',5,5'-tetrahydroxy-4-methoxystilbene which had significant effects at 3 microg/g in diets. In addition to the inhibitory activity on bleaching of crocin induced by alkoxyl radicals, these compounds also demonstrated scavenging properties toward 2,2-diphenyl-1-picrylhydrazyl in TLC autographic and spectrophotometric assays. Our results indicate that these compounds could be involved in interference of sclerotization and moulting. These compounds appear to have selective effects on the pre-emergence metabolism of the insect. The results were fully comparable to known natural insect growth inhibitors such as gedunin and Cedrela extracts and have had a possible role as natural insecticidal agents.