Efecto citotóxico de diterpenos derivados del ácido ent-kaureno aislados de Coespeletia moritziana (Sch. Bip. ex Wedd.) Cuatrec / Cytotoxic effect of ent-kaurene acid-derived diterpenes isolated from Coespeletia moritziana (Sch. Bip. Ex Wedd.) Cuatrec

The objective of the work was to study the cytotoxic effect of ent-kaurene acid derivatives obtained from Coespeletia moritziana (Sch. Bip. Ex Wedd.) Cuatrec., After analysis by GC/MS, IR and NMR. Isolating: kaurenic acid (I), grandifloric acid (II), 15-α-hydroxy kaurenic acid (III), 15 α-acetoxy-kaur 16-en-19-oic acid (IV), Kaurenol (V); and by hemisynthesis: 15,16-epoxy-17-acetoxy-kauran 19-oic acid (VI), 15-oxo-ent-kaur-16-en-19-oic acid (VIII), ester 2,3,4,6 -15-oxo-kaur-16-en-19-oic acid acetyl α-D-pyranosyl tetra-tetra (VII). Cytotoxicity was tested in human cancer cell lines: uterus (HeLa), lung (A-549), breast (MCF-7), African green monkey kidney non-tumor line (Vero) and human peripheral blood mononuclear cells (CMPS). Compound (I) was active against HeLa, A-549 and Vero. Compounds (II and VIII) showed moderate and good (IC50 ≤ 9 µM) cytotoxicity, respectively, against the five cell lines. Compound (V) showed moderate activity against A-549 and compound (VII), slight cytotoxicity against HeLa and A-549. Results that show the cytotoxic specificity of the isolated kaurenes and derivatives of Coespeletia moritzianaand their therapeutic potential.

El objetivo del trabajo fue estudiar el efecto citotóxico de derivados del ácido ent-kaureno obtenidos de Coespeletia moritziana (Sch. Bip. ex Wedd.) Cuatrec., previo análisis mediante GC/MS, IR y RMN. Aislandose: ácido kaurénico(I), ácido grandiflorénico (II), ácido 15-α-hidroxi kaurénico(III), ácido 15 α-acetoxi-kaur 16-en-19-oico (IV), Kaurenol (V); y por hemisíntesis: ácido 15,16-epoxi-17-acetoxi-kauran 19-oico (VI), ácido15-oxo-ent-kaur-16-en-19-oico (VIII), éster 2,3,4,6-tetra acetil α-D-piranosilo del ácido 15-oxo-kaur-16-en-19-oico (VII). La citotóxicidad fue ensayada en líneas celulares cancerosas humanas: útero (HeLa), pulmón(A-549), mama (MCF-7), línea no tumoral de riñón de mono verde africano (Vero) y células mononucleares humanas de sangre periférica (CMPS). El compuesto (I) resultó activo frente a HeLa, A-549 y Vero. Los compuestos (II y VIII), mostraron moderada y buena (IC50≤9µM) citotoxicidad respectivamente, frente a las cinco líneas celulares. El compuesto (V) presentó moderada actividad frente a A-549 y el (VII), leve citotoxicidad frente a HeLa y A-549. Resultados que evidencian la especificidad citotóxica de los kaurenos aislados y derivados de Coespeletia moritzianay su potencial terapéutico.

Chemical and morpho-functional aspects of the interaction between a Neotropical resin bug and a sticky plant

Rubus adenotrichos is an Andean blackberry plant bearing glandular trichomes which secrete an adhesive exudate. The resin bug Heniartes stali is frequently found on this plant and collects this exudate using the forelegs to enhance its preying capacity. Here, we describe the morphology of the plant's glandular trichomes with the aid of light and scanning electron microscopy, as well as the chemical components of the exudate by histochemical and gas chromatography-mass spectrometry analysis. We have also combined behavioral observations with the analysis of the insect leg morphology to identify possible morpho-functional adaptations evolved by H. stali for collecting the sticky secretions. Glandular trichomes exhibited a multicellular long stalk and a calyx-shaped head with radially aligned cells. The composition of the resinous fluid was mainly terpenes and phenolics, which may contribute to its sticky properties. Brush-like structures on the tibia of forelegs in H. stali suggests an adaptive trait for collecting the trichomes exudate. A profusely hair-covered area on metatibiae operated as a resin storage structure. Abundant pore-like openings were observed in the cuticle of this area through which substances could be conceivably secreted to prevent resin hardening. These findings combine morphological and chemical features of a fascinating insect-plant interaction in the Neotropics.

Rubus adenotrichos es una planta de mora andina que contiene tricomas glandulares los cuales secretan un exudado pegajoso. El chinche de las resinas Heniartes stali se encuentra con frecuencia en esta planta recogiendo el exudado con sus patas delanteras para mejorar su capacidad en la captura de las presas. En este trabajo empleamos microscopía de luz y microscopía electrónica de barrido para describir la morfología de los tricomas. Los constituyentes químicos del exudado fueron estudiados mediante técnicas histoquímicas, de cromatografía de gases y espectrometría de masas. También combinamos observaciones del comportamiento del insecto en la recolección y almacenamiento del exudado con el análisis de la morfología de sus patas, empleando microscopía de luz y microscopía electrónica de barrido para identificar las posibles adaptaciones morfo-funcionales desarrolladas para la manipulación de estas secreciones adhesivas. Los tricomas glandulares exhibieron un tallo largo multicelular y una cabeza glandular en forma de cáliz con células alineadas radialmente. El fluido resinoso estaba compuesto principalmente por terpenos y compuestos fenólicos, los cuales parecen contribuir con sus propiedades adhesivas. La presencia de estructuras tipo pincel en las puntas de las tibias de las patas delanteras sugieren un carácter adaptativo para recoger el exudado de los tricomas. También describimos un área en las patas traseras profusamente cubierta de pelos, que funcionaban como estructuras de almacenamiento de la resina. En la cutícula de éstas observamos abundantes aberturas similares a poros y sugerimos que a través de ellos se secretan sustancias que impiden el endurecimiento de la resina almacenada. Estos hallazgos aportan información sobre características morfológicas y químicas de un novedoso modelo de interacción insecto-planta en el neotrópico.

Triterpene saponins from Billia rosea.

Five previously undescribed triterpene saponins, billiosides A-E, and a known analogue, were isolated from the seeds of Billia rosea (Planch. & Linden) C. Ulloa & P. Jørg. Their structures were elucidated on the basis of extensive 1D and 2D NMR experiments (1H, 13C, DEPT, COSY, TOCSY, NOESY, ROESY, HSQC, and HMBC) and mass spectrometry as (3ß,21ß,22α)-3-[(2-O-ß-D-glucopyranosyl-O-[α-L-arabinopyranosyl-(1 â†’ 4)]-ß-D-glucopyranosyl)oxy]-21-[((2E,6S)-2,6-dimethyl-6-hydroxyocta-2,7-dienoyl)oxy]-22-(acetyloxy)-24-hydroxyolean-12-en-28-oic acid, (3ß,21ß,22α)-3-[(2-O-ß-D-galactopyranosyl-ß-D-glucopyranosyl)oxy]-21,22-dihydroxyolean-12-en-28-yl O-α-L-arabinopyranosyl-(1 â†’ 4)-ß-D-glucopyranoside, (3ß,21ß,22α)-3-[(2-O-ß-D-galactopyranosyl-O-[α-L-arabinopyranosyl-(1 â†’ 4)]-ß-D-xylopyranosyl)oxy]-21,22-dihydroxyolean-12-en-28-yl O-ß-D-glucopyranoside, (3ß,21ß,22α)-3-[(2-O-ß-D-galactopyranosyl-O-[α-L-arabinopyranosyl-(1 â†’ 4)]-ß-D-glucopyranosyl)oxy]-21,22-dihydroxyolean-12-en-28-yl O-ß-D-glucopyranoside, (3ß,21ß,22α)-3-[(2-O-ß-D-galactopyranosyl-O-[α-L-arabinopyranosyl-(1 â†’ 4)]-ß-D-glucopyranosyl)oxy]-21,22-dihydroxyolean-12-en-28-yl O-ß-D-glucopyranosyl-(1 â†’ 6)-ß-D-glucopyranoside, and dipteroside A. Billiosides B and C exhibited moderate effects when tested as hepatic glucose-6-phosphatase inhibitors and as glucose intestinal absorption inhibitors, using in situ rat intestinal segments.

Oleanane-type glycosides from Pittosporum tenuifolium "variegatum" and P. tenuifolium "gold star".

The phytochemical study of two cultivars of Pittosporum tenuifolium Banks & Sol. ex Gaertn, "variegatum" and "gold star", led to the isolation of eight oleanane-type glycosides: seven previously undescribed and a known one. Their aglycons are oxygenated oleanane derivatives as barringtogenol C, camelliagenin A, hederagenin, and 22α-hydroxyoleanolic acid. Their structures were established by 2D NMR spectroscopic techniques and mass spectrometry as 3-O-ß-D-galactopyranosyl-(1 â†’ 2)-[α-L-arabinopyranosyl-(1 â†’ 3)]-ß-D-glucuronopyranosyl-21-O-angeloyl-22-O-acetylbarringtogenol C, 3-O-ß-D-galactopyranosyl-(1 â†’ 2)-[α-L-arabinopyranosyl-(1 â†’ 3)]-ß-D-glucuronopyranosyl-21,22-di-O-angeloylbarringtogenol C, 3-O-ß-D-galactopyranosyl-(1 â†’ 2)-[α-L-arabinopyranosyl-(1 â†’ 3)]-ß-D-glucuronopyranosyl-22-O-angeloylcamelliagenin A, 3-O-ß-D-glucopyranosyl-(1 â†’ 2)-[ß-D-glucopyranosyl-(1 â†’ 6)]-ß-D-glucopyranosyl-22-O-[(6-O-acetyl)-ß-D-glucopyranosyl]camelliagenin A, 3-O-ß-D-galactopyranosyl-(1 â†’ 2)-[α-L-arabinofuranosyl-(1 â†’ 4)]-ß-D-glucuronopyranosylhederagenin 28-O-ß-D-glucopyranosyl ester, 3-O-α-L-arabinofuranosyl-(1 â†’ 4)-ß-D-glucuronopyranosylhederagenin 28-O-ß-D-glucopyranosyl ester, 3-O-ß-D-galactopyranosyl-(1 â†’ 2)-[α-L-arabinofuranosyl-(1 â†’ 4)]-ß-D-glucuronopyranosyl-22α-hydroxyoleanolic acid 28-O-ß-D-glucopyranosyl ester, and the known ilexoside XLIX. These results represent a significative contribution to the chemotaxonomy of the genus Pittosporum, highlighting hederagenin-type saponins as chemotaxonomic markers of P. tenuifolium cultivars.

Chemical Composition and in vitro Antibacterial Activity of the Essential Oil of Verbesina negrensis from the Venezuelan Andes.

The composition and antimicrobial activity of the essential oil from Verbesina negrensis Steyerm. leaves is reported. Analysis was performed by GC/MS. Major constituents were α-pinene (43.1%), α-humulene (13.8%), Δ-cadinene (8.1%), limonene (4.6%) and bicyclogermacrene (4.2%). The essential oil showed in vitro activity against the Gram-positive bacteria Staphylococcus aureus ATCC 25923 and Enterococcus faecalis ATCC 29212 (MIC 500 and 350 µL/mL respectively).

Volatile Constituents from the Flowers of Spathodea campanulata from the Venezuelan Andes.

The chemical composition is reported of the essential oil obtained by hydrodistillation of Spathodea campanulata P. Beauv. (Bignoniaceae) flowers collected in the Andes region of Venezuela. Thirty compounds were characterized, representing 96.5% of the total oil composition; benzyl benzoate (17.5%) was the major constituent. Others major components were a mixture of geranyl acetone with a-humulene (12.7%), ß-caryophyllene (9.5%), farnesyl acetone (6.0%), aromadendrene (4.3%), α-gurjunene (3.9%) and tricosane (3.7%). This is the first report related to the chemical composition of the essential oil of S. campanulata flowers.

Acylated oleanane-type saponins from Ganophyllum giganteum.

Five oleanane-type saponins, 3-O-ß-D-glucuronopyranosylzanhic acid 28-O-ß-D-xylopyranosyl-(1→3)-[α-L-rhamnopyranosyl-(1→2)]-(4-O-acetyl)-ß-D-fucopyranosyl ester (1), 3-O-ß-D-glucopyranosylzanhic acid 28-O-ß-D-xylopyranosyl-(1→3)-[α-L-rhamnopyranosyl-(1→2)]-(4-O-acetyl)-ß-D-fucopyranosyl ester (2), zanhic acid 28-O-ß-D-xylopyranosyl-(1→3)-[α-L-rhamnopyranosyl-(1→2)]-(4-O-acetyl)-ß-D-fucopyranosyl ester (3), zanhic acid 28-O-α-L-rhamnopyranosyl-(1→2)-4-O-[(3'-hydroxy-2'-methyl-butyroyloxy)-3-hydroxy-2-methyl-butyroyloxy]-ß-D-fucopyranosyl ester (4), medicagenic acid 28-O-α-L-rhamnopyranosyl-(1→2)-4-O-[(3'-hydroxy-2'-methyl-butyroyloxy)-3-hydroxy-2-methyl-butyroyloxy]-ß-D-fucopyranosyl ester (5), were isolated from the root barks of Ganophyllum giganteum. Compounds 4 and 5 possessed an unusual substitution of the C-4 position of the ß-D-fucopyranosyl moiety by a C10 ester group formed by two symmetrical C5 nilic acid. From a chemotaxonomic point of view, their structures are in accordance with the previous saponins isolated from the Doratoxyleae tribe of the Sapindaceae family. Their cytotoxicity and anti-inflammatory activity were also evaluated.

Chemical composition of the essential oil from the leaves of Carapa guianensis collected from Venezuelan Guayana and the antimicrobial activity of the oil and crude extracts.

The essential oil obtained by hydrodistillation of Carapa guianensis Aubl. (Meliaceae) leaves was analyzed by GC-FID and GC-MS. Twenty-three components were identified, which made up 93.7% of the oil. The most abundant constituents were bicyclogermacrene (28.5%), alpha-humulene (17.2%), germacrene B (11.9%), and trans-beta-caryophyllene (9.9%). Antimicrobial activity of the essential oil, as well as the crude extracts of the leaves obtained by refluxing the dried leaves with n-hexane, dichloromethane, and methanol, was determined using the disc diffusion assay. Activity against Staphylococcus aureus ATCC 29923 and Enterococcus faecalis ATCC 29212 was only found for the essential oil and the methanolic extract, at minimal inhibitory concentrations (MIC) of 400 microg/mL and 50 microg/mL.

Steroidal saponins from the fruits of Solanum torvum.

Seven steroidal glycosides have been isolated from the fruits of Solanum torvum Swartz. Their structures were established by 2D NMR spectroscopic techniques ((1)H,(1)H-COSY, TOCSY, NOESY, HSQC, and HMBC) and mass spectrometry as (25S)-26-(ß-D-glucopyranosyloxy)-3-oxo-5α-furost-20(22)-en-6α-yl-O-ß-D-xylopyranoside (1), (25S)-26-(ß-D-glucopyranosyloxy)-3-oxo-22α-methoxy-5α-furostan-6α-yl-O-ß-D-xylopyranoside (2), (25S)-26-(ß-D-glucopyranosyloxy)-3ß-hydroxy-22α-methoxy-5α-furostan-6α-yl-O-α-L-rhamnopyranosyl-(1→3)-ß-D-glucopyranoside (3), (25S)-3ß-hydroxy-5α-spirostan-6α-yl-O-ß-D-xylopyranoside (4), (25S)-3-oxo-5α-spirostan-6α-yl-O-ß-D-xylopyranoside (5), (25S)-3ß-hydroxy-5α-spirostan-6α-yl-O-ß-D-glucopyranoside (6), (25S)-3ß,27-dihydroxy-5α-spirostan-6α-yl-O-ß-D-glucopyranoside (7).

Chemical composition and in vitro antibacterial activity of the essential oil of Phthirusa adunca from Venezuelan Andes.

In this paper, preliminary studies on the chemical characterization of Phthirusa adunca Meyer essential oil, obtained by hydrodistillation, is presented. The separation of the components was performed by GC-MS. Twenty-three compounds (94.5% of the sample) were identified of which the three major ones (76% of the sample) were beta-phellandrene (38.1%), germacrene D (26.8%) and beta-pinene (11.5%). The essential oil showed a broad spectrum of activity against Salmonella Typhi CDC 57 (100 microg/mL), Staphylococcus aureus ATCC 25923 (200 microg/mL), Enterococcus faecalis ATCC 29212 (250 microg/mL), Escherichia coli ATCC 25922 y Klebsiella pneumoniae ATCC 23357 (500 microg/mL). This is the first report on the composition and activity of the essential oil of this species.

Chemical composition of the essential oil from Carramboa littlei (Asteraceae).

The essential oil from the leaves of Carramboa littlei Aristeg. was isolated by hydrodistillation yielding 0.09%, w/v. The chemical composition was determined by GC-FID and GC-MS. Sixteen components were identified by comparison of their mass spectra with Wiley and NIST library data. The major constituents of the oil were germacrene-D (50.0%), bicyclogermacrene (4.8%) and ent-kaur-16-en-19-al (21.8%).

Steroidal saponins from the fruits of Cestrum ruizteranianum.

Seven spirostane and furostane-type glycosides were isolated from the aqueous methanolic extract of the fruits of Cestrum ruizteranianum and characterized mainly by 2D NMR spectroscopy and mass spectrometry. These known saponins belong to the delta5-spirostene and delta5-furostene series and are reported in this species for the first time.

Chemical composition of the essential oil from the bark Bursera tomentosa (Jacq) Tr & Planch / Composición química del aceite esencial de la corteza de Bursera tomentosa (Burseraceae) (Jacq) Tr & Planch

The bark of Bursera tomentosa was collected at full flowering stage in September 2002 at Cabudare, Lara State. The essential oil was isolated by hydrodistillation and it was analyzed by GC and GC/MS. Twenty eight components were identified which made up 90.1 percent of the oil. The main constituents of the essential oil were: spatulenol (11.4 percent, globulol (8.9 percent), epi alpha Cadinol (8.8 percent) and cis-ocimene (7.3 percent).

La corteza de Bursera tomentosa, fue recolectada en estado de floración en el mes de septiembre 2002 en Cabudare, Estado Lara. El aceite esencial fue obtenido por hidrodestilación y analizado por CG y CG/EM. Se identificó veinte y ocho compuestos que constituyen el 90.1por ciento del aceite. Los constituyentes mayoritarios del aceite esencial fueron spatulenol (11.4 por ciento), globulol (8.9 por ciento), epi-alfa-cadinol (8.8 por ciento) y cis-ocimeno (7.3 por ciento).

Volatile compounds from Tagetes pusilla (Asteraceae) collected from the Venezuela Andes.

The essential oil from the leaves of Tagetes pusilla Kunth (Asteraceae) collected from Mérida, Venezuela, was analyzed by GC/MS. A yield of 0.38% oil was obtained by hydrodistillation. Only two components, trans-anethole and 4-allylanisole were identified by comparison of their mass spectra with those in the Wiley GC-MS Library data base.

Chemical composition of the essential oil of leaves and roots of Ottoa oenanthoides (Apiaceae) from Mérida, venezuela.

Essential oils extracted by hydrodistillation from leaves and roots of Ottoa oenanthoides Kunth (Apiaceae) were analyzed by GC/MS. The oils, obtained in yields of 0.10% and 0.66%, respectively, each contained four compounds, which were identified from their mass spectra and retention indices (RI). The major compound identified was 2-methoxy-8-methyl-1,4-naphthalindione (59.9% leaves, and 62.8%, roots), followed by 7-methoxy-1-naphthol (18.3% leaves and 17.3% roots), 2-naphthalenol (18.6% leaves and 15.0% roots), and 3-methoxy-2-naphthalenol (3.1% leaves and 2.1% roots). To the best of our knowledge, this is the first time that naphthalene derivatives have been reported for any species of the Apiaceae family.

The volatile constituents of Salvia leucantha.

Salvia leucantha Cav. (Lamiaceae), native to Mexico, is found in Venezuela in parks and gardens. Hydrodistillation of the fresh leaves of this plant yielded 0.05% of essential oil. GC and GC/MS analyses permitted the identification of 30 compounds, which made up 95.9% of the oil. The most abundant constituents were bornyl acetate (24.1%), beta-gurjunene (14.8%), beta-caryophyllene (14.1%), dillapiol (11.0%) and bicyclogermacrene (8.9%).

Chemical composition and larvicidal activity of Eugenia triquetra essential oil from Venezuelan Andes.

The chemical constituents of the essential oil obtained by hydrodistillation of the leaves of Eugenia triquetra O. Berg, collected in Táchira State, Venezuela, were identified by GC-MS analysis. Twenty-six components, which made up 88.5% of the oil, were identified. The major constituents were linalool (17.5%), limonene (16.9%), alpha-pinene (11.6%), beta-pinene (8.7%), and p-cymene (3.7%). The essential oil was tested against third-instar larvae of Aedes aegypti, showing a LC50 value of 64.8 +/- 5.6 ppm.

Triterpene saponins from the fruits of Phytolacca rugosa (Phytolaccaceae).

Four known serjanic acid glycosides were isolated from the fruits of Phytolacca rugosa and characterized mainly by 2D NMR spectroscopy and mass spectrometry. This aglycon has a chemotaxonomic significance for the genus Phytolacca.

Analysis of chemical constituents of the volatile oil from leaves of Solanum bicolor.

The volatile components from the leaves of Solanum bicolor Roemer & Schultes, was obtained by hydrodistillation and was analizad by GC/MS. A total of 20 compounds, representing 96.3 % of the oil, were identified. The dominant compounds were trans-caryophyllene (23.2%), trans-2-pentadecene (22.6%), germacrene D (12.2%), biciclogermecrene (8.0%) and caryophyllene oxide (4.7%).

Chemical composition and antibacterial activity of the essential oil from fruits of Bursera tomentosa.

The hydrodistilled oil from the fruits of Bursera tomentosa, obtained in 0.2% yield, was analyzed by GC-MS. Nine components were identified, which made up 99.3% of the oil. The most abundant constituents were cis-ocimene (47.6%), n-nonane (28.2%) and germacrene-D (11.1%). The oil showed antibacterial activity against Staphylococcus aureus (ATCC 25923), Enterococcus faecalis (ATCC 29212) and Salmonella typhi (CDC 57), with MIC values of 80 microg/mL, 120 microg/mL and 100 microg/mL, respectively.