Synergistic effects of binary mixtures of linalool with pyrethroids against fall armyworm / Efeitos sinérgicos de misturas binárias de linalol com piretroides contra lagarta-do-cartucho

The present work aimed to determine the toxicity of linalool and evaluate the lethal and toxic effects of linalool associated with pyrethroids in binary mixtures to fall armyworm (Spodoptera frugiperda). The insects used in the experiment were obtained from stock breeding initiated from larvae collected from conventional corn plants, grown in an experimental area, in the city of Uberlândia, Minas Gerais. Also, it was obtained essential oil from a variety of Ocimum basilicum, with a high content of linalool (80%), found naturally, as a measure of comparison of different linalool (97.5%) assays. Dose-response bioassays with 3rd instar larvae were performed to determine lethal dose for 50% mortality (LD50) of linalool. Toxicity tests were also performed with O. basilicum essential oil and with pyrethroid insecticides: deltamethrin and its commercial product (Decis 25 EC, Bayer®). After this, combinations between different doses of these products were made and applied on 3rd instar larvae of Spodoptera frugiperda (Smith). Linalool presented high toxicity to S. frugiperda (LD50 = 0.177 µL a.i. µL-1). It was observed neurotoxic effects after the linalool application since the insects presented an aspect of confusion, followed by extreme agitation and finally death. All binary mixtures caused mortality higher than the products applied alone (deltamethrin and linalool) used at 100% LD50, except to 75% LD50 deltamethrin added to 25% LD50 linalool, whose mortality did not differ the products alone, in 24 hours. It was obtained over 90% larval mortality when linalool was combined with 25% LD50 of deltamethrin, in 24 and 48 hours after application, and over 80% of mortality when linalool was combined with 25% LD50 of Decis, only in 48 hours after application. We conclude that linalool is a potential insecticidal and can be associated with pyrethroids to control of S. frugiperda. Further studies are required in order to evaluate the synergistic combinations against field populations of S. frugiperda.

O objetivo deste trabalho foi determinar a toxicidade do linalol e avaliar os efeitos tóxicos e letais do linalol associado a piretroides em misturas binárias para lagarta do cartucho do milho (Spodoptera frugiperda). Os insetos utilizados no experimento foram obtidos de criação estoque iniciada a partir de larvas coletadas em plantas de milho convencional, cultivado em área experimental, no município de Uberlândia, Minas Gerais. Também foi obtido óleo essencial de uma variedade de Ocimum basilicum, com alto teor de linalol (80%), encontrado naturalmente, como medida de comparação para ensaios com linalol (97.5%). Os bioensaios do tipo dose-resposta com larvas de 3º instar foram realizados para determinar a dose letal do linalol para 50% de mortalidade da população (DL50). Também foram realizados testes de toxicidade com óleo essencial de Ocimum basilicum e com inseticidas piretroides: deltametrina e seu produto comercial (Decis 25 EC, Bayer®). Em seguida, foram realizadas combinações entre diferentes doses desses produtos e aplicadas em larvas de 3º instar de Spodoptera frugiperda (Smith). De acordo com os resultados, observou-se que o linalol apresentou alta toxicidade para S. frugiperda (DL50 = 0,177 µL a. i. µL-1). Foram observados efeitos neurotóxicos após a aplicação do linalol, uma vez que os insetos apresentaram um aspecto de confusão, seguido de extrema agitação e, por fim, morte. Todas as combinações binárias causaram mortalidade maior que os produtos aplicados isoladamente (deltametrina e linalol) utilizando-se 100% da DL50, exceto para 75% DL50 de deltametrina somada a 25% DL50 de linalol, cuja mortalidade não diferiu dos produtos isolados, em 24 horas após a aplicação. Foi obtida mais de 90% de mortalidade de larvas quando se combinou linalol com 25% da DL50 de deltametrina, em 24 e 48 horas após a aplicação, e mais de 80% de mortalidade quando se combinou linalol com 25% da DL50 do produto comercial, somente 48 horas após a aplicação. Concluímos que o linalol é um potencial inseticida e pode ser associado a piretroides no controle de S. frugiperda. Mais estudos são necessários em vista de avaliar as combinações sinérgicas contra populações de campo de S. frugiperda.

In vitro effect of terpenoids - rich extract of Momordica charantia on alpha glucosidase activity / Efecto in vitro del extracto rico en terpenoides de Momordica charantia sobre la actividad de la alfa-glucosidasa

Background: Momordica charantia is a vine, native to tropics and subtropics that has found use in herbal medicine. In Nigeria, the plant is locally used in the treatment of diabetes. Objective: To investigate the inhibitory effect of terpenoid-rich extract from Momordica charantia on α-glucosidase activity. Method: The inhibitory effect of the terpenoid-rich extract from Momordica charantia on the activity of alpha-glucosidase from Saccharomyces cerevisiae as well as the determination of the mode of inhibition were investigated using in vitro assay methods. Results: The results revealed that the terpenoid-rich extract had a high IC50 of 1.60 mg/mL. The Lineweaver-Burk plot revealed that the extract exhibited partially mixed­type inhibition of α-glucosidase. Conclusions: It can be inferred from this study that although terpenoid-rich extract inhibited α-glucosidase, further purification will be necessary on the extract so as to increase its potency as an inhibitor of α-glucosidase. The action of the extract on α-glucosidase provided an insight into the probable mechanism of action of Momordica charantia in reducing hyperglycemia.

Antecedentes: Momordica charantia es una vid, nativa de las regiones tropicales y subtropicales que ha sido usada en la medicina herbal. En Nigeria, esta planta se ha usado localmente en el tratamiento de la diabetes. Objetivo: Investigar el efecto inhibitorio del extracto rico en terpenoides de Momordica charantia sobre la actividad de la α-glucosidasa. Método: El efecto inhibitorio del extracto rico en terpenoides de Momordica charantia sobre sobre la actividad de la α-glucosidasa y el modo de inhibición se evaluó con un ensayo in vitro. Resultados: Los resultados mostraron que el extracto rico en terpenoides tiene un alto IC50 de 1,60 mg/mL. El gráfico Lineweaver-Burk reveló que el extracto presenta una inhibición combinada de la α-glucosidasa. Conclusión: De este estudio se infiere que aunque el extracto rico en terpenoides inhibió la α-glucosidasa, es necesario realizar una purificación con el fin de incrementar su potencia como inhibidor de la α-glucosidasa. La acción del extracto sobre la α-glucosidasa proporciona un entendimiento del mecanismo de acción probable de Momordica charantia en la reducción de la hiperglicemia.

Essential oils of Baccharis trinervis (Asteraceae) from Costa Rica / Constituyentes de los aceites esenciales de Baccharis trinervis (Asteraceae) de Costa Rica

Abstract Baccharis is an Asteraceae genus of flowering plants, which has about 340 to 400 species, ranging from the Southern United States to the Southern extreme of Argentina and Chile through Central America and the Caribbean regions. The species Baccharis trinervis is a native shrub from Mexico, Central America and throughout South America. In Costa Rica, this species is commonly known as alcotán and the fresh leaves are used as a poultice on wounds and ulcers. The objective of the present research was to characterize the chemical composition of seven hydrodistilled essential oils of diverse morphological parts of B. trinervis. For this, samples were obtained from three locations in Costa Rica and standard laboratory analyses were followed. The essential oils were analyzed by capillary gas chromatography-flame ionization detector (GC-FID) and gas chromatography-mass spectrometry (GC-MS) using the retention indices on a 5 % phenyl/dimethylpolysiloxane fused silica column in addition to mass spectral fragmentation patterns, which allowed the identification of 268 compounds. The essential oils consisted mainly of terpenoids (92.3 to 97.8 %). The major constituents from the leaf oils were caryophyllene oxide (0.1-22.5 %), viridiflorol (8.8-21.0 %), germacrene D (0.5-19.1 %), germacrene B (0.2-16.0 %), β-caryophyllene (3.5-9.1 %), spathulenol (0.1-8.3 %), δ-3-carene (2.0-6.8 %), and α-pinene (2.5-5.9 %). The flower oil consisted mainly of globulol (0-24 %), β-caryophyllene (9.5-17.1 %), cismuurola-4(14), 5-diene (traces-13.7 %), germacrene D (4.3-9.9 %), bicyclogermacrene (5.9-8.3 %), ar-curcumene (0-8.0 %), spathulenol (4.3-4.8 %), caryophyllene oxide (3.1-4.7 %), and viridiflorol (0.3-4.7 %). The major components of the branch oil were germacrene B (1.4-18.7 %), germacrene D (14.7-15.6 %), β-caryophyllene (10.1-12.4 %), viridiflorol (0-11.5 %), globulol (0.6-11.3 %), δ-3-carene (4.1-8.1 %), β-phellandrene (1.5-6.5 %), and bicyclogermacrene (3.6-4.9 %). The essential oil composition differed markedly from that of previously studied oils of plants growing in Brazil, which contain two characteristic stereoisomeric methyl dec-2-en4,6-diynoate compounds not detected in this study. This is the first report about the chemical composition of the essential oils obtained from this species growing wild in Costa Rica.

Resumen Baccharis (Asteraceae) es un género de plantas con flor que consta de 340 a 400 especies que habitan desde el sur de EE. UU. hasta Argentina y Chile, incluyendo América Central y varias islas del Caribe. Baccharis trinervis es un arbusto nativo de México, América Central y América del Sur. En Costa Rica, esta especie se conoce popularmente como alcotán y las hojas frescas se utilizan en forma de cataplasma para curar heridas y úlceras. El objetivo del presente estudio fue el de identificar los constituyentes químicos de los aceites esenciales obtenidos de diferentes partes morfológicas de B. trinervis en tres localidades de Costa Rica, obtenidos mediante el método de hidrodestilación. Se analizó la composición química de los aceites por cromatografía capilar de gases con detector de ionización de flama (GCFID) y cromatografía de gases acoplada a un detector de masas (GC-MS), utilizando los índices de retención en una columna tipo DB-5 y los patrones de fragmentación, lo cual permitió la identificación de 268 constituyentes. Los siete aceites están constituidos principalmente por terpenoides (92.3 a 97.8 %). Los compuestos mayoritarios de los aceites de las hojas se identificaron como óxido de cariofileno (0.1-22.5 %), viridiflorol (8.8-21.0 %), germacreno D (0.5-19.1 %), germacreno B (0.2-16.0 %), β-cariofileno (3.5-9.1 %), espatulenol (0.1-8.3 %), δ-3-careno (2.06.8 %), α-pineno (2.5-5.9 %), biciclogermacreno (0-4.4 %), δ-cadineno (0.8-3.4 %), β-elemeno (0.8-3.0 %), limoneno (0.9-2.9 %) y β-pineno (1.3-2.5 %). Los aceites de las flores contienen principalmente globulol (0-24 %), β-cariofileno (9.5-17.1 %), cis-muurola-4(14),5-dieno (t-13.7 %), germacreno D (4.3-9.9 %), biciclogermacreno (5.9-8.3 %), ar-curcumeno (0-8.0 %), espatulenol (4.3-4.8 %), óxido de cariofileno (3.1-4.7 %), viridiflorol (0.3-4.7 %), β-elemeno (2.5-4.3 %), germacreno B (1.8-4.3 %), γ-cadineno (0.32.5 %), δ-3-careno (0.9-2.2 %) y α-humuleno (1.8-2.2 %). Los constituyentes mayoritarios del aceite de las ramitas fueron: germacreno B (1.4-18.7 %), germacreno D (14.7-15.6 %), β-cariofileno (10.1-12.4 %), viridiflorol (0-11.5 %), globulol (0.6-11.3 %), δ-3-careno (4.1-8.1 %), β-felandreno (1.5-6.5 %), biciclogermacreno (3.6-4.9 %), δ-cadineno (3.5-4.3 %), β-copaeno (0.6-2.8 %), β-elemeno (1.3-2.7 %) y γ- muuroleno (1.6-2.6 %). Los aceites estudiados presentan una composición compleja y se diferencian de los aceites obtenidos de la misma especie que crece en Brasil por la ausencia de los compuestos isoméricos diacetilénicos dec-2-en-4,6-diinoato de metilo(Z y E). También se diferencian de los aceites de las plantas de Brasil y Venezuela por la presencia de sesquiterpenoides de la familia de los guayanos, en especial por cantidades apreciables de viridiflorol, globulol y espatulenol.

Anti-proliferative effect of terpenes on human prostate cancer cells: Natural sources and their potential role as chemopreventive agents / Efecto anti-proliferativo de los terpenos en células de cáncer de próstata humana: Fuentes naturales y su rol potencial como agentes quimiopreventivos

ABSTRACT Prostate cancer is one of the neoplastic diseases with the highest morbidity and mortality in the world. The diversity of available treatments and side effects related to therapeutic treatments are severe and affect a patient's quality of life. Thus, to creating new therapeutic alternatives to reduce morbidity and creating safe and effective therapies is a constant challenge. Recently, the use of traditional medicine and chemoprevention has gained importance. Several clinical and epidemiological studies suggest that a high-terpenoid compound-based diet is associated with a reduced risk of prostate cancer. This review is focused on the anti-proliferative effects of different terpenoids isolated from natural sources on human prostate cancer cells, with the aim of setting the basis to use these compounds as phytotherapeutic, nutraceutical and functional ingredients.

RESUMEN El cáncer de próstata es una de las neoplasias que produce gran morbilidad y mortalidad en el mundo. Los tratamientos y los efectos secundarios de la terapia son severos y afectan la calidad de vida del paciente. Por esto, es necesario crear nuevas alternativas terapéuticas para reducir la morbilidad y generar terapias seguras y efectivas es un desafío permanente. En los últimos años, el uso de la medicina tradicional y agentes quimiopreventivos han adquirido importancia. Estudios clínicos y epidemiológicos sugieren que una dieta basada en altas dosis de terpenoides se asocia a una reducción en el riesgo de presentar cáncer de próstata. Esta revisión se centra en los efectos anti-proliferativos sobre las células de cáncer de próstata en humanos de diferentes terpenoides aislados de fuentes naturales, con el objetivo de establecer las bases para utilizar estos compuestos como ingredientes fitoterapéuticos, nutracéuticos y funcionales.

Volatile compounds profile of Bromeliaceae flowers / Perfil de compuestos volátiles de las flores en las Bromeliaceae

Abstract:Volatile compounds play a vital role in the life cycle of plants, possessing antimicrobial and anti-herbivore activities, and with a significant importance in the food, cosmetic, chemical, and pharmaceutical industry. This study aimed to identify the volatile compounds emitted by flowers of thirteen species belonging to four genera of Bromeliaceae, using headspace solid-phase micro-extraction and detection by gas chromatography-mass spectrometry. A total of 71 volatile compounds belonging to nine chemical groups were identified. The compounds identified represented more than 97 % of the major components in Aechmea bicolor, Ae. bromeliifolia, Ae. distichantha, Ae. fasciata, and Vriesea friburgensis. In the Ananas varieties, over 99 % of the components were identified, and around 90 % in V. simplex. V. friburgensis presented the largest diversity of volatiles with 31 compounds, while Alcantarea nahoumii presented only 14. All three Ananas varieties presented the same 28 compounds in relatively similar abundance, which has been confirmed by principal component analysis. Current taxonomy and pollination syndrome studies available can adequately explain the variation in volatile compounds among species. Rev. Biol. Trop. 64 (3): 1101-1116. Epub 2016 September 01.

ResumenLos compuestos volátiles tienen un papel vital en el ciclo de vida de las plantas. Poseen actividad antimicrobiana y anti-herbivoría biológica y una gran importancia en la industria de alimentos, cosméticos, perfumes, productos químicos y farmacéuticos. Este estudio tuvo como objetivo identificar los compuestos volátiles de trece flores de especies, pertenecientes a cuatro géneros de Bromeliaceae utilizando microextracción en fase sólida mediante cromatografía de gases hifenada con espacio de cabeza acoplada a espectrometría de masas. Se han identificado setenta y un diferentes compuestos volátiles pertenecientes a nueve grupos. Los compuestos identificados representaron más del 97 % de los componentes principales en Aechmea bicolor, Ae. bromeliifolia, Ae. distichantha, Ae. fasciata, Vriesea friburgensis, 99 % en las variedades de Ananas y 90 % en V. Simplex. V. friburgensis mostró la mayor diversidad de compuestos volátiles con 31, mientras que en Al. nahoumii se han encontrado sólo 14 compuestos. Las tres variedades de Ananas presentan los mismos 28 compuestos en cantidades relativamente similares, lo que se confirmó por el análisis de componentes principales. Estudios taxonómicos y síndromes de polinización disponibles podrían explicar la variación de los compuestos volátiles entre especies.

Triterpenes and Beta-agarofurane sesquiterpenes from tissue culture ofMaytenus boaria / Triterpenos y Beta-agarofuranos sesquiterpenos desde cultivo de tejidos de Maytenus boaria

Leaf explants of Maytenus boaria were induced towards callus tissue culture with different mixture of cytokinins and auxins. MeOH extract of callus was partitioned with AcOEt and water, and through repeated chromatography procedures were isolated and identified, four triterpenes and three beta-agarofuran sesquiterpenes.

Explantes de hojas de Maytenus boaria fueron inducidos a formar callos mediante diferentes mezclas de citoquininas y auxinas. Un extracto metanólico de los callos fue fraccionado con AcOEt y agua, y mediante repetidas cromatografías fueron aislados e identificados siete compuestos, cuatro triterpenos y 3 sesquiterpenos del tipo agarofurano.

ANTIFUNGAL ACTIVITY OF NEEM (Azadirachta indica: MELIACEAE) EXTRACTS AGAINST DERMATOPHYTES / Actividad antifúngica de extractos de neem (Azadirachta indica: Meliaceae) sobre hongos dermatofitos

In order to assess the antifungal activity of methanolic extracts from neem tree (Azadirachta indica A. Juss.), several bioassays were conducted following M38-A2 broth microdilution method on 14 isolates of the dermatophytes Trichophytonmentagrophytes, Trichophyton rubrum, Microsporum canis and Epidermophyton floccosum. Neem extracts were obtained through methanol-hexane partitioning of mature green leaves and seed oil. Furthermore, high performance liquid chromatography (HPLC) analyses were carried out to relate the chemical profile with their content of terpenoids, ofwidely known antifungal activity. The antimycotic Terbinafine served as a positive control. Results showed that there was total growth inhibition of the dermatophytes isolates at minimal inhibitory concentrations (MIC) between 50 μg/mL and 200 μg/mL for leaves extract, and between 625 μg/mL and 2500 μg/mL for seed oil extract. The MIC of positive control (Terbinafine) ranged between 0.0019 μg/mL and 0.0313 μg/mL. Both neem leaves and seed oil methanol extracts exhibited different chromatographic profiles by HPLC, which could explain the differences observed in their antifungal activity. This analysis revealed the possible presence of terpenoids in both extracts, which are known to have biological activity. The results of this research are a new report on the therapeutic potential of neem to the control of dermatophytosis.

Se determinó la actividad antifúngica de extractos metanólicos de la especie Azadirachta indica A. Juss. (Meliaceae), conocida comúnmente como neem, empleando el método de microdilución en caldo M38-A2 de referencia para hongos filamentosos y dermatofitos. Se evaluaron 14 aislamientos de los dermatofitos Trichophyton mentagrophytes, Trichophyton rubrum, Microsporum canis y Epidermophyton floccosum. Los extractos de neem fueron obtenidos mediante partición metanol-hexano a partir de aceite de semillas y hojas verdes maduras. Adicionalmente, se analizaron por cromatografía líquida de alta resolución (CLAR) con el fin de relacionar su perfil químico con el contenido de terpenoides, de conocida actividad antifúngica. Se empleó como control positivo el antimicótico Terbinafina. Los resultados mostraron inhibición total del crecimiento de los aislamientos de dermatofitos a concentraciones mínimas inhibitorias (CMI) entre 50 μg/mL y 200 μg/mL para el extracto de hojas y entre 625 μg/mL y 2500 μg/mL para el extracto de aceite de semillas. La CMI encontrada para el control positivo (Terbinafina) fluctuó entre 0,0078 μg/mL y 0,0313 μg/mL. Los extractos metanólicos de hojas y aceite de semillas de neem exhibieron diferentes perfiles cromatográficos en CLAR, lo cual podría explicar las diferencias observadas en su actividad antifúngica. Éste análisis químico reveló la posible presencia de compuestos terpenoides en ambos extractos, los cuales se conocen por su actividad biológica. Los resultados de esta investigación son un nuevo aporte sobre el potencial terapéutico del neem para el control de dermatofitosis.

Variabilidad de la composición química del aceite esencial de nectandra megapotamica (spreng. ) mez (lauraceae) / Variability of chemical composition of essential oil from nectandra megapotamica (spreng. ) mez (lauraceae)

Este trabajo describe la variabilidad química del aceite esencial (AE) de N. megapotamica, utilizando análisis multivariado. Se colectaron hojas de tres individuos en una población en Santa Maria, Brasil, en cada estación durante un año y se clasificaron en hojas jóvenes y viejas. Los AE se obtuvieron por hidrodestilación y la composición química fue determinada por cromatografía de gases acoplada a espectrometría de masas. Se realizó un análisis de agrupamiento jerárquico para formación de grupos químicos (GQ) y análisis de componentes principales (ACP) para verificar cuáles constituyentes influenciaron la formación de grupos. Inicialmente se observaron dos agrupamientos en el dendrograma debido a concentraciones de α-pineno y biciclogermacreno, constituyentes mayoritarios. En el segundo corte se discriminaron cinco GQ, siendo este también el número de componentes principales con valores propios superiores a 1. Los isómeros de asarona se observaron solamente en el AE de dos individuos (GQ5), constituyendo los principales elementos de diferenciación.

This work describes the chemical variability of the essential oils (EO) of N. megapotamica using multivariate analysis. Leaves of three individuals of a population in Santa Maria-RS were collected per season for a year, and classified into young and old. The EO were obtained by hydrodistillation and the chemical composition was determined by gas chromatography coupled to mass spectrometry (GC/MS). Cluster analysis (HCA) were performed for formation of chemical groups (CG), and principal component analysis was done (PCA) to determine which constituents influenced the formation of groups. Initially, two clusters were observed in the dendrogram, due to the concentration of α-pinene and bicyclogermacrene, major constituents of the EO. The second section showed five different CG, which is also the number of principal components with eigenvalues greater than 1. The occurrence of isomers of asarone was observed only in EO of two individuals (CG5), containing the main elements of differentiation.

Anti-fertility and other biological activities of zoapatle (Montanoa spp. )with biotechnological application / Anti-fertilidad y otras actividades biológicas del zoapatle (Montanoa spp. ) con aplicación biotecnológica

Species from the Montanoa genus have been used for hundreds of years in Mexican traditional medicine. The Náhuatl name given by Aztecs to this plant was “cihuapahtli”, meaning “woman’s medicine” (cihua, woman; pahtli, medicine), because M. tomentosa has been used to treat female health disorders since pre-Hispanic times due to its uterotonic properties. Later on, the Spanish pronunciation transformed the word into “zoapatle”, the name still used by herb sellers in México. Despite its use in folk medicine, intensive scientific research on this plant did not begin until the early 1970’s. The only two available reviews exclusively focused on the Montanoa species cover the period from 1529 to 1985. However, in the last two decades, important phytochemical, biochemical and biotechnological advances were achieved. This is a review of the history, botany, most relevant chemistry, biological activity and biotechnology of the secondary metabolites from the Montanoa genus so far.

Especies del género Montanoa han sido empleadas por siglos en la medicina tradicional Mexicana. El nombre asignado a esta planta por los Aztecas fue “cihuapahtli”, ó “medicina para la mujer” (cihua, mujer; pahtli, medicina). Específicamente, M. tomentosa es usada para tratar desordenes de la mujer desde tiempos prehispánicos por sus propiedades uterotónicas. La castellanización transformó esta palabra en “zoapatle”, este nombre sigue siendo usado por los curanderos en México. A pesar de su uso en la medicina folklórica, la investigación científica intensa en esta planta comenzó desde inicios de 1970. Las únicas dos revisiones disponibles y dedicadas exclusivamente a las especies de Montanoa cubren el periodo de 1529 a 1985. Sin embargo, en las últimas dos décadas, se han logrado importantes avances fitoquímicos, bioquímicos y biotecnológicos. Este trabajo presenta una revisión de la historia, botánica, química más relevante, actividades biológicas y biotecnología de los metabolitos secundarios del género Montanoa a la fecha.

Potencial inseticida de óleos de origem vegetal sobre Grapholita molesta (Busck) (Lepidoptera: Tortricidae) / Insecticidal potential of vegetable oil extracts on Grapholita molesta (Busck) (Lepidoptera: Tortricidae)

Em decorrência do estudo das interações químicas entre insetos e herbívoros, e do avanço da pesquisa fitoquímica, é conhecida ampla variedade de produtos naturais com potencial inseticida. Grapholita molesta (Busck) (Lepidoptera: Tortricidae), mariposa-oriental, é uma das principais pragas do pessegueiro, danificando brotações e frutos. O objetivo do presente estudo foi verificar a mortalidade, atratividade e deterrência de óleos vegetais em G. molesta. Ovos e pupas de insetos provindos de criação artificial foram imersos nos óleos essenciais de Elionurus muticus (Spreng.) Kuntze e Cymbopogon winterianus Jowitt ex Bor nas concentrações de 0,25%, 0,5%, 1% e 0,5%, 1%, 5%. Os testes de atratividade foram realizados em olfatômetro do tipo "Y". A deterrência à oviposição foi testada em gaiolas sem escolha e de dupla escolha. O óleo de E. muticus aplicado em ovos de G. molesta nas três concentrações causou mortalidades maiores que 30%, diferindo significativamente dos controles (p<0,05). A mortalidade causada pelo óleo de citronela foi em torno de 70%, significativamente superior ao controle (p<0,01). O óleo de citronela aplicado a 1% em pupas causou mortalidade de 99,8%. No teste com o olfatômetro, não houve atratividade dos adultos para nenhum dos óleos. A média de ovos no substrato com o tratamento (0,33±0,33), foi significativamente menor que no controle (7,3±0,88) (p<0,01), indicando deterrência à oviposição.

As a result of the study on the chemical interactions between insects and herbivores and the advancement of phytochemical research studies, a variety of natural products with great insecticidal potential are described in the literature. The Grapholita molesta (Busck) (Lepidoptera: Tortricidae), commonly known as Oriental Fruit Moth, is a major peach pest damaging shoots and fruits. The purpose of this study was to assess the mortality, attractiveness and deterrence of vegetable oils in G. molesta. Insect eggs and pupae artificially created were immersed in the essential oils of Elionurus muticus (Spreng.) Kuntze and/or Cymbopogon winterianus Jowitt ex Bor at the concentrations of 0.25%, 0.5%, 1% and 0.5%, 1%, 5%, respectively. The attractiveness tests were performed in a Y-Tube olfactometer. Oviposition deterrence was tested in no-choice and dual-choice cages. Oil of E. muticus applied in eggs of G. molesta at three concentrations caused mortality above 30%, which differs significantly from controls (p<0.05). Mortality caused by citronella oil was approximately 70%, significantly higher than control (p<0.01). The application of citronella oil at 1% in pupae caused mortality of 99.8%. There was no attractiveness of adults in the olfactometer test for any of the oils. Citronella oil presented oviposition deterrence, as the mean number of eggs in the substrate with the treatment (0.33 ± 0.33) is significantly lower than in the control (7.3 ± 0.88) (p<0.01).

Study of the chemical composition of the resinous exudate isolated from Psoralea glandulosa and evaluation of the antioxidant properties of the terpenoids and the resin / Estudio de la composición química del exudado resinoso aislado de Psoralea glandulosa y la evaluación de las propiedades antioxidantes de la resina y sus terpenoides

Otholobium glandulosum (L.) J.W. Grimes (= Psoralea glandulosa L.) (Fabaceae) is a resinous bush that grows in Chile. The chemical composition of its resinous exudate was determined for the first time. Three meroterpenic: bakuchiol (8), 3-hydroxybakuchiol (11), 12-hydroxyisobakuchiol (12) and a new compound kuchiol (13) were isolated and their structures were determined. The antioxidant activity of the terpenic compounds and resin was evaluated using the bleaching of DPPH radical, Ferric Reducing Antioxidant Power (FRAP) and Total Reactive Antioxidant Properties (TRAP) assays.

Otholobium glandulosum (L.) J.W. Grimes (= Psoralea glandulosa L.) (Fabaceae) es un arbusto resinoso que crece en Chile. La composición química de su exudado resinoso fue determinada por primera vez. Tres meroterpenos: bakuchiol (8), 3-hidroxibakuchiol (11), 12-hidroxiisobakuchiol (12) y un nuevo compuesto kuchiol (13) fueron aislados y sus estructuras fueron determinadas espectroscópicamente. La actividad antioxidante de los compuestos terpénicos y la resina se evaluó mediante tres métodos antioxidantes DPPH, Poder Reductor de Hierro III (FRAP) y Capacidad Antioxidante Total (TRAP).

Investigação das propriedades anticariogênicas de óleos essenciais: atividade antimicrobiana e caracterização química / Investigation of the anti-cariogenic properties of essential oils: antimicrobial activity, and chemical characterization

O objetivo desse trabalho foi avaliar os óleos essenciais de Thymus vulgaris, Hyptis spicigera, Cymbopogon citratrus, Cymbopogon martinii, Cymbopogon flexuosus bem como os terpenos (citral e cineoli), com relação ao seu potencial para aplicação em terapia anticariogênica. Inicialmente, e a seguir foram realizados testes microbiológicos para a determinação da concentração inibitória mínima (CIM), concentração bactericida mínima (CBM), utilizando os micro-organismos Actinomyces naeslundii ATCC 19039, Lactobacillus acidophilus ATCC 4356, Streptococcus gordonii ATCC 10558, Streptococcus mitis ATCC 9811, Streptococcus mutans ATCC 35688, Streptococcus sanguinis ATCC 10556 e Streptococcus sobrinus ATCC 33478, além de isolados clínicos de estreptococos do grupo mutans e Lactobacillus spp., ambos isolados de dentina cariada. Os três óleos essenciais com maior atividade antibacteriana foram selecionados e caracterizados quimicamente por cromatografia gasosa e avaliados frente ao biofilme de microcosmo, analisando a influência dos óleos essências na adesão de micro-organismo cariogênicos ao esmalte dentário. Além disso, foi analisada a capacidade de eliminação do biofilme de microcosmo sobre a lamínula de vidro. Os resultados revelaram a ação bactericida e bacteriostática de todos os óleos essenciais testados frente às cepas padrão e clínica, com CIMs variando de 0,78 a 3,125μl /mL. Para os terpenos os valores de CIM variaram de 3,125 to 50 μl/mL. No teste de adesão, os resultados apresentam 100% de inibição da adesão do microcosmo em esmalte dentário. Este resultado também foi observado no estudo frente ao biofilme. Diante disso, conclui-se que todos os óleos essenciais e os terpenóides testados possuem atividade promissora frente micro-organismos cariogênicos, além disso, os óleos essenciais de T. vulgaris, H. spicigera e C. citratus, foram capazes de impedir a adesão de micro-organismos bucais ao esmalte dentário

The aim of this study was to evaluate the essential oils of Thymus vulgaris, Hyptis spicigera, Cymbopogon citratrus, Cymbopogon martinii, Cymbopogon flexuosus, as well as the terpenes (citral and cineole),regarding their potential for application in anti-cariogenic therapy. The antimicrobial activity was determined by minimal inhibitory concentration (MIC) and minimal bactericidal concentration (MBC) for the following microorganisms: Actinomyces naeslundii ATCC 19039, Lactobacillus acidophilus ATCC 4356, Streptococcus gordonii ATCC 10558, S. mitis ATCC 9811, S. mutans ATCC 35688, S. sanguinis ATCC 10556 and S. sobrinus ATCC 33478, addition of clinical isolates of mutans streptococci and Lactobacillus sp., both isolated from carious dentin. The three essential oils with higher antibacterial activity were selected and chemically characterized by gas chromatography and evaluated against the biofilm microcosm, analyzing the influence of essential oils on the adhesion of cariogenic micro-organism to dental enamel. Furthermore, we analyzed the capacity of eliminating biofilm microcosm on glass coverslips. The results showed bactericidal and bacteriostatic action of all essential oils tested against standard and clinical strains, with MICs ranging from 0.78 to 3.125 μl / ml. Terpenes for the MIC values ranging from 3.125 to 50 μl / ml. In the adhesion test, the results showed 100% inhibition of the adhesion of tooth enamel in microcosm. This result was also observed when biofilm was evaluated. Therefore, it is concluded that all essential oils and terpenoids tested show promising activity against cariogenic microorganisms, mainly the essential oils of T. vulgaris, H. spicigera and C. citratus, were able to prevent the adhesion of oral microorganisms in dental enamel

Caracterización química por cromatografía de gases/espectrometría de masas de dos extractos obtenidos de Phyllanthus orbicularis HBK / Chemical characterization using gas chromatography/mass spectrometry of two extracts from Phyllanthus orbicularis HBK

El objetivo del presente trabajo consistió en la caracterización química por cromatografía de gases/espectrometría de masas de 2 extractos obtenidos de Phyllanthus orbicularis HBK, para lo cual se llevó a cabo un método de extracción por maceración con n-hexano y acetato de etilo, a fin de obtener los extractos correspondientes. El estudio del extracto hexánico permitió identificar 17 componentes y resultaron predominantes estructuras del tipo hidrocarbonada, entre ellas, el ciclooctacosano como componente mayoritario. En el extracto de acetato de etilo se identificaron 19 compuestos y constituyeron los terpenoides las estructuras mayoritarias, aunque el más abundante resultó ser el esterol ã-sitosterol. Los compuestos identificados se informan por primera vez para la especie

The objective of this paper was the chemical characterization of two extracts from Phyllanthus orbicularis HBK through gas chromatography/mass spectrometry. To this end, maceration with N-hexane and ethyl acetate was used to obtain the respective extracts. The study of the hexane extract identified 17 components in which hydrocarbonate structures prevailed, mainly cyclooctacosane. In the ethyl acetate extract, 19 compounds were detected, being the terpenoids the predominant, although the most abundant was sterol ã-sitosterol. For the first time, the identified compounds are reported for this species

Presence of 3-(pentadec-10-enyl)-catechol allergen in the epicuticular components of Lithrea caustica (Anacardiaceae) / Presencia del alérgeno 3-(pentadec-10-enil)-catecol en los componentes epicuticulares de Lithrea caustica (Anacardiaceae)

Epicuticular components were obtained using methylene chloride extraction of fresh leaves from two populations of Lithrea caustica. The methylene chloride extracts were analyzed using GC and GC-MS. The extracts from both sampled populations showed a mixture of a hydrocarbon fraction of n-alkanes from C-21 to C-33 as their main components and small amounts of monoterpene hydrocarbons. The allergen 3-(pentadec-10-enyl)-catechol was also identified in the epicuticular sample in very different proportions in both extracts. A second extract obtained after the epicuticle had been removed from the sample revealed oxygenated monoterpenes, sesquiterpene hydrocarbons and an increased amount of the allergen 3-(Pentadec-10-enyl)-catechol. These results demonstrate that the cuticle hydrocarbons of the leaves function as a lipophylic barrier that controls allergen release.

Los componentes epicuticulares se obtuvieron mediante la extracción con cloruro de metileno de hojas frescas de dos poblaciones de Lithrea caustica. Los extractos de cloruro de metileno fueron analizados mediante CG y CG-EM. Los extractos de ambas poblaciones mostraron una mezcla de una fracción de hidrocarburos n-alcanos de C-21 a C-33 como sus componentes principales y pequeñas cantidades de hidrocarburos monoterpenicos. El alérgeno 3 - (pentadec-10-enil)-catecol también fue identificado en epicuticula en proporciones muy diferentes en ambos extractos. Un segundo extracto obtenido después que la epicutícula había sido eliminada de la muestra mostró monoterpenos oxigenados, hidrocarburos sesquiterpenos y una mayor cantidad del alérgeno 3 - (Pentadec-10-enil)-catecol. Estos resultados demuestran que los hidrocarburos de la cutícula de las hojas funcionan como una barrera lipofílica que controla la liberación del alérgeno.

Chemical constituents of Piptadenia gonoacantha (Mart.) J.F. Macbr (pau jacaré)

The phytochemical investigation of Piptadenia gonoacantha (Mart.) J.F. Macbr. (Leguminosae-Mimosoideae), commonly known as "pau jacaré" (alligator stick), afforded sitosterol, campesterol, stigmasterol, the N-benzoylphenylalanine-2-benzoylamide-3-phenylpropyl ester, known as asperphenamate, sitosterol-3-O-β-D-glucopyranoside, besides three flavonoids, apigenin, 5-O-methylapigenin and 7,4'-dihydroxy-3',5-dimethoxyflavone from its branches. From its leaves, the methyl gallate and two flavonoids, vitexin and isovitexin, were isolated. From its bark, a mixture of sitosterol, campesterol, and stigmasterol, besides a mixture of cycloartenone, cycloartan-25-en-3-one, and 24-methylene-cycloartenone, and the pure triterpenes 24-methylenecycloartanol, friedelin, lupeol and lupenone, were isolated. Their structures were established on the basis of spectral analysis, comparison with literature data and GC-MS analysis of the mixtures. The ester, flavonoids and the cycloartanes are been identified for first time in the genus Piptadenia.

O estudo fitoquímico de galhos de Piptadenia gonoacantha (Mart.) J.F. Macbr. (Leguminosae-Mimosoideae), comumente conhecida como "pau jacaré", forneceu sitosterol, estigmasterol, o éster N-benzoilfenilalaninato de 2-N-benzoil-3-fenilpropila, conhecido como asperfenamato, 3-O-β-D-glicopiranosil-sitosterol, além de três flavonóides, apigenina (5,7,4'-triidroxiflavona), apigenina-5-O-metil éter e 7,4'-dihidroxi-3' , 5-dimetoxiflavona. Das folhas isolaram-se galato de metila e dois flavonóides, 8-C-glicopiranosil-5,7,4' -trihidroxiflavona e 6-C-glicopiranosil-5,7,4'-trihidroxiflavona, conhecidas como vitexina e isovitexina. Das cascas desta planta isolaram-se uma mistura de sitosterol, campesterol e estigmasterol; mistura de cicloartenona, cicloartan-25,26-en-3-ona e 24-metileno-cicloartanona, além dos triterpenos, 24-metilenocicloartenol, fridelina, lupeol e lupenona. As estruturas foram estabelecidas através de análise de espectros de IV, RMN ¹H e 13C e massas, além de análise com CG-EM para identificar os componentes das misturas de cicloartanos e esteróides. O éster conhecido como asperfenamato, os flavonóides e os cicloartanos estão sendo registrados pela primeira vez em Piptadenia.

SINTESIS DE ESTEVIOSIDOS EN ESTEVIA (Stevia rebaudiana Bert.) / STEVIOSIDE SYNTHESIS IN STEVIA (Stevia rebaudiana Bert)

Stevia rebaudiana Bert. es una planta selvática subtropical nativa de Paraguay, que posee un potente edulcorante de hasta 300 veces más dulce que la sacarosa y no tiene calorías. Las moléculas responsables de esta característica son glucósidos de diterpeno, presentes en hojas y sintetizados, al menos en los estados iniciales, usando la misma ruta de síntesis del ácido giberélico, en la que el ácido shiquímico, da origen a muchos compuestos aromáticos. El acetato es el precursor de los terpenos o isoprenoides por la ruta del acetato-mevalonato, donde se encuentran los esteviósidos, aunque en este artículo se discute una ruta alternativa. La presente actualización pretende aportar algunas herramientas para el entendimiento de las principales rutas de síntesis de los glucósidos de esteviol.

Stevia rebaudiana Bert. is a subtropical wild plant of Paraguay , that possesses a potent sweetener up to 300 times higher than sucrose and has no calories. The molecules responsible for these characteristics are diterpen glycosides, found in leaves and synthesized at least, at initial states, which use the same pathway of the gibberellic acid in which the shiquimic acid gives origin to many aromatic compounds. The acetate is the precursor of the terpens or isoprenoids through the acetate-mevalonate pathway, where steviosides are found. Although in this article, an alternative route is discussed. This updating pretends to contribute tools for the understanding of the main pathways of steviol glycosides synthesis.

Chemical composition and seasonal variation of the volatile oils from leaves of Michelia champaca L., Magnoliaceae / Composição química e variação sazonal dos óleos voláteis das folhas de Michelia champaca L., Magnoliaceae

The volatile oils from leaves of Michelia champaca L. collected bimonthly during one year (four times on the fifteenth day of January, March, May, July, September, and November - 2004) were subjected to GC/FID and GC-MS analysis, from which thirteen components were identified. Additionally, part of the oil obtained from January collection was subjected to fractionation over silica gel soaked with AgNO3 to afford five of the main sesquiterpenes (β-elemene, β-caryophyllene, α-humulene, β-selinene, and α-cadinol). The obtained data showed a significative variation in the proportions of the components, which could be associated to climatic parameters in each collection periods.

Os óleos voláteis das folhas de Michelia champaca L., coletadas bimestralmente ao longo de um ano (quatro vezes no décimo quinto dia de janeiro, março, maio, julho, setembro e novembro de 2004), foram submetidos à análise por CG/DIC e CG-EM, de onde foram identificados treze componentes. Adicionalmente, parte do óleo obtido na coleta de janeiro foi submetida a fracionamento em gel de sílica impregnada com AgNO3 fornecendo cinco dos principais sesquiterpenos (β-elemeno, β-cariofileno, α-humuleno, β-selineno e α-cadinol). Os dados obtidos mostram uma variação significativa na proporção dos componentes, a qual pode estar associada a parâmetros microclimáticos em cada período de coleta.

Chemical constituents from Swartzia apetala Raddi var. glabra and evaluation of their antifungal activity against Candida spp / Constituintes químicos de Swartzia apetala Raddi var. glabra e avaliação da atividade antifúngica contra espécies de Candida

From the hexanic extract of the stem from Swartzia apetala Raddi var. glabra were isolated one stilbene (1), one flavanone (2), one pterocarpan (3), one triterpene (4) and a mixture of three steroids (5 to 7). The crude extract and the compounds isolated were submitted to evaluation of the antifungal activity against nine yeast standard ATCC of the Candida genus. Among the compounds only the triterpene (4) and the mixture of steroids (5 to 7) showed no activity. The structures of the compounds were determined by spectral data analysis of GC/MS and ¹H and 13C NMR (1D and 2D experiments), as well as comparison with literature values.

Do extrato hexânico da madeira de Swartzia apetala Raddi var. glabra foram isolados um estilbeno (1), uma flavanona (2), um pterocarpano (3), um triterpeno (4) e uma mistura de esteróides (5 a 7). O extrato bruto e as substâncias isoladas foram submetidas à avaliação do potencial antifúngico usando nove cepas padrão ATCC do gênero Candida. Entre as substâncias testadas apenas o triterpeno (4) e a mistura de esteróides (5 a 7) não apresentaram atividade. As estruturas das substâncias foram determinadas através da análise dos espectros de CG/EM, e RMN (1D e 2D) e comparação com dados da literatura.

Terpenóides com atividade sobre o Sistema Nervoso Central (SNC): [revisão] / Terpenoids with activity in the Central Nervous System (CNS): [review]

Os terpenóides constituem um vasto grupo de metabólitos secundários com ações sobre o SNC, destacando-se suas atividades sedativa, ansiolítica, antinociceptiva, anticonvulsivante, pró-convulsivante e alucinógena. Neste trabalho foi realizada uma revisão bibliográfica sobre terpenóides com ações descritas no SNC, enfocando moléculas e sistemas neurotransmissores relacionados com sua atividade. As substâncias abordadas encontram-se divididas em mono, sesqui, di, tri e meroterpenóides e incluem compostos isolados e plantas que apresentam ação principalmente sobre os sistemas neurotransmissores GABAérgico, glutamatérgico, dopaminérgico e opióide.

The terpenoids are a large group of secondary metabolites which display many activities in the CNS, such as sedative, ansiolytic, antinociceptive, anticonvulsant, pro-convulsant and hallucinogenic. In this work we performed a research on terpenoids that exert effects on the CNS, focusing molecules and neurotransmitter systems related to their actions. The substances approached were classified as mono, sesqui, di, tri and meroterpenoids and include isolated compounds and plants which exert activities mainly on GABAergic, glutamatergic, dopaminergic and opioid neurotransmitter systems.

Larvicidal activity of oil-resin fractions from the Brazilian medicinal plant Copaifera reticulata Ducke (Leguminosae-Caesalpinoideae) against Aedes aegypti (Diptera, Culicidae)

Oil-resin fractions from Copaifera reticulata Ducke (Leguminosae-Caesalpinoideae) were evaluated for larvicidal activity on third larval instars of Aedes aegypti, in searching for alternative control methods for this mosquito. The bioactive fractions were chemically monitored by thin-layer chromatography, ¹H and 13C nuclear magnetic resonance and mass spectrometry. Bioassays were performed using five repetitions, at a temperature of 28 ± 1°C, relative humidity of 80 ± 5 percent and light and dark cycles of 12h. Mortality was indicated by darkening of the cephalic capsule after 24h of exposure of the larvae to the solutions. The most active fractions were CRM1-4 (sesquiterpenes) and CRM5-7 (labdane diterpenes), which showed LC50 values of 0.2 and 0.8ppm, respectively.

A atividade larvicida das frações do óleo-resina de Copaifera reticulata Ducke (Leguminosae-Caesalpinoideae) foi avaliada em larvas de 3° estádio de Aedes aegypti, na busca de alternativas para o controle desse mosquito. As frações bioativas foram monitoradas quimicamente através de cromatografia de camada delgada, analisada por ressonância magnética nuclear de hidrogênio (¹H e 13C) e espectrometria de massas. Os bioensaios foram realizados à temperatura de 28±1°C, 80±5 por cento de umidade relativa e fotofase de 12h, com cinco repetições. A mortalidade foi determinada através do escurecimento da cápsula cefálica, após 24h de exposição das larvas às soluções. As frações mais ativas foram CRM1-4 (sesquiterpenos) e CRM5-7 (diterpeno labdano), que mostraram os valores de CL50 de 0,2 e 0,8ppm, respectivamente.