Lethal and sublethal effects of essential oils fromPiper capitarianumYunck andPiper krukoffiiYunck onPlutella xylostellaL.

Plutella xylostella (L.) is responsible for considerable vegetable crop losses in the metropolitan region of Manaus, Brazil. In recent decades, essential oils have been investigated as an alternative to synthetic insecticides. The genusPiperis widely distributed in Amazonia and essential oils from these plants have insecticidal properties. This study describes the chemical composition of the essential oils fromPiper capiterianumandPiper krukoffiias well as the lethal and sublethal effects onP. xylostella. The phytotoxicity of the oils on the host plant was also evaluated. Globulol was the major constituent of theP. krukoffiioil ando-cymene was the major constituent of theP. capitarianumoil. The oil fromP. capiterianumexhibited greater toxicity to larvae and eggs. This oil also presented greater repellant action, feeding deterrence and mild phytotoxicity to the host plant (Brassicae oleraceae). The findings suggest that this oil can be used in the preparation of a formulated insecticide for the management ofP. xylostellain different development phases. However, further studies are needed to evaluate the effect of this oil on crops under field conditions as well as non-target organisms and determine the cost-benefit ratio of a product formulated withP. capitarianumoil.

Synthesis of new 1,4-disubstituted 1,2,3-triazoles using the CuAAC reaction and determination of their antioxidant activities.

This study describes the synthesis and antioxidant activity of new 1,4-disubstituted 1,2,3-triazoles. These compounds were generated semi-synthetically using the Cu(I)-catalysed azide-alkyne cycloaddition (CuAAC) reaction between ethyl 2-azidoacetate and terminal acetylenes derived from the natural products carvacrol, eugenol, isovanillin, thymol and vanillin. The products were obtained at 50 to 80% yield and characterised through several spectrographic techniques. Antioxidant activity was assayed using 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS). The products exhibited moderate antioxidant activity, with ethyl 2-(4-((4-formyl-2-methoxyphenoxy)methyl)-1H-1,2,3-triazol-1-yl) acetate showing the highest antioxidant capacity (EC50 = 75.5 µg/mL) among the generated 1,4-disubstituted 1,2,3-triazoles. In conclusion, the generation of these compounds opens new possibilities for the development of new antioxidant agents.

Insecticidal properties and chemical composition of Piper aduncum L., Lippia sidoides Cham. and Schinus terebinthifolius Raddi essential oils against Plutella xylostella L.

In the laboratory, were evaluated the effects (residual contact and feeding deterrence) of the essential oils from the leaves of Piper aduncum, Lippia sidoides and Schinus terebinthifolius, as well as eleven selected constituents and binary blends of oils in different proportions against 3rd instar larvae of Plutella xylostella (L.). The Piper oil demonstrated the greatest toxicity (LC50 = 0.31 µL/mL) and feeding deterrence (DC50 = 1.08 µL/mL) between oils tested. Dillapiole (LC50 = 1.01 µL/mL; DC50 = 1.10 µL/mL) and carvacrol (LC50 = 6.03 µL/mL; DC50 = 0.075 µL/mL) demonstrated the greatest toxicity and feeding deterrence between constituents tested, respectively. Based on the fractional effects indices for the blends, a synergistic interaction was found for the blend of the Lippia and Schinus oils at a proportion of 75 and 25%, respectively. The present findings indicate that this blend could be used in the control of P. xylostella, as the literature reports populations resistant to the active ingredient in the positive control, Premio®. Further studies are needed for the development of a new botanical insecticide based on the active ingredients in oils from L. sidoides and S. terebinthifolius to improve efficiency, stability and the cost-benefit in the control of P. xylostella.

Comparative toxicity of essential oil and blends of selected terpenes of Ocotea species from Pernambuco, Brazil, against Tetranychus urticae Koch.

Essential oils from the leaves of two species of the genus Ocotea that occur in the Atlantic Forest in the state of Pernambuco, Brazil, were analyzed using gas chromatography-mass spectrometry. The acaricidal activity of these oils as well as 11 selected components and blends were evaluated in fumigation and residual contact tests against the two-spotted spider mite (Tetranychus urticae). Sixty-seven constituents were identified, totaling 97.3 ± 0.3% and 97.8 ± 0.5% of the oils from O. duckei and O. glomerata, respectively. Sesquiterpene was the dominant class. The compounds ß-caryophyllene (18.6 ± 0.1%) and aromadendrene (17.3 ± 0.6%) were the main constituents of the oils from O. duckei and O. glomerata, respectively. Acaricidal action varied depending on the method employed, species and chemical nature of the selected constituents. The mites were susceptible to the oils and chemical constituents using the fumigation method. The O. duckei oil was respectively 2.5-fold and 1.5-fold more toxic than the O. glomerata oil using the fumigation and residual contact methods. Among the selected constituents, ß-caryophyllene was the most toxic, independently of the method employed. The individual toxicity of the selected compounds and their blends as well as the role of these constituents in the overall toxicity of the essential oils are also discussed.

Acaricidal activity and repellency of essential oil from Piper aduncum and its components against Tetranychus urticae.

The chemical composition of essential oil of leaves of Piper aduncum L., growing wild in a fragment of the Atlantic Rainforest biome in northeastern Brazil, was determined through gas chromatography-mass spectrometry. The acaricidal activity and repellency of the essential oil and its components [dillapiole (0.28 g/ml), α-humulene (0.016 g/ml), (E)-nerolidol (0.0007 g/ml) and ß-caryophyllene (0.0021 g/ml)] were evaluated in the laboratory against adults of Tetranychus urticae Koch. The mites were more susceptible to the oil in fumigation tests (LC(50) = 0.01 µl/l of air) than in contact test with closed Petri dish (LC(50) = 7.17 µl/ml); mortality was reduced by approximately 50 % in the latter test. The repellent action of the oil and toxicity by fumigation and contact did not differ significantly from the positive control (eugenol). The repellent activity was attributed to the components (E)-nerolidol, α-humulene and ß-caryophyllene, whereas toxicity by fumigation and contact was attributed to ß-caryophyllene. The effect of Piper oil and the role of its components regarding host plant preference with a two-choice leaf disk test are also discussed.

The chemical ecology of tropical forest diversity: Environmental variation, chemical similarity, herbivory, and richness.

Species richness in tropical forests is correlated with other dimensions of diversity, including the diversity of plant-herbivore interactions and the phytochemical diversity that influences those interactions. Understanding the complexity of plant chemistry and the importance of phytochemical diversity for plant-insect interactions and overall forest richness has been enhanced significantly by the application of metabolomics to natural systems. The present work used proton nuclear magnetic resonance spectroscopy (1 H-NMR) profiling of crude leaf extracts to study phytochemical similarity and diversity among Piper plants growing naturally in the Atlantic Rainforest of Brazil. Spectral profile similarity and chemical diversity were quantified to examine the relationship between metrics of phytochemical diversity, specialist and generalist herbivory, and understory plant richness. Herbivory increased with understory species richness, while generalist herbivory increased and specialist herbivory decreased with the diversity of Piper leaf material available. Specialist herbivory increased when conspecific host plants were more spectroscopically dissimilar. Spectral similarity was lower among individuals of common species, and they were also more spectrally diverse, indicating phytochemical diversity is beneficial to plants. Canopy openness and soil nutrients also influenced chemistry and herbivory. The complex relationships uncovered in this study add information to our growing understanding of the importance of phytochemical diversity for plant-insect interactions and tropical plant species richness.

Biosynthesis of Pellucidin A in Peperomia pellucida (L.) HBK.

Peperomia pellucida (L.) HBK (Piperaceae) ("jabuti herb") is an herbaceous plant that is widespread in the tropics and has several ethnomedicinal uses. The phytochemical study of leaf extracts resulted in the isolation of 2,4,5-trimethoxycinnamic acid, 5,6,7-trimethoxyflavone, 2,4,5-trimethoxystyrene, 2,4,5-trimethoxybenzaldehyde, dillapiol, and sesamin in addition to pellucidin A. The co-occurrence of styrene and cyclobutane dimers suggested the formation of pellucidin A by a photochemical [2+2] cycloaddition of two molecules of 2,4,5-trimethoxystyrene. To investigate this biogenesis, analysis of plant leaves throughout ontogeny and treatments such as drought, herbivory and, exposure to jasmonic acid and UV365 light were carried out. Significant increases in the content of dillapiol (up to 86.0%) were found when P. pellucida plants were treated with jasmonic acid, whereas treatment under UV365 light increase the pellucidin A content (193.2%). The biosynthetic hypothesis was examined by feeding various 13C-labeled precursors, followed by analysis with GC-MS, which showed incorporation of L-(2-13C)-phenylalanine (0.72%), (8-13C)-cinnamic acid (1.32%), (8-13C)-ferulic acid (0.51%), (8-13C)-2,4,5-trimethoxycinnamic acid (7.5%), and (8-13C)-2,4,5-trimethoxystyrene (12.8%) into pellucidin A. The enzymatic conversion assays indicated decarboxylation of 2,4,5-trimethoxycinnamic acid into 2,4,5-trimethoxystyrene, which was subsequently dimerized into pellucidin A under UV light. Taken together, the biosynthesis of pellucidin A in P. pellucida involves a sequence of reactions starting with L-phenylalanine, cinnamic acid, ferulic acid, 2,4,5-trimethoxycinnamic acid, which then decarboxylates to form 2,4,5-trimethoxystyrene and then is photochemically dimerized to produce pellucidin A.

Stabilization and detection of hydrophylloquinone as di-O-methyl derivative.

Phylloquinone is a redox active naphthoquinone involved in electron transport in plants. The function of this reduced form remains unclear due to its instability, which has precluded detection. Herein, a simple method that permits the stabilization of the reduced form of phylloquinone by di-O-methylation and HPLC detection is described.

New sources of botanical acaricides from species of Croton with potential use in the integrated management of Tetranychus urticae / Nuevas fuentes de acaricidas botánicos de especies de Croton con uso potencial en el manejo integrado de Tetranychus urticae

Essential oils from the leaves and stems of Croton adenocalyx, C. grewioides, C. heliotropiifoliusand C. blanchetianus obtained through hydrodistillation were analyzed by GC-MS. We then investigated the lethal and sublethal effects of the Croton oils and 15 major constituents against Tetranychus urticae. ß-Caryophyllene was the major component in the leaf and stem oils from C. heliotropiifolius and C. adenocalyx. Spathulenol and (E)-anethole were the major constituents identified in the leaf and stem oils of C. blanchetianus and C. grewioides, respectively. The oil with the greatest lethal and sublethal effects was those from C. adenocalyx. Among the constituents ß-caryophyllene and spatulenol were the most toxic to the mite, where as eugenol and methyl eugenol were the most repellent. The toxicity and repellency of the Croton oils, particularly the oils from C. adenocalyx, demonstrate that these oils constitute a promising alternative to synthetic acaricides for use in the control of T. urticae.

Los aceites esenciales de las hojas y tallos de Croton adenocalyx, C. growioides, C. heliotropiifolius y C. blanchetianus obtenidos mediante hidrodestilación fueron analizados a través de GC-MS. Se investigaron los efectos letales y subletales de los aceites de Croton y 15 componentes principales contra Tetranychus urticae. El ß-cariofileno fue el componente principal en los aceites de hojas y tallos de C. heliotropiifolius y C. adenocalyx. El espatulenol y el (E)-anetol fueron los principales componentes identificados en los aceites de hojas y tallos de C. blanchetianus y C. growioides, respectivamente. El aceite con los mayores efectos letales y subletales fue el de C. adenocalyx. Entre los componentes, el ß-cariofileno y el espatulenol fueron los más tóxicos para el ácaro, mientras que el eugenol y el metil eugenol fueron los más repelentes. La toxicidad y la repelencia de los aceites de Croton, particularmente los aceites de C. adenocalyx, demuestran que estos aceites constituyen una alternativa prometedora respecto a los acaricidas sintéticos para uso en el control de T. urticae.

Change in the Chemical Profile of Mangifera indica Leaves after their Metabolism in the Tropidacris collaris Grasshopper.

This present work addresses research on the discovery of new compounds from natural sources. It is based on a study of Mangifera indica leaf metabolism by the Tropidacris collaris grasshopper. We found that the grasshopper hydrolyzed the flavonoid isoquercitrin to quercetin when the O-glycosidic bond was broken and sugar released as a probable energy source for the insect. There was not, however, hydrolysis of the major compound in the leaves, mangiferin, which contains the C-glycosidic bond. All compounds were isolated and their chemical structure determined by UV, IR, MS, 1H and 13C NMR.

Chemical composition and acaricidal activity of essential oils and selected terpenes from two species of Psidium in the Cerrado biome of Brazil against Tetranychus urticae / Composición química y actividad acaricida del aceite esencial y terpenos seleccionados de dos especies de Psidium de Cerrado Biome de Brasil contra Tetranychus urticae

The aim of this study was to investigate the chemical composition and acaricidal effect of two Psidium species essential oils and selected compounds on Tetranychus urticae. Essential oils from the leaves of Psidium laruotteanum and Psidium myrsinites were obtained through hydrodistillation, analyzed using CG-FID and CG-MS and evaluated for toxicity to T. urticae by fumigation and residual contact. The susceptibility of T. urticae to monoterpenes and sesquiterpenes was also investigated. The major constituents of the P. laruotteanum oil were (E)-nerolidol (9.6 ± 0.4%) and γ-terpinene (9.4 ± 0.6%) and the major constituents of the P. myrsinites oil were ß-caryophyllene (21.2 ± 0.9%) and α-humulene (10.3 ± 0.5%). Based on the LC50 estimates, no significant differences were found between the two oils regarding toxicity by fumigation or residual contact. ß-Caryophyllene and (E)-nerolidol had the highest level of toxicity, independently of the method investigated. The findings indicate that both oils and selected constituents, especially ß-caryophyllene and (E)-nerolidol, are promising as natural acaricidal agents that affect T. urticae through more than one mode of action.

Los aceites esenciales de las hojas de Psidium laruotteanum y Psidium myrsinites se obtuvieron por hidrodestilación, se analizaron por CG-FID y CG-MS, y se evaluaron sus toxicidades por fumigación y contacto residual contra Tetranychus urticae. Se investigó también la susceptibilidad del T. urticae a monoterpenos y sesquiterpenos. En el aceite esencial de P. laruotteanum, (E)-nerolidol (9.6 ± 0.4%) y γ-terpinene (9.4 ± 0.6%) se identificaron como constituyentes mayoritarios, mientras que en el aceite esencial de P. myrsinites, ß-caryophyllene (21.2 ± 0.9%) y α-humulene (10.3 ± 0.5%) se encontraron como mayoritarios. Con base en las CL50 estimadas, no se observaron diferencias significativas entre las toxicidades de los aceites por fumigación, y tampoco por contacto residual. ßCaryophyllene y (E)-nerolidol presentaron las mayores toxicidades, independientemente del método investigado. Estos resultados indican, que los dos aceites, así como los constituyentes seleccionados, entre los que se destacan ß-caryophyllene y (E)-nerolidol, son promisores agentes acaricidas naturales por actuar en el T. urticae por más de un mecanismo de acción.

Chemical composition, leishmanicidal and cytotoxic activities of the essential oils from Mangifera indica L. var. Rosa and Espada.

The essential oils from Mangifera indica var. Rosa and Espada latex were obtained by hydrodistillation and analyzed using GC-FID and GC-MS. Twenty-seven components were identified. The main compound in the essential oil from M. indica var. Espada (EOMiE) was terpinolene (73.6%). The essential oil of M. indica var. Rosa (EOMiR) was characterized by high amounts of ß-pinene (40.7%) and terpinolene (28.3%). In the test for leishmanicidal activity against promastigotes forms of L. amazonensis, EOMiR and EOMiE showed IC50 (72 h) of 39.1 and 23.0 µg/mL, respectively. In macrophages, EOMiR and EOMiE showed CC50 of 142.84 and 158.65 µg/mL, respectively. However, both were more specific to the parasite than macrophages, with values of selectivity index of 6.91 for EOMiE and 3.66 for EOMiR. The essential oils were evaluated for their cytotoxicity against the human tumor cells HEp-2, HT-29, NCI-H292, and HL-60. The EOMiR and EOMiE were most effective against the HL-60, with IC50 values of 12.3 and 3.6 µg/mL, respectively. The results demonstrated that the essential oils of M. indica can destroy L. amazonensis and inhibit tumor cell growth. These findings contribute to the knowledge of the Brazilian biodiversity as a source of potential therapeutic agents.

Comparative toxicity of essential oil and blends of selected terpenes of Ocotea species from Pernambuco, Brazil, against Tetranychus urticae Koch

ABSTRACT Essential oils from the leaves of two species of the genus Ocotea that occur in the Atlantic Forest in the state of Pernambuco, Brazil, were analyzed using gas chromatography-mass spectrometry. The acaricidal activity of these oils as well as 11 selected components and blends were evaluated in fumigation and residual contact tests against the two-spotted spider mite (Tetranychus urticae). Sixty-seven constituents were identified, totaling 97.3 ± 0.3% and 97.8 ± 0.5% of the oils from O. duckei and O. glomerata, respectively. Sesquiterpene was the dominant class. The compounds β-caryophyllene (18.6 ± 0.1%) and aromadendrene (17.3 ± 0.6%) were the main constituents of the oils from O. duckei and O. glomerata, respectively. Acaricidal action varied depending on the method employed, species and chemical nature of the selected constituents. The mites were susceptible to the oils and chemical constituents using the fumigation method. The O. duckei oil was respectively 2.5-fold and 1.5-fold more toxic than the O. glomerata oil using the fumigation and residual contact methods. Among the selected constituents, β-caryophyllene was the most toxic, independently of the method employed. The individual toxicity of the selected compounds and their blends as well as the role of these constituents in the overall toxicity of the essential oils are also discussed.

Chemical composition of essential oil from leaves of Ocotea limae Vattimo Gil. and Ocotea gardneri (Meisn. ) Mez. growing wild in Atlantic forest of North-Eastern Brazil / [Composición química del aceite esencial de las hojas de Ocotea limae Vattimo Gil. y Ocotea gardneri (Meisn. ) Mez. nativas de la floresta Atlántica del Nordeste de Brasil

Essential oils from leaves of Ocotea limae and Ocotea gardneri species were analyzed by GC-FID and GC-MS. The analysis revealed the presence of 48 components accounting for 98.1 ± 1.3% e 98.0 ± 0.5% of the essential oils from the O. limae and O. gardneri, respectively. The oils were characterized by high percentage of sesquiterpenes. The mains compounds identified in the essential oils were spathulenol (13.3 ± 0.5%), ß-caryophyllene (12.4 ± 0.5%), bicyclogermacrene (11.3 ± 0.4%) and germacrene D (10.9 ± 0.3%) from the O. limae and germacrene D (26.9 ± 0.9%) e bicyclogermacrene (21.7 ± 0.7%) from the O. glomerata.

Los aceites esenciales de hojas de Ocotea limae y Ocotea gardneri fueron analizados por GC-FID y GC-MS. El análisis reveló la presencia de 48 componentes que representan 98,1 ± 1,3% y 98,0 ± 0,5% de los aceites esenciales de O. limae y O. gardneri, respectivamente. Los aceites se caracterizaron por un alto porcentaje de sesquiterpenos. Los principales compuestos identificados en los aceites esenciales fueron espatulenol (13,3 ± 0,5%), ß-cariofileno (12,4 ± 0,5%), biciclogermacreno (11,3 ± 0,4%) y germacreno D (10,9 ± 0,3%) de O. limae y germacreno D (26,9 ± 0,9%) y bicyclogermacreno (21,7 ± 0,7%) de la O. glomerata.

Circadian variation of essential oil from Piper marginatum Jacq / Variaciones circadiana de aceite esencial de Piper marginatum Jacq

The composition of the essential oil from the leaves of Piper marginatum (Piperaceae) shows circadian variation and a higher yield during high solar incidence. The essential oils samples were investigated by GC-FID and GC-MS, which allowed identification of 29 compounds. Principal component analysis (PCA) and cluster analysis (CA) showed a significant quantitative variability in the chemical composition of the studied samples as well as a correlation between the oil profiles and the collection time. Two main groups were observed, with predominance of phenylpropanoids or sesquiterpenes. The predominant chemical compounds were phenylpropanoids, having as main representative (Z)-asarone and (E)-asarone.

La composición del aceite esencial de hojas de Piper marginatum (Piperaceae) muestra una variación circadiana y un mayor rendimiento durante la mayor incidencia solar. Las muestras de aceites esenciales se investigaron por GC-FID y GC-MS, lo que permitió la identificación de 29 compuestos. El análisis de componentes principales y el análisis de conglomerados mostraron una variación cuantitativa significativa en la composición química de las muestras estudiadas, así como una correlación entre los perfiles del aceite esencial y el tiempo de recolección. Se observaron dos grupos principales, con predominio de fenilpropanoides o sesquiterpenos. Los compuestos predominantes fueron los fenilpropanoides, (Z)-asarona y (E)-asarona.