Taxonomic Insights and Its Type Cyclization Correlation of Volatile Sesquiterpenes in Vitex Species and Potential Source Insecticidal Compounds: A Review.

Sesquiterpenes (SS) are secondary metabolites formed by the bonding of 3 isoprene (C5) units. They play an important role in the defense and signaling of plants to adapt to the environment, face stress, and communicate with the outside world, and their evolutionary history is closely related to their physiological functions. This review considers their presence and extensively summarizes the 156 sesquiterpenes identified in Vitextaxa, emphasizing those with higher concentrations and frequency among species and correlating with the insecticidal activities and defensive responses reported in the literature. In addition, we classify the SS based on their chemical structures and addresses cyclization in biosynthetic origin. Most relevant sesquiterpenes of the Vitex genus are derived from the germacredienyl cation mainly via bicyclogermacrene and germacrene C, giving rise to aromadrendanes, a skeleton with the highest number of representative compounds in this genus, and 6,9-guaiadiene, respectively, indicating the production of 1.10-cyclizing sesquiterpene synthases. These enzymes can play an important role in the chemosystematics of the genus from their corresponding routes and cyclizations, constituting a new approach to chemotaxonomy. In conclusion, this review is a compilation of detailed information on the profile of sesquiterpene in the Vitex genus and, thus, points to new unexplored horizons for future research.

Volatile Metabolomic Composition of Vitex Species: Chemodiversity Insights and Acaricidal Activity.

The Vitex genus (Lamiaceae) produces a plethora of metabolites that include ecdysteroids and terpenoids, some of which have demonstrated insect repellent properties. The volatile composition of several members of this genus has not been chemically defined, as many taxa are endemic to remote ecosystems. In this study, leaves were collected from the northeast of Brazil from Vitex capitata, V. megapotamica, V. gardneriana, and V. rufescens plants and examined for their chemical profile via GC-MS/FID of essential oil extracts. The analyses showed a diversity of terpenoids. Of particular note were seven-member ring sesquiterpenes which were present in great abundance; a dendrogram showed clades separating by the production of bicyclogermacrene, aromadendrane and 5,10-cycloaromadendrane sesquiterpenoids for the four species. Comparison of volatile metabolite profiles to 13 other Vitex species showed strong similarities in the production of some monoterpenes, but varied by their production of larger terpenes, especially those with gem-dimethylcyclopropyl subunits on seven-member ring compounds. From this work, we suggest that the sesquiterpene skeleton with seven member rings is a good chemosystematic biomarker candidate for the Vitex genus. Separation using this biomarker was then validated using Inter-Simple Sequence Repeat profiling. Lastly, experiments examining the toxicity of these four oils against the coconut mite Aceria guerreronis showed that only the oil of V. gardneriana had strong acaricidal activity, with an LC50 of 0.85 mg/mL, thus demonstrating its potential for use as a natural pesticide.

Toxicity of vegetable oils to the coconut mite Aceria guerreronis and selectivity against the predator Neoseiulus baraki.

The coconut mite, Aceria guerreronis (Acari: Eriophyidae), is a major tropical pest of coconut. Here, we assessed the chemical profiles and the potential use of babassu, degummed soybean, and coconut oils to control A. guerreronis as well as their side-effects on the predatory mite Neoseiulus baraki (Acari: Phytoseiidae), a key natural enemy of the coconut mite. Babassu and coconut oils had similar fatty acids chemical profiles. All vegetable oils showed toxicity to A. guerreronis; degummed soybean oil exhibited the highest toxicity (LC50 = 0.15 µL/cm2). Although all oils were less toxic to N. baraki, their potential to attract/repel this predatory mite differed. Whereas N. baraki females were unresponsive to coconut oil at both concentrations (i.e., LC50 and LC99 estimated for A. guerreronis), irrespective of exposure period (i.e., 1 or 24 h), the babassu oil repelled the predator, independent of exposure period, when applied at its LC99 (1.48 µL/cm2). Intriguingly, this oil also exhibited attractiveness to N. baraki 24 h after exposure when applied at its LC50 (0.26 µL/cm2). A similar attractiveness pattern was recorded 24 h after N. baraki was exposed to degummed soybean oil at both concentrations tested (LC50 = 0.15 µL/cm2; LC99 = 1.39 µL/cm2). However, N. baraki was repelled by degummed soybean oil at its LC50 after 1 h of exposure. Therefore, the present study demonstrated that all the vegetable oils used here had higher toxicity to the coconut mite and considerable selectivity to the predator N. baraki, indicating they are promising tools that can potentially be included in management programs to control A. guerreronis in commercial coconut plantations.

Erythroxylum pungens elicits vasorelaxation by reducing intracellular calcium concentration in vascular smooth muscle cells of rats

The cardiovascular effects elicited by the ethanolic extract obtained from the roots of Erythroxylum pungens O.E. Schulz, Erythroxylaceae (EEEP) and the vasorelaxant effect induced by its main tropane alkaloid (pungencine) were investigated. In normotensive rats, administration of EEEP (1, 10, 30 and 60 mg/kg i.v., randomly) produced dose-dependent hypotension (-2±1, -7±0.5 -17.6±1, -24±1 Δ mmHg, n=5) followed by tachycardia (3±0.5, 7±2, 7.1±1, 10±5 Δ bpm, n=5). In intact phenylephrine (Phe, 10 µM)-pre-contracted rings, EEEP (0.01-500 µg/mL) induced concentration-dependent vasorelaxation (EC50 13.7±5.5 µg/mL, Maximal Response= 92±2.6%), and this effect was unchanged after the removal of the vascular endothelium (EC50 27.2±4.7 µg/ml, Maximal Response= 88.3±3.3 %). In KCl (80 mM)-pre-contracted-endothelium-denuded rings, EEEP elicited concentration-dependent relaxation (EC50= 128.2±11.2 µg/mL, Maximal Response 76.8±3.4%). Vasorelaxation has also been achieved with tonic contractions evoked by the L-type Ca2+ channel agonist Bay K 8644 (EC50 80.2±9.1 µg/mL, Maximal Response 86.3±8.3%). In addition, in a depolarizing medium, EEEP inhibited CaCl2 (30-500 µg/mL) induced contractions and caused a concentration-dependent rightward shift of the relaxation curves. Lastly, the tropane alkaloid pungencine caused vasorelaxation in mesenteric arteries resembling to the EEEP responses. These results suggests that EEEP induces hypotension and vasorelaxation, at least in part, due to the reduction in [Ca2+]i in vascular smooth muscle cells.

Atividade farmacológica da monocrotalina isolada de plantas do gênero Crotalaria / Pharmacological activity of monocrotalina isolated from plants of the genus Crotalaria

Crotalaria retusa é uma planta encontrada no Nordeste brasileiro, pertence ao gênero Crotalaria e à família Leguminosae, e possuem mais de seissentas espécies no mundo e mais de quarenta no Brasil. As variedades tóxicas mais conhecidas são C. spectabilis, C. crispata, C. retusa, C. dura e C. globifera. Plantas do gênero Crotalaria são de interesse porque são usadas na medicina popular. Esses gêneros são ricos em alcaloides pirrolizidínicos (AP), que são as principais toxinas e apresentam efeitos pneumotóxicos, nefrotóxicos, cardiotóxicos, fetotóxicos, carcinogênicos, inflamação, hemorragia e fibrose. A monocrotalina é o principal alcaloide pirrolizidínico encontrado nessas plantas e é ativamente oxidada in vivo pelo citocromo P450 no fígado, formando intermediários altamente reativos tipo pirrólicos que são responsáveis pela ligação cruzada do DNA-DNA e DNA-proteína. O presente trabalho teve como objetivo fazer um levantamento bibliográfico via internet, utilizando bancos de dados, programas de pesquisa científica e pesquisa em livros relacionados, acerca da atividade farmacológica e do mecanismo de ação da monocrotalina extraída de plantas do gênero Crotalaria, ressaltando desde os aspectos botânicos da planta, estrutura química dos alcaloides pirrolizidínicos, exemplos experimentais de toxicidade e provável mecanismo de ação.

Crotalia retusa is a plant found in Brazilian Northeast and belongs to the genus Crotalaria and the family Leguminosae, which comprises more than 600 species throughout the world and more than forty in Brazil. The most known toxic species are C. spectabilis, C. crispata, C. retusa, C. dura and C. globifera. Plants of the Crotalaria genus are of great interest because they are used by humans for folk medicine. These plants are rich in pyrrolizidine alkaloids (PA), which are the main toxins that cause effects such as pneumotoxic, nefrotoxic, cardiotoxic, fetotoxic, carcinogenic, inflammation, hemorrhage and fibrosis. Monocrotaline is the main pirrolizidinic alkaloid found in plants and is actively oxidated in vivo by the cytochrome P450 in the liver, yielding highly reactive pyrrolic type intermediates, which are responsible for DNA-DNA and DNA-protein cross-links reaction. The aim of this work is to make a bibliographic survey via internet, using databases, scientific research programs and related books, about pharmacological activity and mechanism of action of monocrotaline extracted from plants of Crotalaria genus, emphasizing plant botanical aspects, chemical structure of pirrolizidinic alkaloid, experimental examples of toxicity and probable action mechanism.

Chemical epigenetics alters the secondary metabolite composition of guttate excreted by an atlantic-forest-soil-derived Penicillium citreonigrum.

Chemical epigenetic manipulation of Penicillium citreonigrum led to profound changes in the secondary metabolite profile of its guttate. While guttate from control cultures exhibited a relatively simple assemblage of secondary metabolites, the guttate collected from cultures treated with 50 muM 5-azacytidine (a DNA methyltransferase inhibitor) was highly enriched in compounds representing at least three distinct biosynthetic families. The metabolites obtained from the fungus included six azaphilones (sclerotiorin (1), sclerotioramine (6), ochrephilone (2), dechloroisochromophilone III (3), dechloroisochromophilone IV (4), and 6-((3E,5E)-5,7-dimethyl-2-methylenenona-3,5-dienyl)-2,4-dihydroxy-3-methylbenzaldehyde (5)), pencolide (7), and two new meroterpenes (atlantinones A and B (9 and 10, respectively)). While pencolide was detected in the exudates of both control and 5-azacytidine-treated cultures, all of the other natural products were found exclusively in the guttates of the epigenetically modified fungus. All of the metabolites from the P. citreonigrum guttate were tested for antimicrobial activity in a disk diffusion assay. Both sclerotiorin and sclerotioramine caused modest inhibition of Staphylococcus epidermidis growth; however, only sclerotioramine was active against a panel of Candida strains.

A chemical marker proposal for the Lantana genus: composition of the essential oils from the leaves of Lantana radula and L. canescens.

Essential oil extracts from the leaves of two Lantana species (L. radula Sw. and L. canescens Kunth), for which no prior analysis has been reported, were analyzed by GC-MS. This information was utilized to propose chemical markers for Lantana species so that identification between physically similar plant species can be achieved through chemical analysis. Results showed 33 constituents for L. canescens, among which beta-caryophyllene (43.9%), beta-cubebene (10.1%), elixene (8.6%), beta-phellandrene (6.1%), alpha-caryophyllene (2.6%) and dehydro-aromadendrene (2.6%) were the principle components. L. radula revealed the presence of 21 compounds, the most abundant of which were beta-cubebene (31.0%), beta-caryophyllene (20.8%), elixene (10.0%), alpha-salinene (6.4%), beta-phellandrene (6.1%), copaene (4.9%) cadinene (1.4%) and psi-limonene (1.4%). The high concentration of beta-caryophyllene in the samples tested here and those in the literature make it a good candidate for a chemical marker for Lantana species, with beta-cubebene, elixene and beta-phellandrene following as minor compounds identified more sporadically in this genus. On the other hand, Lippia species, which are morphologically similar to those from the Lantana genus, would contain limonene, citral, carvacrol, beta-myrcene, camphor and thymol as the main chemical markers. These chemical markers would be a powerful tool for maintaining quality control in the extraction of essential oils for use in medicinal applications, as well as in identification of plant specimens to a taxonomist.

Tropane alkaloids from Erythroxylum genus: distribution and compilation of 13C-NMR spectral data.

Erythroxylum, the most representative genus of the Erythroxylaceae family, presents tropane alkaloids as main constituents. This class of compounds greatly contributes to the chemotaxonomic characterization of plants of this genus, and it has important medical uses and shows toxic effects. This review describes 186 tropane alkaloids in the 35 species of Erythroxylum distributed worldwide. In addition, a compilation of their (13)C-NMR spectral data is presented.

Phenylethanoid and lignan glycosides from polar extracts of Lantana, a genus of verbenaceous plants widely used in traditional herbal therapies.

Many references to the use of Lantana spp. can be found in the ethnopharmacological literature from locations around the globe. This study was focused on examining constituents from the polar extracts of Lantana radula Sw. and Lantana canescens Kunth, for which no prior chemical investigations had been reported. A new phenylethanoid glycoside, raduloside, and lignan glycoside, radulignan, were identified along with the known compounds alyssonoside, arenarioside, calceolarioside E, isonuomioside, samioside, and verbascoside.

Acanthospermum hispidum DC (Asteraceae): perspectives for a phytotherapeutic product: [revision] / Acanthospermum hispidum DC (Asteraceae): perspectivas para um produto fitoterápico: [revisão]

The "Espinho-de-cigano" plant (Acanthospermum hispidum DC) is used throughout northeastern (NE) Brazil as a folk medicine for asthma. Although little is actually known about the effectiveness and safety of this plant extract product, it is possible to find numerous medicines prepared from it in public health services or in stores selling natural products. This study aimed to undertake a literature review relative to Acanthospermum hispidum covering the period between 1926-2006 within the areas of ethnobotany, phytochemistry and pharmacology. The objective was to contribute to a better knowledge of this species and its uses, as well as to aid in improving its performance as a natural medicine. The species is easily identifiable and grows abundantly during the rainy seasons in NE Brazil; is amenable to cultivation without lose of its phytochemical profile, and toxicological studies have showed its safety as a medicine (although more studies will be required in that direction). As such, the compilation of the accumulated knowledge concerning this species will aid in evaluating its pharmacological value, guaranteeing quality control of the final product, and in preparing recommendations for usages and dosages that offer both safety and efficiency to the user.

A planta "Espinho-de-cigano" (Acanthospermum hispidum DC) é amplamente usada no nordeste do Brasil como medicamento popular para a asma. Embora muito pouco seja conhecido atualmente sobre a eficácia e segurança deste extrato vegetal, é possível encontrar numerosos medicamentos preparados com ele nos serviços públicos ou em lojas que vendem produtos naturais. Este estudo visa proceder a uma revisão de literatura relativa à A. hispidum, no período entre 1926-2006, nas áreas de etnobotânica, fitoquímica e farmacologia. O objetivo foi contribuir para um melhor conhecimento desta espécie e seus usos, assim como auxiliar na melhora de seu desempenho como um medicamento natural. A espécie é facilmente identificável e cresce abundantemente durante a estação chuvosa no nordeste do Brasil; é possível cultivá-la sem perda de seu perfil fitoquímico e os estudos toxicológicos têm mostrado sua segurança como um medicamento (embora mais estudos sejam requeridos nestes aspectos). Assim sendo, a compilação do conhecimento acumulado relativo a esta espécie auxiliará na avaliação de seu valor farmacológico, garantindo o controle de qualidade do produto final, e no preparo das recomendações para usos e dosagens que ofereçam segurança e eficiência ao usuário.

Ecdysteroids from Vitex species: distribution and compilation of their 13C-NMR spectral data.

Iridoids and ecdysteroids are found in some genera of the family Verbenaceae. In such cases, they are used as chemotaxonomic markers for the difficult task of taxonomic identification by using morphological characteristics of plants belonging to this family. The present work describes the distribution of ecdysteroids in plants from the genus Vitex from a review of previous work on seventeen Vitex species. In addition, (13)C-NMR data of the main ecdysteroids found in this genus are described. This study attempted to summarize previous research on ecdysteroids distribution in Vitex species with the addition of (13)C-NMR analysis to further refine the characterization of these compounds in the Verbenaceae family.

Sources of alpha-, beta-, gamma-, delta- and epsilon-carotenes: a twentieth century review / Fontes de alfa-, beta-, gama-, delta-, e epsilon-carotenos: uma revisão do século XX

Since humans cannot synthesize carotenoids, they depend upon the diet exclusively for the source of these micronutrients. It has claimed that they may alleviate chronic diseases such as cancers. The present communication constitutes a global review of the scientific literature on plants and others organisms that biosynthesize carotenoids, which include the series alpha-, beta-, gamma-, delta- and epsilon-carotenes. The results of the literature survey lists more than five hundred sources.

Uma vez que os humanos não podem sintetizar carotenóides, dependem exclusivamente da dieta como fonte desses micronutrientes. Tem sido afirmado que eles podem aliviar doenças crônicas, tais como cânceres. O presente artigo constitui uma revisão global da literatura científica sobre plantas e outros organismos que biossintetizam carotenóides, que incluem as séries alfa-, beta-, gama-, delta-, e epsilon-carotenos. Os resultados das listas de pesquisa da literatura mostram mais de quinhentas fontes.

Antimicrobial activity and phytochemical profile from the roots of Lippia alba (Mill.) N.E. Brown

Lippia alba (Mill.) N.E. Brown (Verbenaceae) is commonly used in the Brazilian folk medicine to the treatment of gastric illnesses, diarrhea, fever, asthma, and as a tranquilizer. This work evaluated the antimicrobial activity of ethyl acetate, methanol and aqueous extracts from the roots of the L. alba using plates-holes diffusion assay and the phytochemical profile. The results obtained showed that the ethyl acetate and methanol extracts presented antimicrobial activity against Staphylococcus aureus (ATCC 6538P), Staphylococcus aureus (ATCC 6538) and Klebsiella pneumonia (ATCC 10031). Terpenoids, phenylpropanoids and sugars were detected in the phytochemical analysis.

Lippia alba (Mill.) N.E. Brown (Verbenaceae) é geralmente usada na medicina popular brasileira para o tratamento de doenças gástricas, febre, asma e como tranqüilizante. Este trabalho avaliou a atividade antimicrobiana dos extratos acetato de etila, metanol e aquoso das raízes de L. alba usando métodos de difusão em poços e o perfil fitoquímico. Os resultados obtidos mostraram que os extratos acetato de etila e metanol apresentaram atividade antimicrobiana contra Staphylococcus aureus (ATCC 6538P), Staphylococcus aureus (ATCC 6538) e Klebsiella pneumonia (ATCC 10031). Terpenóides, fenilpropanóides e açúcares foram detectados na análise fitoquímica.