Valdir F. Veiga-Junior

Chemistry and Biological Activities of Terpenoids from Copaiba (Copaifera spp.) Oleoresins

Copaiba oleoresins are exuded from the trunks of trees of the Copaifera species (Leguminosae-Caesalpinoideae). This oleoresin is a solution of diterpenoids, especially, mono- and di-acids, solubilized by sesquiterpene hydrocarbons. The sesquiterpenes and diterpenes (labdane, clerodane and kaurane skeletons) are different for each Copaifera species and have been linked to several reported biological activities, ranging from anti-tumoral to embriotoxic effects. This review presents all the substances already described in this oleoresin, together with structures and activities of its main terpenoids.

Amazon acai: chemistry and biological activities: a review.

Acai (acai or assai) is one of the Amazons most popular functional foods and widely used in the world. There are many benefits to its alleged use in the growing market for nutraceuticals. The acai extracts have a range of polyphenolic components with antioxidant properties, some of those present in greater quantity are orientin, isoorientin and vanillic acid, as well as anthocyanins cyanidin-3-glucoside and cyanidin-3-rutinoside. The presence of these substances is linked mainly to the antioxidant, anti- inflammatory, anti-proliferative and cardioprotective activities. Importantly, there are two main species of the Euterpe genus which produce acai. There are several differences between them but they are still quite unknown, from literature to producers and consumers. In this review are highlighted the chemical composition, botanical aspects, pharmacological, marketing and nutrition of these species based on studies published in the last five years in order to unify the current knowledge and dissimilarities between them.

Antileishmanial activity of diterpene acids in copaiba oil

Leishmaniasis is a neglected tropical disease. According to the World Health Organization, there are approximately 1.5-two million new cases of cutaneous leishmaniasis each year worldwide. Chemotherapy against leishmaniasis is based on pentavalent antimonials, which were developed more than a century ago. The goals of this study were to investigate the antileishmanial activity of diterpene acids in copaiba oil, as well as some possible targets of their action against Leishmania amazonensis. Methyl copalate and agathic, hydroxycopalic, kaurenoic, pinifolic and polyaltic acids isolated from Copaifera officinales oleoresins were utilised. Ultrastructural changes and the specific organelle targets of diterpenes were investigated with electron microscopy and flow cytometry, respectively. All compounds had some level of activity against L. amazonensis. Hydroxycopalic acid and methyl copalate demonstrated the most activity against promastigotes and had 50% inhibitory concentration (IC50) values of 2.5 and 6.0 µg/mL, respectively. However, pinifolic and kaurenoic acid demonstrated the most activity against axenic amastigote and had IC50 values of 3.5 and 4.0 µg/mL, respectively. Agathic, kaurenoic and pinifolic acid caused significant increases in plasma membrane permeability and mitochondrial membrane depolarisation of the protozoan. In conclusion, copaiba oil and its diterpene acids should be explored for the development of new antileishmanial drugs.

Leishmania amazonensis: Effects of oral treatment with copaiba oil in mice

Leishmaniasis is a severe public-health problem, with high rates of morbidity and mortality. Efforts to find new, effective and safe oral agents for the treatment of leishmaniasis have been ongoing for several decades, in order to avoid the problems with the currently used antimonials. In the present study, we found that a copaiba oil oral treatment (Group IV) caused a significant reduction in the average lesion size (1.1±0.4mm) against Leishmania amazonensis lesions compared with untreated mice (Group I) (4.4±1.3mm). To prove the safety of the oil, the toxicity and genotoxicity were also determined. Histopathological evaluation did not reveal changes in the copaiba oil-treated animals compared to the control animals. In the mutagenicity evaluation, (micronucleus test) the dose tested (2000mg/kg) showed no genotoxic effects. Morphological and ultrastructural analyses demonstrated notable changes in parasite cells treated with this oleoresin. The main ultrastructural effect was mitochondrial swelling. We also demonstrated that in vitro copaiba oil treatment of L. amazonensis led to an increase in plasma membrane permeability, and depolarization in the mitochondrial membrane potential in parasite cells. Although the mechanism of action of the oleoresin is still unclear, these findings indicate that copaiba oil is a possible new drug, which would provide a safer, shorter, less-expensive, and more easily administered treatment for leishmaniasis.

Influence of abiotic factors on the chemical composition of copaiba oil (Copaifera multijuga Hayne): soil composition, seasonality and diameter at breast height

Oleos de copaiba sao importantes produtos naturais que tem sido amplamente utilizados por suas atividades cicatrizantes e anti-inflamatorias. Constituidos de sesquiterpenos e diterpenos, estes oleos apresentam composicao quimica variavel que, segundo a literatura pode ser originada por diversos fatores bioticos e abioticos. Com o objetivo de analisar a relacao entre a composicao quimica e fatores abioticos como sazonalidade, diâmetro a altura do peito (DBH) e composicao do solo, dezesseis amostras de oleo-resina de Copaifera multijuga Hayne, provenientes da Reserva Florestal Ducke (Manaus-AM, Brasil), foram analisadas por cromatografia gasosa com detector de ionizacao de chama (GC-FID) e acoplada a espectrometria de massas (GC-MS). Trinta e cinco substâncias foram identificadas e os resultados avaliados por tecnicas de analise multivariada (analises de agrupamento hierarquico (HCA) e a analise de componentes principais (PCA)), permitindo a diferenciacao das amostras em dois grupos com composicoes distintas. Um deles apresentou como substância majoritaria b-cariofileno enquanto o outro apresentou o oxido de cariofileno, essa variacao na composicao parece depender do tipo de solo. Outros fatores, anteriormente descritos como essenciais para a definicao da composicao quimica dos oleos de copaiba, como sazonalidade e DBH, nao mostraram influencia significativa sobre a composicao quimica dos oleos-resina desta especie.

Phytochemical Fingerprints of Copaiba Oils (Copaifera multijuga Hayne) Determined by Multivariate Analysis

Oils of various species of Copaifera are commonly found in pharmacies and on popular markets and are widely sold for their medicinal properties. However, the chemical variability between and within species and the lack of standardization of these oils have presented barriers to their wider commercialization. With the aim to recognize patterns for the chemical composition of copaiba oils, 22 oil samples of C. multijuga Hayne species were collected, esterified with CH2N2, and characterized by GC‐FID and GC/MS analyses. The chromatographic data were processed using hierarchical cluster analysis (HCA) and principal component analysis (PCA). In total, 35 components were identified in the oils, and the multivariate analyses (MVA) allowed the samples to be divided into three groups, with the sesquiterpenes β‐caryophyllene and caryophyllene oxide as the main components. These sesquiterpenes, which were detected in all the samples analyzed in different concentrations, were the most important constituents in the differentiation of the groups. There was a prevalence of sesquiterpenes in all the oils studied. In conclusion, GC‐FID and GC/MS analyses combined with MVA can be used to determine the chemical composition and to recognize chemical patterns of copaiba oils.

True and common balsams

Balsams have been used since ancient times, due to their therapeutic and healing properties; in the perfume industry, they are used as fixatives, and in the cosmetics industry and in cookery, they are used as preservatives and aromatizers. They are generally defined as vegetable material with highly aromatic properties that supposedly have the ability to heal diseases, not only of the body, but also of the soul. When viewed according to this concept, many substances can be considered balsams. A more modern concept is based on its chemical composition and origin: a secretion or exudate of plants that contain cinnamic and benzoic acids, and their derivatives, in their composition. The most common naturally-occurring balsams (i.e. true balsams) are the Benzoins, Liquid Storaque and the Balsams of Tolu and Peru. Many other aromatic exudates, such as Copaiba Oil and Canada Balsam, are wrongly called balsam. These usually belong to other classes of natural products, such as essential oils, resins and oleoresins. Despite the understanding of some plants, many plants are still called balsams. This article presents a chemical and pharmacological review of the most common balsams.

Chemodiversity of Ursane‐ and Oleanane‐Type Triterpenes in Amazonian Burseraceae Oleoresins

The oleoresins exuded from species of the Burseraceae family present high potential due to their biological and pharmacological properties. The evaluation of the chemodiversity of the oleoresins of 23 Amazonian species of Burseraceae provided a profile of the principal constituents, viz., the ursane‐type triterpenes α‐amyrin (1), α‐amyrenone (3), and brein (5) and the oleanane‐type triterpenes β‐amyrin (2), β‐amyrenone (4), and maniladiol (6), and allowed to determine which of these species have the highest biotechnological potential and which ones are rich in other, potentially new, triterpenes or volatile compounds of interest for the cosmetics industry. The oleoresin compositions obtained by GC‐FID and GC/MS analyses were submitted to principal component analysis (PCA) and hierarchical clustering on principal components (HCPC), which divided the 23 samples in five clusters. Protium giganteum and Trattinnickia peruviana, constituting the first cluster, presented high oleoresin contents of 3 and 4 (28.8 and 16.3% on average, resp.). The seven species of Burseraceae composing the second cluster were potential producers of new triterpenes and volatile compounds. Dacryodes hopkinsii and five Protium species (third cluster) presented average contents for all the triterpenes analyzed. The highest contents of 5 and 6 (averages of 3.9 and 5.4%, resp.) were observed in P. heptaphyllum ssp. ullei and T. glaziovii (fourth cluster). Finally, the six Protium species forming the fifth cluster showed high contents of 1 and 2 (48.0 and 19.9% on average, resp.). Moreover, this study allowed the description of the triterpene composition of 13 not previously investigated species.

Biomass production and essential oil yield from leaves, fine stems and resprouts using pruning the crown of Aniba canelilla (H.B.K.) (Lauraceae) in the Central Amazon

Aniba canelilla (H.B.K.) Mez. e uma especie arborea da Amazonia que produz oleo essencial. A extracao do oleo de suas folhas e galhos pode ser uma forma alternativa de evitar a derrubada do tronco para sua producao de oleo essencial. O objetivo deste estudo foi analisar os fatores que podem influenciar a producao de oleo essencial e sua biomassa da rebrota apos a poda de folhas e galhos das arvores de A. canelilla. As copas das arvores foram podadas na estacao chuvosa e, apos nove meses, as folhas e os galhos da copa remanescente e da rebrota foram coletadas na estacao seca. Os resultados mostraram que o rendimento e a composicao quimica de oleo essencial diferiram entre os galhos finos, as folhas e as rebrotas. A producao de oleo essencial de galhos diferiu entre as estacoes e teve maior producao nos galhos da rebrota do que nos galhos velhos da copa remanescente. A producao de oleo essencial e de biomassa das folhas da rebrota foram diferentemente relacionadas com a abertura de dossel, indicando que a luz aumenta a producao de oleo essencial e diminui a de biomassa nas folhas da rebrota. Este estudo revelou que as diferencas entre os orgaos da planta na producao de oleo essencial e a abertura de dossel devem ser levadas em consideracao para podar a copa da arvore da A. canelilla e alcancar maior produtividade de oleo.

Essential oils of Protium spp. samples from Amazonian popular markets: chemical composition, physicochemical parameters and antimicrobial activity

Species belonging to the Burseraceae family, especially of the genus Protium, are well known for producing fragrant oleoresins known in Brazil as breus. In this study, the physicochemical properties and antimicrobial activities of essential oils obtained from commercials samples of breu from the Brazilian Amazon were evaluated. Essential oils were extracted by hydrodistillation using a modified Clevenger apparatus and analyzed by gas chromatography/mass spectrometry (GC/MS) and GC/flame ionization detector (GC/FID). p-Cymene was the major constituent in all of the analyzed breu samples, with concentrations ranging from 21.9% to 51.9%, except for the white breu sample from Adolfo Lisboa Popular Market (ALPM), which contained α-pinene (22.7%). Other common monoterpenes were β-phellandrene, α-phellandrene, β-pinene, trans-dihydro-α-terpineol, α-terpineol and α-terpinene. The refractive indices ranged from 1.4769 to 1.4849 and the optical rotation ranged from −14.15° to +29.96°. The antimicrobial activity was low for all of the samples. The essential oil of black breu from ALPM was the only sample exhibiting antimycobacterial activity.