ABSTRACT Campomanesia adamantium (Cambess.) O. Berg., Myrtaceae, is a plant popularly used for its anti-inflammatory, anti-diarrhoeal and urinary antiseptic activities. The aims of this study were to obtain the crude ethanolic extract and the hexane, dichloromethane, ethyl acetate, aqueous and concentrated aqueous tannin fractions from C. adamantium leaves, perform biomonitored fractionation to isolate and identify chemical compounds, study the chemical composition of the volatile oils of the leaves and flowers and test the antimicrobial activity of the ethanolic extract, fractions, isolated substances and volatile oils. Phytochemical screening and chromatographic and spectrometric techniques were used. Volatile oils were isolated by hydrodistillation in a Clevenger apparatus and analyzed by gas chromatography/mass spectrometry. The antimicrobial activity was tested by a broth microdilution test. The component stictane-3,22-diol was isolated and identified from the hexane fraction, while valoneic and gallic acid were isolated and identified from the concentrated aqueous tannin fraction. The major constituents of the volatile oils of the leaves were verbenene (13.91%), β-funebrene (12.05%) and limonene (10.32%), while those of the volatile oils of the flowers were sabinene (20.45%), limonene (19.33%), α-thujene (8.86%) and methyl salicylate (8.66%). Antibacterial activity was verified for the hexane fraction, while antifungal activity was observed for the aqueous fraction and concentrated aqueous tannin fraction and for vanoleic acid. These results may justify the popular use of C. adamantium.

ABSTRACT Spiranthera odoratissima A. St.-Hil., Rutaceae, known as “manacá” is a shrub native of the Brazilian Cerrado. Their leaves and roots are popularly used to treat rheumatism, infection and abdominal pain. This study analyzed the chemical composition of volatile oils from leaves of S. odoratissima and verified the seasonal variability of its chemical composition. The volatile oils were obtained by hydrodistillation using a Clevenger type apparatus and analyzed by gas chromatography coupled to mass spectrometry. The main chemical components found in samples of volatile oils were β-caryophyllene, bicyclogermacrene, δ-cadinene, amorphous-4,7(11)-diene, α-epi-muurolol, α-cadinol, α-muurolol and γ-cadinene. The hierarchical clustering identified three groups: the first was characterized by α-epi-muurolol, the second by amorphous-4,7(11)-diene and the third group was characterized by α-muurolol. The discriminant canonical analysis was used to differentiate between clusters on the basis of oil composition. The results suggest that the rainfall presented a relationship with the chemical composition of the volatile oil. This is the first study conducted on the seasonal behavior of the chemical constituents in volatile oil from leaves of S. odoratissima.

ABSTRACT Trembleya phlogiformis DC., Melastomataceae, is a shrub whose leaves are used as a dye for dyeing wool and cotton. The present article aimed to carry out the morphological description of the species, to study the chemical composition of volatile oils from the leaves and flowers and the seasonal variability from the leaves during a year. Macroscopic characterization was carried out with the naked eye and with a stereoscopic microscope. Volatile oils were isolated by hydrodistillation in Clevenger apparatus and analyzed by gas chromatography/mass spectrometry. The major components of the volatile oil of T. phlogiformis flowers were: n-heneicosane (33.5%), phytol (12.3%), n-tricosane (8.4%) and linoleic acid (6.1%). It was verified the existence of a large chemical variability of the volatile oils from the leaves of T. phlogiformis over the months, with the majority compound (oleic alcohol, ranging from 5.7 to 26.8%) present in all samples. A combination of Cluster Analysis and Principal Component Analysis showed the existence of three main clusters, probably related to the seasons. The results suggested that the volatile oils of T. phlogiformis leaves possess high chemical variability, probably related to variation associated with rainfall and the variation in the behavior of specimens throughout the year. This research provides insights for future studies on the volatile oils obtained from the T. phlogiformis leaves and flowers, mainly related to biological markers of applications monitored in the leaves and flowers of this species.

ABSTRACT Hyptis carpinifolia Benth., Lamiaceae, is a species known popularly as "rosmaninho" and "mata-pasto", and leaves are employed in Brazilian folk medicine to treat colds, flu, and rheumatism. The aim of this study was to perform a morphological description of H. carpinifolia and to evaluate the seasonal chemical variability of the leaf essential oils during 12 months. Macroscopic characterization of H. carpinifolia was carried out with the naked eye and with a stereoscopic microscope. Essential oils were isolated from leaves by hydrodistillation in Clevenger apparatus and analyzed by gas chromatography/mass spectrometry. Major compounds were found to be 1,8-cineole (39.6-61.8%), trans-cadina-1(6),4-diene (2.8-17.5%), β-caryophyllene (4.4-10.0%), prenopsan-8-ol (4.2-9.6%) and β-pinene (2.9-5.3%). Results of essential oils compositions were processed by cluster analysis and principal component analysis. Data showed high variability in the concentration of the components. Besides, there was a seasonal variability of chemical composition, probably related mainly to the rainfall regime.

Abstract Hortia oreadica Groppo, Kallunki & Pirani, Rutaceae, known as “para-tudo”, “quina”, and “quina-do-campo”, is used in traditional medicine locally to treat stomach pain and fevers. The aims of this study were: analyze the chemical composition of essential oils from leaves, flowers and fruits of H. oreadica and verify the seasonal variation of the chemical components of essential oils from leaves. The essential oils were obtained by hydrodistillation using a Clevenger type apparatus and analyzed by GC/MS. The major components found in the samples of the essential oils were the amorpha-4,7(11)-diene (29.27% – flowers, 20.26% – fruits, 27.66–37.89% – leaves), bicyclogermacrene (23.28% – flowers, 20.64% – fruits, 14.71% to 31.37% – leaves). This work represents the first study of the chemical composition of essential oils from leaves, flowers and fruits and seasonal variation in the essential oils from leaves of H. oreadica.

Os óleos essenciais de quatro espécies de Marsypianthes (Lamiaceae) foram investigados por meio de cromatografia gasosa e análise multivariada. Cada espécie foi representada por duas a sete populações, totalizando dezessete populações. β-Elemeno, (E)-cariofileno, α-humuleno, germacreno D, biciclogermacreno, δ-cadineno, espatulenol, óxido de cariofileno e globulol ocorreram em todas as amostras. As análises de componentes principais e de agrupamento hierárquico evidenciaram a presença de duas seções, uma contendo M. chamaedrys/M. montana (seção A) e a outra contendo M. burchellii (seção B). M. foliolosa apresentou maior complexidade, dividindo-se nas duas seções. Resultados similares foram obtidos de acordo com os esqueletos carbônicos biosssintéticos. Germacranos e biciclogermacranos preponderaram na seção A, enquanto aromadendranos e guaianos caracterizaram a seção B. A análise de redundância canônica mostrou que os agrupamentos não foram influenciados por variáveis edáficas dos locais de amostragem.

Essential oils of four species of Marsypianthes (Lamiaceae) were investigated via gas chromatography and multivariate analysis. Each species was represented by two to seven populations, totaling seventeen populations. β-Elemene, (E)-caryophyllene, α-humulene, germacrene D, bicyclogermacrene, δ-cadinene, spathulenol, caryophyllene oxide, and globulol were found in all samples. Principal component and hierarchical cluster analyses revealed the presence of two sections, one containing M. chamaedrys/M. montana (section A) and the other M. burchellii (section B). M. foliolosa showed higher complexity, being divided in both sections. Similar results were obtained according to biosynthetic carbon skeletons. Germacranes and bicyclogermacranes predominated in section A, whereas aromadendranes, bourbonanes and guaianes characterized section B. Canonical redundancy analysis revealed that clusters were not influenced by edaphic factors in sampling sites.

Oenoteína B é um tanino hidrolisável dimérico com um amplo espectro de atividades biológicas, tais como antitumoral, anti-inflamatória e anti-viral. Seus espectros de ressonância magnética nuclear (RMN) à temperatura ambiente apresentam duplicações e alargamento de sinais. Experimentos de RMN uni e bidimensionais a baixas temperaturas foram úteis no assinalamento de todos os sinais de hidrogênios e carbonos sem a necessidade de derivatização. A estrutura tridimensional do confôrmero mais estável foi determinada pela primeira vez através do experimento de espectroscopia de efeito nuclear Overhauser (NOESY) (-20 ºC) e cálculos computacionais usando métodos de teoria do funcional de densidade (DFT) (B3LYP/6-31G) e modelo contínuo polarizado (PCM). A conformação mais favorecida apresentou uma geometria altamente compactada e sem simetria, onde os dois grupos valoneoila mostraram diferentes parâmetros conformacionais e estabilidades.

Oenothein B is a dimeric hydrolysable tannin with a wide range of biological activities, such as antitumour, anti-inflammatory and antiviral. Its nuclear magnetic resonance (NMR) at room temperature show duplications and broadening of signals. Experiments of 1D and 2D NMR at lower temperatures were useful for the complete NMR assignments of all hydrogens and carbons. The 3D structure of the most stable conformer was determined for the first time by nuclear Overhauser effect spectroscopy (NOESY) experiment (-20 ºC) and density functional theory (DFT)(B3LYP/6-31G)/ polarizable continuum model (PCM) quantum chemical calculations. The favoured conformation showed a highly compacted geometry and a lack of symmetry, in which the two valoneoyl groups showed distinct conformational parameters and stabilities.

Syzygium jambos (L.) Alston, Myrtaceae, occurs in tropical regions and is a widespread medicinal plant used to treat several diseases, such as hemorrhage, dysentery, diabetes, inflammation, diabetes and gastrointestinal disorders. Leaf essential oils of ten specimens of S. jambos collected from two localities of Central Brazilian Cerrado were investigated by GC-MS. Soil and foliar nutrients were analyzed to determine the mineral compositions. The aims of this study was to evaluate the influence of environmental factors on chemical composition of leaf essential oils of S. jambos. Studies on the influence of environmental factors over composition of essential oils are important because they contribute data for its cultivation, harvest and establish parameters to essential oil components. The data were analyzed using stepwise Multiple Regression and Cluster Analysis, and the results suggest that the main factor capable to influence the chemical composition of leaf essential oils was the collection period and the collection site had a minor effect. The results also suggest that the leaf essential oils composition was influenced mainly by foliar nutrients (N, Mn, Co, Fe, S and Mg) and soil nutrients (Na, Al, S and H+Al). The compound with the best model obtained was the (E)-caryophyllene, with a coefficient of determination equal 0.8113.

Variações nos óleos essenciais foram utilizadas para o estudo da estrutura química espacial de oito populações de E. dysenterica do Cerrado central brasileiro. Previamente, o autocorrelograma multivariado de Mantel e o particionamento da variação da matriz química, utilizando os conjuntos de dados espaciais e ambientais como preditores, sugeriram uma significante variação espacial nos óleos essenciais. No presente estudo, os métodos quimiométricos espaciais usando variogramas e mapas de probabilidade permitiram a detecção e a caracterização da estrutura químico-espacial entre populações, bem como dos fatores ambientais responsáveis por ela. Todas essas estratégias indicaram que as populações diferem quimicamente a distâncias geográficas superiores a 120 km, um indicador da distância mínima entre amostras necessária para a conservação da diversidade genética das populações. Embora sendo raramente usadas com metabólitos secundários, essas metodologias possuem uma grande aplicação em conservação de espécies e podem permitir uma efetiva integração de perspectivas genética, química e ecológica.

Chemovariations in essential oils were used for studying the spatial chemical structure of eight E. dysenterica populations in Central Brazilian Cerrado. Previously, multivariate Mantel autocorrelogram and chemical matrix variation partitioning, using the spatial and environmental data sets as predictors, have suggested a highly significant spatial variation in essential oils. In the present study, spatial chemometric methods using variograms and probability maps detected and characterized the spatial chemical structure among populations, as well as the environmental factors responsible for them. All these strategies indicated that the populations differ chemically whenever the geographical distance exceeds 120 km, an indicator of the minimal distance between samples required for conserving the genetic diversity of populations. Although being scarcely used with secondary metabolites, these methodologies may be used in a wide range of applications in species management and may lead to an effective integration of genetic, chemical and ecological perspectives.

Pterodon emarginatus Vogel, Fabaceae, is a tree species commonly known as "sucupira-branca". It is a popular medicinal plant in the Brazilian cerrado (Savanna). This study investigates the chemical variability of the essential oils from fruits of P. emarginatus. The fruits were collected from five sites in the Brazilian Cerrado and their essential oils were analyzed by GC/MS. The results obtained by Principal Component and Cluster Analysis identified two groups: cluster I containing β-caryophyllene and δ-elemene and cluster II containing α-copaene, β-cubebene, allo-aromadendrene, α-cubebene and γ-muurulene. The Canonical Discriminant Analysis was used to differentiate between clusters on the basis of essential oil composition. The results showed high variability in the composition of the essential oils from fruits of P. emarginatus, contributing to studies of domestication of this species.

Species in the Myrtaceae family are used in folk medicine to treat gastrointestinal disorders, infectious diseases and hemorrhagic conditions and are known for their essential oil contents. Gas chromatography coupled with mass spectrometry (GC-MS) was used to characterize the chemical composition of essential oils of the leaves, stem bark and flowers of Myrcia tomentosa (Aubl.) DC., as well as to assess the chemical variability in the constituents of the essential oils of the leaf. Soil and foliar analyses were also performed to determine the mineral compositions. Principal component analysis (PCA) was used to examine the interrelationships between the obtained data. The most abundant component in the essential oils of the flowers was (2E,6E)-methyl farnesoate, whereas hexadecanoic acid was the most abundant essential oil component in the stem bark. The leaf essential oils showed seasonal variation in their chemical composition, with bicyclogermacrene and (2E,6E)-methyl farnesoate as the major chemical components. Forty-four constituents were identified, and only nine compounds were found in all of the samples. Sesquiterpenes were mainly produced in the flowers and leaves. The PCA showed a positive correlation between the oxygenated sesquiterpenes and the foliar nutrients Cu and P. Significant statistical correlations were verified between the climatic data, foliar nutrients and essential oil compositions.

A composição química dos óleos essenciais foi utilizada para estudar a estrutura espacial de oito populações de Eugenia dysenterica do Cerrado central brasileiro. O particionamento da variação utilizando os conjuntos de dados espaciais e ambientais como preditores foi altamente significativo e explicou 7,8 e 8,1% da variação total dos óleos essenciais, respectivamente. Os resultados sugeriram que o polimorfismo nos óleos essenciais foi determinado mais por fatores genéticos do que ambientais. Além disso, o intercepto do autocorrelograma multivariado de Mantel entre as matrizes de distância dos constituintes químicos e dos locais de coleta sugere que as populações se diferenciam quimicamente a distâncias geográficas superiores a 120 km, contribuindo como indicador alternativo da distância mínima entre amostras necessária para a conservação da diversidade genética das populações.

The chemical composition of essential oils was used to study the spatial structure of eight Eugenia dysenterica populations in central Brazilian Cerrado. Variation partitioning using spatial and environmental data sets as predictors was highly significant and explained 7.8 and 8.1% of oil chemovariations, respectively. Results suggested that essential oil polymorphism was genetically rather than environmentally determined. Furthermore, the intercept of the multivariate Mantel autocorrelogram between the distance matrices of oil constituents and sampling sites suggested that the populations differ chemically whenever geographical distance exceeds 120 km. It stands, therefore, as an alternative indicator of the minimal distance between samples required for conserving the genetic diversity of populations.

O Cerrado Central brasileiro é considerado o centro de origem e dispersão de Hypenia (Lamiaceae: subtribo Hyptidineae) na América do Sul. O gênero tem sido mantido sem divisão, ou subdividido em duas ou cinco seções taxonômicas, baseadas quase exclusivamente a partir de um conjunto limitado de características florais. Neste trabalho, uma delimitação química interespecífica é descrita a fim de complementar as análises das características botânicas. Análise multivariada dos óleos essenciais de dez espécies na fase vegetativa suporta a divisão taxonômica do gênero em duas seções. Grupo I incluiu quatro espécies da seção Laxiflorae em adição à H. irregularis, os quais foram caracterizados pelos mais altos percentuais de espatulenol e óxido de cariofileno. Grupo II conteve cinco espécies da seção Densiflorae com α-cadinol, a-muuroleno e a-muurolol como constituintes principais. Cadinanos e germacranos/aromadendranos parecem ser as classes marcadoras quimiotaxonômicas nas seções Densiflorae e Laxiflorae, respectivamente.Além disso, análise de redundância canônica não indicou correlação significante entre fatores edáficos com quimiovariação nos óleos essenciais, sugerindo que em Hypenia os óleos são constituídos por substâncias constitutivas e não induzidas pelo ambiente.

Central Brazilian Cerrado is regarded as the center of origin and dispersion of Hypenia (Lamiaceae: subtribe Hyptidineae) in South America. The genus has either remained undivided or been divided into two or seven taxonomic sections, based almost exclusively on a limited range of floral features. Interspecific chemical delimitation to complement analyses of botanical traits is described. Multivariate analysis of essential oils of ten species in the vegetative stage supports the taxonomic division in two sections. Cluster I included four species belonging to section Laxiflorae in addition to H. irregularis, which were characterized by the highest percentages of spathulenol and caryophyllene oxide. Cluster II contained five species belonging to section Densiflorae with α-cadinol, α-muurolene and a-muurolol as major constituents. Cadinanes and germacranes/ aromadendranes seem to be chemotaxonomic markers of sections Densiflorae and Laxiflorae, respectively. Furthermore, redundancy analysis revealed no significant correlation between edaphic factors and oil chemovariations, suggesting that Hypenia oils consist of constitutive rather than induced compounds.

Ácidos orgânicos, açúcares, álcoois, compostos fenólicos, propriedades de cor, pH e acidez titulável foram monitorados durante fermentação comercial de jabuticaba (Myrciaria cauliflora) através da espectroscopia de ressonância magnética nuclear (NMR) de ¹H, ensaios espectrofotométricos e métodos usuais de análise. Os dados coletados foram analisados por meio de análise de componentes principais (PCA), agrupamentos (HCA) e correlação canônica (CCA). Dois grupos de amostras foram reconhecidos, e as variáveis responsáveis pela separação foram açúcares, antocianinas, álcoois, tonalidade e ácidos acéticos e succínico. A análise de correlação canônica confirmou a influência dos álcoois (etanol, metanol e glicerol), ácidos orgânicos (ácidos cítrico, acético e succínico), pH e acidez titulável na extração e estabilidade das antocianinas e copigmentos. Consequentemente, as propriedades de cor também foram afetadas pelas variações nos níveis de compostos fenólicos durante o processo de fermentação.

Organic acids, sugars, alcohols, phenolic compounds, color properties, pH and titratable acidity were monitored during the commercial fermentation of jabuticaba (Myrciaria cauliflora) by ¹H nuclear magnetic resonance (NMR) spectroscopy, spectrophotometric assays and standard methods of analysis. Data collected was analyzed by principal component (PCA), hierarchical cluster (HCA) and canonical correlation (CCA) analyses. Two sample groups were distinguished and the variables responsible for separation were sugars, anthocyanins, alcohols, hue and acetic and succinic acids. The canonical correlation analysis confirmed the influence of alcohols (ethanol, methanol and glycerol), organic acids (citric, succinic and acetic acids), pH and titratable acidity on the extraction and stability of anthocyanins and copigments. As a result, color properties were also affected by phenolic variation throughout the fermentative process.

A composição química dos óleos essenciais e o conteúdo em fenóis (fenóis totais, taninos e antocianinas) bem como os teores de açúcares redutores e da acidez dos frutos de M. cauliflora foram obtidos de plantas cultivadas sob seis tipos de solo. As análises de redundância canônica (RDA) e de discriminante indicaram a presença de quatro grupos de amostras, tendo o α-copaene e os teores de taninos, açúcares redutores e da acidez do fruto como variáveis preditoras. O particionamento da variância, conduzida por meio de RDAs parciais, revelou uma forte influência de fatores edáficos sobre o conteúdo dos fenólicos, açúcares redutores e da acidez dos frutos, enquanto que o polimorfismo nos óleos essenciais foi atribuído majoritariamente a fatores genéticos. Para todos os constituintes a influência espacial na variabilidade química foi significativa, embora menos pronunciada para os óleos essenciais.

Essential oil chemical composition and phenolics (total phenols, tannins and anthocyanins), reducing sugar and fruit acidity contents of Myrciaria cauliflora were obtained from cultivated populations in six sampling sites. Canonical redundancy (RDA) and discriminant analyses revealed four clusters of samples based on contents of α-copaene, tannins, reducing sugar and fruit acidity as predictor variables. The total variation partition performed by partial RDAs showed a strong influence of edaphic factors on phenolics, reducing sugar and fruit acidity data set. However, the polymorphism of essential oils may be genetically determined. Spatial influence on chemovariations was significant for all constituents, but less pronounced for essential oil data.