The composition of eight samples of commercial copaiba oils, used in the Amazonian region as antiinflammatory agents and available in popular markets, were analysed by gas chromatography/mass spectrometry (HRGC-MS). Major differences were observed in their chemical composition and some adulterations were pointed out. When tested in vivo oils 1 and 3, and to a lesser extent oil 6, significantly inhibited bradykinin-induced oedema formation. The other tested oils had no effect. When assessed in carrageenan-induced oedema formation, oils 1, 2 and 6, but not oil 3, significantly attenuated the oedema formation. The other tested oils failed to affect carrageenan-induced paw oedema. Oils 1 and 6 were further fractionated and several sesquiterpenes and diterpenes were detected. It is suggested that the naturally occurring sesquiterpenes present in the copaiba oils seem to be responsible for the antiinflammatory action reported in the folk medicine. Furthermore, our results clearly show an adulteration in copaiba oils available in Brazil.

Recebido em 16/8/96; aceito em 18/6/97 AUTHENTICITY CONTROL OF COMMERCIAL COPAIBA OILS BY HIGH RESOLUTION GAS CHROMATOGRAPHY. Copaiba oil is a resin extracted from the trunk of trees of Copaifera species which grow in Brazil where it is widely used in popular medicine as an anti-inflammatory, antiseptic anti-bactericidal, diuretic, dermatological, expectorant, and anti-infective. The comparative study of the composition of commercial copaiba oils was carried out by high resolution gas chromatography (HRGC) and high resolution gas chromatography-mass spectrometry (HRGC-MS) analysis. The commercial oils were compared with authentic oils, collected from the southeast and northern regions of Brazil. Sixteen commercial oils were analysed and two of them revealed adulterations with fatty acids. Using the chromatographic profile of authentic copaiba species oils, it is possible to analyse commercial oils and determine the authenticity of these materials.Keywords: Copaifera; copaiba oil; diterpenes; high resolution gas chromatography. ARTIGO INTRODUÇÃOO óleo de copaíba, também descrito como bálsamo de copaíba 1 , é extraído do tronco de árvores de diversas espécies do gênero Copaifera (Leguminosae). Este gênero ocorre no norte da América do Sul, principalmente nos estados brasileiros do Pará e Amazonas. Os óleos de copaíba são constituídos majoritariamente de hidrocarbonetos sesquiterpênicos 2 e encontram aplicações na indústria de tintas e vernizes 3 . Devido ao seu valor comercial são exportados para as indústrias de cosméticos européias 4,5 . No Brasil, os óleos de copaíba são amplamente utilizados na medicina popular 6,7 , sendo administrados oralmente e por aplicação tópica do óleo in natura 8 ou em pomadas. Nos estados do norte é comum a prática da embrocação do óleo de copaíba para tratar infecções na garganta.As propriedades anti-inflamatórias dos óleos de copaíba são conhecidas desde o início da colonização do Brasil. Existem descrições de sua utilização por tribos indígenas, que aplicavam-no em umbigos de recém-nascidos para evitar infecções. Pero Magalhães Gandavo, um dos primeiros cronistas da histó-ria brasileira, descreve as virtudes do óleo de copaíba como transcritas no texto a seguir 9 : ...É bom untar com êle o peito, contra o estômago frouxo; e no ventre, contra as dores de cólicas; gotasinhas convenientemente ingeridas pela bôca aumentam a fôrça às visceras e restitui-lhes a vitalidade; também estariam os fluxos femininos, os cursos do ventre e as gonorreias..."O interesse pela medicina natural vem crescendo em todo o mundo, principalmente na Europa, e artigos recentes demonstram que um percentual muito grande de recursos está envolvido na comercialização de fitoterápicos, que vem tomando o lugar de medicamentos alopáticos nas prateleiras das farmáci-as, cujo comércio mundial atinge a cifra astronômica de US$ 12,4 bilhões por ano 11 . O Brasil não é exceção a esta onda e hoje observa-se um aumento significativo do número de farmácias de produtos naturais nas suas grandes cidades.O uso crescente de f...

O uso de cromatografia sob pressão ("flash chromatography") utilizando-se coluna de gel de sílica impregnada com hidróxido de potássio levou ao fracionamento dos constituintes químicos de Copaifera cearensis Huber ex Ducke. A fração ácida, após esterificação com diazometano, foi analisada por cromatografia gasosa de alta resolução acoplada à espectrometria de massas ou à espectrometria no infravermelho, possibilitando a identificação de onze diterpenos ácidos. Fracionamentos adicionais da fração ácida por cromatografia líquida de alta eficiência em fase reversa levaram ao isolamento de diversos ácidos diterpênicos e de um sesquiterpênico que foram identificados através de seus dados espectroscópicos. A análise da sílica impregnada com hidróxido de potássio mostrou que, além da deposição do hidróxido na superfície da sílica, ocorreu troca iônica com formação de resíduos Si-OK.Various acid diterpenes of Copaifera cearensis Huber ex Ducke were isolated from the crude extract by flash Silica Gel/Potassium Hydroxide Chromatography. The main components were identified by GC-MS analyses. Further fractionation by reversed phase (RP) semi-preparative HPLC allowed isolation and identification of minor components and provided additional spectral data of those compounds. It was possible to detect the presence of eleven acid diterpenes in addition to a sesquiterpene acid. In addition to potassium hydroxide deposition on the silica surface, the presence of Si-OK residues, resulting from a cation exchange process, was established.

-Aromas and fragrances can be obtained through the microbial oxidation of monoterpenes. Many microorganisms can be used to carry out extremely specific conversions using substrates of low commercial value. However, for many species, these substrates are highly toxic, consequently inhibiting their metabolism. In this work, the conversion ability of Aspergillus niger IOC-3913 for terpenic compounds was examined. This species was preselected because of its high resistance to toxic monoterpenic substrates. Though it has been grown in media containing R-limonene (one of the cheapest monoterpenic hydrocarbons, which is widely available on the market), the species has not shown the ability to metabolize it, since biotransformation products were not detected in high resolution gas chromatography analyses. For this reason, other monoterpenes (alpha-pinene, beta-pinene and camphor) were used as substrates. These compounds were shown to be metabolized by the selected strain, producing oxidized compounds. Four reaction systems were used: a) biotransformation in a liquid medium with cells in growth b) with pre-grown cultures c) with cells immobilized in a synthetic polymer network and d) in a solid medium to which the substrate was added via the gas phase. The main biotransformation products were found in all the reaction systems, although the adoption of previously cultivated cells seemed to favor biotransformation. Cell immobilization seemed to be a feasible strategy for alleviating the toxic effect of the substrate. Through mass spectrometry it was possible to identify verbenone and alpha-terpineol as the biotransformation products of alpha-pinene and beta-pinene, respectively. The structures of the other oxidation products are described.

The ethanolic extracts of two Brazilian propolis samples were submitted to a fractionation procedure based on the pK a values of their components. The fractions obtained were evaluated for their antimicrobial activity against Staphylococcus aureus as well as for their antioxidant properties (reduction of DPPH radical). Their phenolic and flavonoid contents were measured spectrophotometrically, in order to establish the correlations between these contents and the measured activities. Further, the most active fractions of both extracts were analyzed by HRGC-MS and about twenty compounds could be characterized. Among them were 3-prenyl-4-hydroxycinnamic acid (drupanin) and 3,5-diprenyl-4-hydroxycinnamic acid (artepillin C), which seem to be the major antioxidant components of the bioactive fractions.