Copaiba oilresins present medicinal uses that demand the development of methodologies that could ensure the authenticity and guarantee the species differentiation. The usual way to differentiate the copaiba oils is analyze the terpene composition, mainly the diterpenic acids profile. Unlike caryophyllene and its oxide, copaiba diterpenes are not commercially available and lab obtention is expensive and time consuming. At this paper, a new methodology is presented that allows the fast and reliable detection of copaiba biomarkers using HPTLC retention factor relative to an appropriate standard. Several commercially available substances were analyzed and the monoterpene linalool oxide was chosen. The comparison of relative retention factors allowed the confirmation of caryophyllene and its oxides and the diterpenic acids copalic, hydroxy-copalic, acetoxy-copalic, agathic, and hardwickiic. Calibration curve showed strong correlation (│r│ ≥0.9962) with R2 ≥0.9928.

Copaifera multijuga Hayne is the main species of the genus in the Amazon region, being exploited for copaiba oil production mainly because of its therapeutic properties. The plant parts (leaves, branches, and barks) are widely used in folk medicine. However, they are little explored in terms of chemical composition. In this study, the polar extracts of leaves, branches, and barks of the species were analysed by direct infusion in ESI-MS with the aid of reference standards and MS2 fragmentation experiments. Twenty-six substances (carboxylic acids, flavonoids, condensed tannins, a diterpene and fifteen isomers of galoylquinic acids) were detected. Metabolic profiles were similar between extracts of leaves and branches, especially with the detection of galloylquinic acids and carboxylic acids. In bark extract, condensed tannins epicatechin-(4β-8)-epiafzelechin (dimer) and epicatechin-(4β-8)-epiafzelechin-(4β-8)-epiafzelechin (trimer) were detected. The PCA showed differences and similarities in the chemical composition of the copaíba mari-mari extracts. Thus, galloylquinic acids and flavonoids kaempferol, 7-O-methyl-kaempferol, quercetin-3-O-L-pentoside, and quercetin-3-O-L-rhamnoside are described for the first time in C. multijuga. The phytotherapeutic properties of teas of the plant parts of the species may be associated with the suggested polyphenols.

Civilian defense devices are physical and chemical artefacts used to incapacitate an aggressor without causing death or injury. As city violence increases, safety feelings became worst and a growing commercial demand for these materials supply faces technologically challenges not only to riot control but also to self-protection. Controversies on the use of these devices have been discussed, especially on their toxicity when synthetic chemical agents are used. Natural metabolites are a less explored alternative to meet this demand. They have the capacity to generate a temporary disabling effect due to their pungency. Those metabolites, which include capsaicinoids, gingerols and piperine, can be used as deterrent agents in civilian defense devices due to their low toxicity to humans. Although they are a viable alternative, there are few studies focused on their quality control, efficiency and toxicity. This review aimed to present relevant aspects about the development and use of natural products as deterrent agents in self-defense devices against aggressors and animals, and as non-lethal weapons for riot control in order to help the scientific development of this type of bioproduct.

Óleos de copaíba são importantes produtos naturais que têm sido amplamente utilizados por suas atividades cicatrizantes e anti-inflamatórias. Constituídos de sesquiterpenos e diterpenos, estes óleos apresentam composição química variável que, segundo a literatura pode ser originada por diversos fatores bióticos e abióticos. Com o objetivo de analisar a relação entre a composição química e fatores abióticos como sazonalidade, diâmetro à altura do peito (DBH) e composição do solo, dezesseis amostras de óleo-resina de Copaifera multijuga Hayne, provenientes da Reserva Florestal Ducke (Manaus-AM, Brasil), foram analisadas por cromatografia gasosa com detector de ionização de chama (GC-FID) e acoplada à espectrometria de massas (GC-MS). Trinta e cinco substâncias foram identificadas e os resultados avaliados por técnicas de análise multivariada (análises de agrupamento hierárquico (HCA) e a análise de componentes principais (PCA)), permitindo a diferenciação das amostras em dois grupos com composições distintas. Um deles apresentou como substância majoritária b-cariofileno enquanto o outro apresentou o óxido de cariofileno, essa variação na composição parece depender do tipo de solo. Outros fatores, anteriormente descritos como essenciais para a definição da composição química dos óleos de copaíba, como sazonalidade e DBH, não mostraram influência significativa sobre a composição química dos óleos-resina desta espécie.

Copaiba oils are important medicinal products used primarily for their healing and anti-inflammatory activities. Consisting of sesquiterpenes and diterpenes, these oils have variable composition which, according to the literature, may originate from several factors. In order to analyze the relationship between chemical composition and abiotic factors such as seasonality, diameter at breast height (DBH) and soil composition, sixteen of oilresin samples of Copaifera multijuga Hayne, from the Ducke Forest Reserve (Manaus City, Amazon State, Brazil), were analyzed by gas chromatography with flame ionization detection (GC-FID) and coupled with mass spectrometry (GC-MS). Thirty-five compounds were identified and the results evaluated by multivariate analysis (hierarchical cluster analysis (HCA) and principal component analysis (PCA)), allowing differentiation of the samples into two groups with different compositions. One of them presented β-caryophyllene as the major constituent, while the other presented caryophyllene oxide. This variation in composition appears to depend on soil type. Other factors previously described as essential for defining the chemical composition of copaiba oils, such as seasonality and DBH, showed no significant influence on the chemical composition of oils of this species.

A adição de solventes orgânicos (hidrocarbonetos alifáticos pesados, alifáticos leves e hidrocarbonetos aromáticos) na gasolina brasileira é muito freqüente, e esta prática ilícita prejudica a qualidade da gasolina. Neste trabalho, as adulterações por solventes orgânicos de amostras de gasolina foram analisadas. Para a caracterização e comparação destas amostras, alguns parâmetros físico-químicos foram selecionados como fator para análise estatística hierárquica multivariada (Cluster Analysis). Entretanto estes parâmetros não foram eficientes para detectar todos os tipos de adulteração, em particular a adulteração por hidrocarbonetos alifáticos leves e mistura dos mesmos com hidrocarbonetos aromáticos. Este tipo de adulteração é melhor detectada através da análise do perfil cromatográfico destas amostras. A Cromatografia Gasosa (CG) deve ser usada para uma melhor detecção de gasolinas adulteradas. O uso das propriedades físico-químicas de amostras de gasolina na análise estatística multivariada juntamente com os perfis cromatográficos é um método eficiente e viável à detecção da adulteração.

The addition of organic solvents (heavy aliphatic, light aliphatic and aromatic hydrocarbons) in Brazilian gasoline is unfortunately very frequent, and this illicit practice does not guarantee gasoline quality. Organic solvent adulterations of gasoline samples have been investigated. For characterization and comparison of these samples, physico-chemical parameters were selected as the factor for hierarchic multivariate analysis (Cluster Analysis). However, these parameters are not efficient to detected all kinds of adulteration. Gas Chromatographic (GC) analysis can be used as a procedure to improve the detection of adulterated gasoline. More detailed information of their compositions was revealed. The use of physico-chemical properties of gasoline samples for hierarchic multivariate analysis and gas chromatographic fingerprints is a practicable method to adulteration detection.