Crude ethanolic extracts of propolis, a natural resin, have been directly analysed using electrospray ionization mass (ESI-MS) and tandem mass spectrometry (ESI-MS/MS) in the negative ion mode. European, North American and African samples have been analyzed, but emphasis has been given to Brazilian propolis which displays diverse and region-dependent chemical composition. ESI-MS provides characteristic fingerprint mass spectra, with propolis samples being divided into well-defined groups directly related to their geographical origins. Chemometric multivariate analysis statistically demonstrates the reliability of the ESI-MS fingerprinting method for propolis. On-line ESI-MS/MS tandem mass spectrometry of characteristic [M - H](-) ion markers provides an additional dimension of fingerprinting selectivity, while structurally characterizing the ESI-MS marker components of propolis. By comparison with standards, eight such markers have been identified: para-coumaric acid, 3-methoxy-4-hydroxycinnamaldehyde, 2,2-dimethyl-6-carboxyethenyl-2H-1-benzopyran, 3-prenyl-4-hydroxycinnamic acid, chrysin, pinocembrin, 3,5-diprenyl-4-hydroxycinnamic acid and dicaffeoylquinic acid. The negative mode ESI-MS fingerprinting method is capable of discerning distinct composition patterns to typify, to screen the sample origin and to reveal characteristic details of the more polar and acidic chemical components of propolis samples from different regions of the world.

Aims:The antibacterial activity against Staphylococcus aureus of honey and propolis produced by Apis mellifera and Tetragonisca angustula was evaluated. Secondary aims included the study of the chemical composition of propolis and honey samples and its relationship with antibacterial activity against S. aureus. Methods and Results: The antibacterial activity of honey and propolis was determined by the method of macrodilution. The minimum inhibitory concentration (MICs) of A. mellifera honey ranged from 126AE23 to 185AE70 mg ml )1 and of T. angustula from 142AE87 to 214AE33 mg ml )1 . For propolis, the MIC ranged from 0AE36 to 3AE65 mg ml )1 (A. mellifera) and from 0AE44 to 2AE01 mg ml )1 (T. angustula). Honey and propolis were evaluated by high-performance liquid chromatography. Some typical compounds of Brazilian propolis were also identified in honey samples. Principal component analysis revealed that the chemical composition of honey and propolis samples was distinct based on the geographical location of the samples. Conclusions: Propolis samples had higher antibacterial activity against S. aureus when compared with honey. However, both propolis and honey samples had antibacterial against S. aureus. Significance and Impact of the Study: These antimicrobial properties would warrant further studies on the clinical applications of propolis and honey against S. aureus.

Chemometrics has been shown quite efficient to uncover relationships between chemical composition of a sample and its geographical origin. Forty propolis samples originated from the the South and South East of Brazil were analyzed by HPLC and 18 compounds of interest were studied which included: caffeic, p-coumaric and ferulic acids, and some of their derivatives, pinobanksin, a derivative of kaempferol and five phenolic compounds (assigned as 3-prenyl-4-hydroxycinnamic acid (PHCA ); 2,2-dimethyl-6-carboxyethnyl-2H-l-benzopyran (DCBE); 3,5-diprenyl-4-hydroxycinnamic acid (DHCA ); compound E (still unknown) and 6-propenoic-2,2-dimethyl-8-prenyl-2H-l-benzopyran acid (DPB). Principal Component Analysis (PCA) indicated three different groups of propolis samples, having the same typical chromatogram, evaluated by HPLC. Samples from the South East group were rich in derivatives of kaempferol. Samples from the South group I had a high content of DPB compound, but a low concentration of kaempferol derivatives and of DCBEN compound. Samples from the South group II were characterized by a high concentration of DCBEN , DHCA , p-coum-aric and DPB compounds. Therefore, the identification of new compounds in Brazilian propolis can give useful information about the plant sources of a given geographic region.

Physicochemical characteristics and antimicrobial activity of the extracts propolis of the

The purpose of this investigation was to determine the antimicrobial and healing potential of propolis on direct dental pulp exposures. This study used 25 adult male rats. Pulp expo­sures were performed and animals were allocated to propolis and calcium hydroxide (Ca(OH)2 groups. Animals were killed on days 5, 7, 10, and 14. The teeth were routinely processed for histological evaluation. Non-parametric tests were employed to analyze the data. No significant differences were found between study groups on the wound healing of the dental pulp. Both substances were com parable in exhibiting normal reorganization of the pulp and no increased vascularity, and were equally efficacious in maintaining a low inflammatory and microbial cell population as well as in stimulating the formation of reparative dentin.

Os resultados obtidos com a análise química de 41 amostras de ceras de própolis e 9 amostras de ceras de favos de Apis mellifera, coletadas principalmente no Brasil, foram estudados usando Análise de Componentes Principais e Análise Hierárquica de Grupos. Na análise quimiométrica foram consideradas a distribuição de hidrocarbonetos e de resíduos alcoólicos e ácidos de monoésteres. O dendrograma obtido revelou afinidades químicas e diferenças que não puderam ser constatadas com a simples inspeção visual dos dados. Nenhuma diferença consistente foi detectada entre ceras de própolis e de favos. Os resultados deste e de outros trabalhos sugerem que hidrocarbonetos, ácidos carboxílicos, álcoois alifáticos e ésteres das ceras de própolis e de favos são produzidos pelas abelhas e, portanto, as diferenças detectadas entre uma e outra região são mais dependentes de fatores genéticos relacionados aos insetos do que da flora local. As amostras analisadas reuniram-se segundo dois grandes agrupamentos, um deles contendo exclusivamente amostras coletadas no Estado de São Paulo. Os resultados são discutidos levando em consideração o fato de que a africanização das abelhas teve início nesse estado, ocorrendo posteriormente a sua irradiação para outras partes do Brasil.Chemical composition data for 41 samples of propolis waxes and 9 samples of comb waxes of Apis mellifera collected mainly in Brazil were treated using Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA). For chemometrical analysis, the distribution of hydrocarbons and residues of alcohols and carboxylic acids of monoesters were considered. The clustering obtained revealed chemical affinities and differences not previously grasped by simple eye-inspection of the data. No consistent differences were detected between comb and propolis waxes. These and previous results suggest that hydrocarbons, carboxylic acids, aliphatic alcohols and esters from both comb and propolis waxes are bee-produced compounds and, hence, the differences detected between one and another region are dependent on genetic factors related to the insects rather than the local flora. The samples analyzed were split into two main clusters, one of them comprising exclusively material collected in the State of São Paulo. The results are discussed with respect to the africanization of honeybees that first took place in that State and therefrom irradiated to other parts of Brazil.

Extracts from different samples of Brazilian propolis were obtained by Soxhlet extraction or maceration at room temperature using ethanol, water, and accombination of both solvents. Analysis of their composition using HPLC revealed that no major differences were seen when a propolis sample was subject to different extraction methods. The activity of the 15 extracts was assayed against bloodstream trypomastigotes of Trypanosoma cruzi, the etiologic agent of Chagas' disease. Multivariate analysis was applied to evaluate the efficiency of the different extracts and the trypanocidal activity. The extracts could be divided into two groups. In the first, in which, extracts were obtained by reflux in Soxhlet using 100% ethanol, there was a lower content of bioactive compounds and consequently lower trypanocidal activity. Extract 136-Et100 stands out in this group, since it had the highest levels of bioactive compounds together with highest activity against the parasite when compared with all other extracts. The second group comprises extracts with intermediate levels of bioactive compounds and higher activity against T. cruzi.

. Can. J. Chem. 70, 2420 (1 992). The "B, "B, and I4N spin-lattice relaxation times (TI) for aqueous solutions of BH,NH, were measured by NMR spectroscopy. The results of this investigation are consistent with the nuclear quadrupolar coupling constants reported in previous nuclear quadrupolar resonance and microwave studies. The activation energy associated with rotational reorientation of BH3NH3 in aqueous solution is 1 1.7 * 0.6 kJ/mol. Electric field gradients were calculated at various levels of ab initio molecular orbital theory, in order to obtain theoretical "N and "B quadrupolar coupling constants. At