Detecção in silico e caracterização estrutural dos constituintes micromoleculares majoritários presentes no fungo endofitico Phomopsis stipata isolado de folhas de Styrax camporum Pohl (Styracaceae) usando CLAE-DAD/EMAR e CG-MS

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Detecção in silico e caracterização dos constituintes micromoleculares majoritários do fungo endofítico Colletotrichum gloeosporioides isolado de folhas de Garcinia xanthochymus usando HPLC-DAD-HRMS e GC-MS

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Action Of Essential Oils From Brazilian Native And Exotic Medicinal Species On Oral Biofilms.

Essential oils (EO) obtained from twenty medicinal and aromatic plants were evaluated for their antimicrobial activity against the oral pathogens Candida albicans, Fusobacterium nucleatum, Porphyromonas gingivalis, Streptococcus sanguis and Streptococcus mitis. The antimicrobial activity of the EO was evaluates by microdilution method determining Minimal Inhibitory Concentration. Chemical analysis of the oils compounds was performed by Gas chromatography-mass spectrometry (CG-MS). The most active EO were also investigated as to their actions on the biolfilm formation. The most of the essential oils (EO) presented moderate to strong antimicrobial activity against the oral pathogens (MIC--Minimal Inhibitory Concentrations values between 0.007 and 1.00 mg/mL). The essential oil from Coriandrum sativum inhibited all oral species with MIC values from 0.007 to 0.250 mg/mL, and MBC/MFC (Minimal Bactericidal/Fungicidal Concentrations) from 0.015 to 0.500 mg/mL. On the other hand the essential oil of C. articulatus inhibited 63.96% of S. sanguis biofilm formation. Through Scanning Eletronic Microscopy (SEM) images no changes were observed in cell morphology, despite a decrease in biofilm formation and changes on biofilm structure. Chemical analysis by Gas Chromatography-Mass Spectrometry (GC-MS) of the C. sativum essential oil revealed major compounds derivatives from alcohols and aldehydes, while Cyperus articulatus and Aloysia gratissima (EOs) presented mono and sesquiterpenes. In conclusion, the crude oil from C. articulatus exhibited the best results of antimicrobial activity e ability to control biofilm formation. The chemical analysis showed the presence of terpenes and monoterpenes such as a-pinene, a-bulnesene and copaene. The reduction of biofilms formation was confirmed from SEM images. The results of this research shows a great potential from the plants studied as new antimicrobial sources.

Seasonal Variation, Chemical Composition and Antioxidant activity of Brazilian Propolis Samples

Total phenolic contents, antioxidant activity and chemical composition of propolis samples from three localities of Minas Gerais state (southeast Brazil) were determined. Total phenolic contents were determined by the Folin-Ciocalteau method, antioxidant activity was evaluated by DPPH, using BHT as reference, and chemical composition was analyzed by GC/MS. Propolis from Itapecerica and Paula Candido municipalities were found to have high phenolic contents and pronounced antioxidant activity. From these extracts, 40 substances were identified, among them were simple phenylpropanoids, prenylated phenylpropanoids, sesqui- and diterpenoids. Quantitatively, the main constituent of both samples was allyl-3-prenylcinnamic acid. A sample from Virginopolis municipality had no detectable phenolic substances and contained mainly triterpenoids, the main constituents being alpha-and beta-amyrins. Methanolic extracts from Itapecerica and Paula Candido exhibited pronounced scavenging activity towards DPPH, indistinguishable from BHT activity. However, extracts from Virginopolis sample exhibited no antioxidant activity. Total phenolic substances, GC/MS analyses and antioxidant activity of samples from Itapecerica collected monthly over a period of 1 year revealed considerable variation. No correlation was observed between antioxidant activity and either total phenolic contents or contents of artepillin C and other phenolic substances, as assayed by CG/MS analysis.

Determination of volatiles produced during radiation processing in Laurus cinnamomum

In order to protect food from pathogenic microorganisms as well as increase its shelf-life, while keeping sensorial properties (e.g., odor and taste), which are important properties required by spice buyers, it is necessary to analyze volatile formation from irradiation of medicinal and food herbs. Possible changes in the odor of these herbs are evaluated by characterizing different radiation doses and effects on sensorial properties, in order to allow better application of the irradiation technology. The aim of the present study was to analyze volatile formation on cinnamon (Laurus cinnamomum) samples after gamma irradiation. These samples were irradiated into plastic packages using a (60)Co facility. Radiation doses applied were 0, 5, 10, 15, 20 and 25 kGy. For the analysis of the samples, solid-phase microextraction (SPME) was applied, while for the analysis of volatile compounds, CG/MS. Spice irradiation showed the highest decrease in volatile compounds. For L. cinnamomum, the irradiation decreased volatile compounds by nearly 56% and 89.5%, respectively, comparing to volatile from a sample which had not been previously irradiated. Crown Copyright (C) 2009 Published by Elsevier Ltd. All rights reserved.

Essential Oil of Thymus vulgaris: Preparation of Pharmaceutical Mouthwash Formulation and In Vitro Evaluation of the Bacterial Plaque-Inhibiting Properties.

Essential Oil of Thymus vulgaris: Preparation of Pharmaceutical Mouthwash Formulation and In Vitro Evaluation of the Bacterial Plaque-Inhibiting Properties. The aim of this study was to evaluate the in vitro effect of the essential oil of Thymus vulgaris (thyme) pure or incorporate in a alcohol-free pharmaceutical mouthwash formulation, against Streptococcus mutans (ATCC 25175), being determined the Minimal Inhibitory Concentration (MIC) and the effect in the bacterial plate formation. The MIC value obtained for the essential oil was 100 mu g/mL (1 %). The mouthwash pharmaceutical formulation containing commercial essential oil of T. vulgaris was preparated. Microbiological and macroscopic analysis as well as analyses for MEV confirmed the effectiveness of this new alcohol-free mouthwash formulation containing essential oil of T. vulgaris as agent with plaque-inhibiting properties and possible application in the preventive dentistry. The chemical characterization of the bioactive essential oil was accomplished by CG-MS, being verified the presence of carvacrol, p-cimene and alpha-pinene as major constituents.

Especies nativas del Centro de Argentina: potencial agroindustrial y perspectivas para la producción de energía y biocombustibles

La región centro de Argentina posee una elevada riqueza de especies nativas y endémicas, con potencial valor agroindustrial. Flourensia campestris y F. oolepis (Asteraceae), conforman comunidades denominadas "chilcales". Son reconocidas por sus usos tradicionales como aromática, tintórea, medicinal y para leña -en especial raíz- y presentan potencial aplicación en la agroindustria como insecticida, antimicrobiana, antifúngica y aleloquímica. Trabajos realizados en nuestro laboratorio con extractos acuosos de hojas secas de F. campestris demostraron un potente efecto herbicida sobre semillas de Lactuca sativa. Mediante el fraccionamiento biodirigido por CC y técnicas espectrales (GC-MS, IR, 1H-RMN, 13C-RMN, 2D-RMN) se pudo identificar la estructura molecular del ácido hamanásico ((4S, 8S)–7–carboxi–8–hidroxi- 1(2), 12(13)-dien-bisaboleno). Su presencia en F. campestris, y su actividad biológica, no habían sido descriptos con anterioridad y sugieren un potencial herbicida natural. En ambas especies se puede apreciar a simple vista su alto contenido en resinas, compuestos propuestos para reemplazar a los hidrocarburos en la fabricación de pinturas, pegamentos y adhesivos. Estudios preliminares en nuestro laboratorio señalan un contenido de entre un 20-40 % de resinas en la biomasa aérea de Flourensia, sin embargo, no existen al presente estudios sobre su composición química ni sobre su potencial aplicación industrial. Por otro lado, el desarrollo de cultivos energéticos, para la generación de electricidad por combustión de biomasa, constituye uno de los objetivos principales dentro de las políticas de energías renovables a nivel nacional (programa GENREN) y mundial. Las especies con mayor aptitud deben poseer altas tasas de crecimiento y un alto grado de tolerancia de adversidades bióticas y abióticas, lo que permitiría cultivarlos en áreas marginales para la agricultura tradicional, hechos que coinciden con las especies de Flourensia en estudio. Asimismo, el tratamiento térmico o pirólisis de biomasa proveniente de la agricultura es una de las alternativas de reutilización de la misma con distintos fines. Este pasivo ecológico puede ser transformado en productos de alto valor agregado. En base a lo expuesto, el objetivo general de este proyecto es investigar en las dos especies vegetales endémicas de Argentina y abundantes en la provincia de Córdoba, las características de los metabolitos secundarios en relación a su potencial aplicación agroquímica (herbicidas naturales), la composición de sus resinas para uso industrial y su rendimiento como materia prima de alta densidad energética para la cogeneración de electricidad y producción de biocombustible, en función del desarrollo de una agricultura sustentable. Para ello, el proyecto propone incrementar el rendimiento de la purificación de ácido hamanásico e identificar y cuantificar su presencia en otros órganos de F. campestris y en F.oolepis, con el objetivo de evaluar su efecto herbicida, mediante bioensayos en cápsulas de Petri, en especies cultivables y malezas. Los usos potenciales de las resinas se estudiarán en base a la identificación de sus compuestos químicos mediante su extracción y análisis espectrales (CG-MS). A través de la determinación del poder calorífico, contenido de cenizas y de nitrógeno de la biomasa aérea de las especies, se evaluará su rendimiento energético para emplear como biocombustible sólido en la cogeneración eléctrica, mientras que con la aplicación del método fast pyrolysis y análisis por CG-MS, se determinará su aplicación o su posterior modificación de acuerdo a las características del bio-oil deseado. El destino energético de las especies propuestas permitiría iniciar de manera rápida la etapa de domesticación y puesta en cultivo, y avanzar en el desarrollo de aplicaciones industriales más sofisticadas, como el aprovechamiento de sus propiedades bioactivas o el desarrollo de productos industriales basados en sus metabolitos secundarios.

Especies nativas del Centro de Argentina: potencial agroindustrial y perspectivas para la producción de energía y biocombustibles

La región centro de Argentina posee una elevada riqueza de especies nativas y endémicas, con potencial valor agroindustrial. Flourensia campestris y F. oolepis (Asteraceae), conforman comunidades denominadas "chilcales". Son reconocidas por sus usos tradicionales como aromática, tintórea, medicinal y para leña -en especial raíz- y presentan potencial aplicación en la agroindustria como insecticida, antimicrobiana, antifúngica y aleloquímica. Trabajos realizados en nuestro laboratorio con extractos acuosos de hojas secas de F. campestris demostraron un potente efecto herbicida sobre semillas de Lactuca sativa. Mediante el fraccionamiento biodirigido por CC y técnicas espectrales (GC-MS, IR, 1H-RMN, 13C-RMN, 2D-RMN) se pudo identificar la estructura molecular del ácido hamanásico ((4S, 8S)–7–carboxi–8–hidroxi- 1(2), 12(13)-dien-bisaboleno). Su presencia en F. campestris, y su actividad biológica, no habían sido descriptos con anterioridad y sugieren un potencial herbicida natural. En ambas especies se puede apreciar a simple vista su alto contenido en resinas, compuestos propuestos para reemplazar a los hidrocarburos en la fabricación de pinturas, pegamentos y adhesivos. Estudios preliminares en nuestro laboratorio señalan un contenido de entre un 20-40 % de resinas en la biomasa aérea de Flourensia, sin embargo, no existen al presente estudios sobre su composición química ni sobre su potencial aplicación industrial. Por otro lado, el desarrollo de cultivos energéticos, para la generación de electricidad por combustión de biomasa, constituye uno de los objetivos principales dentro de las políticas de energías renovables a nivel nacional (programa GENREN) y mundial. Las especies con mayor aptitud deben poseer altas tasas de crecimiento y un alto grado de tolerancia de adversidades bióticas y abióticas, lo que permitiría cultivarlos en áreas marginales para la agricultura tradicional, hechos que coinciden con las especies de Flourensia en estudio. Asimismo, el tratamiento térmico o pirólisis de biomasa proveniente de la agricultura es una de las alternativas de reutilización de la misma con distintos fines. Este pasivo ecológico puede ser transformado en productos de alto valor agregado. En base a lo expuesto, el objetivo general de este proyecto es investigar en las dos especies vegetales endémicas de Argentina y abundantes en la provincia de Córdoba, las características de los metabolitos secundarios en relación a su potencial aplicación agroquímica (herbicidas naturales), la composición de sus resinas para uso industrial y su rendimiento como materia prima de alta densidad energética para la cogeneración de electricidad y producción de biocombustible, en función del desarrollo de una agricultura sustentable. Para ello, el proyecto propone incrementar el rendimiento de la purificación de ácido hamanásico e identificar y cuantificar su presencia en otros órganos de F. campestris y en F.oolepis, con el objetivo de evaluar su efecto herbicida, mediante bioensayos en cápsulas de Petri, en especies cultivables y malezas. Los usos potenciales de las resinas se estudiarán en base a la identificación de sus compuestos químicos mediante su extracción y análisis espectrales (CG-MS). A través de la determinación del poder calorífico, contenido de cenizas y de nitrógeno de la biomasa aérea de las especies, se evaluará su rendimiento energético para emplear como biocombustible sólido en la cogeneración eléctrica, mientras que con la aplicación del método fast pyrolysis y análisis por CG-MS, se determinará su aplicación o su posterior modificación de acuerdo a las características del bio-oil deseado. El destino energético de las especies propuestas permitiría iniciar de manera rápida la etapa de domesticación y puesta en cultivo, y avanzar en el desarrollo de aplicaciones industriales más sofisticadas, como el aprovechamiento de sus propiedades bioactivas o el desarrollo de productos industriales basados en sus metabolitos secundarios.

Flavonóides e triterpenos de Baccharis pseudotenuifolia: bioatividade sobre Artemia salina

The phytochemical investigation of the chloroformic and methanolic extracts of the Baccharis pseudotenuifolia led to the isolation of triterpenes, steroids and flavonoids. From chloroformic extract were isolated oleanolic acid and alpha-spinasterol while from methanolic extract were isolated the flavonoids: hispidulin, naringenin, 3'-methoxy-luteolin, apigenin, kaempferol, eriodyctiol, aromadendrin, quercetin, 3'-methoxy-quercetin, quercetin-3-O-rhamnoside and quercetin-3-O-glucoside. The structure of these compounds were identified by IR, CG/MS, ¹H and 13C NMR spectral analysis and comparison with literature. In addition, the extracts were evaluated by means of Brine Shrimp Lethality test and the highier activity was observed in the chloroformic extract.

O enfoque da metrologia química em análises toxicológicas na atividade turfística: validação de método analítico para determinação de cafeína em matrizes biológicas

This paper proposes an alternate method to detect forbidden doping substances present in biological matrices of horseracing. The method was fully validated for caffeine, identified as the most frequent forbidden substance in the analysis conducted by the Antidoping Laboratory of the Brazilian Jockey Club, which adopts a zero threshold limit according to national and international horseracing practices. The metrological reliability of the method applied to toxicological analysis in biological matrices is discussed. Although the analytical method proposed for detection of a zero threshold level of the doping substance is qualitative, it was validated for the determination of the limiting value (also known as quantification limit value) introducing a criterion that prevents the issuing of incorrect results ("false-positives" and "false-negatives").

Aplicação de espectrometria de massas com ionização por elétron na análise de alcaloides do mulungu

Erythrina verna is a medicinal plant used to calm agitation popularly known as mulungu. We purchased the barks of E. verna from a commercial producer and analyzed the alkaloid fraction of the bark by CG-MS and HRESI-MS. Five erythrinian alkaloids were identified: erysotrine, erythratidine, erythratidinone, epimer, and 11-hydroxieritratidinone. Here we report the compound 11-hydroxieritratidinone for the first time as a natural product.

Phenolic compounds and antioxidant activity of hydroalcoholic extracts of wild and cultivated murtilla (Ugni molinae Turcz.)

Over the last decade a considerable increase in the number of studies addressing the use of antioxidants from natural sources has led to the identification and understanding of the potential mechanisms of biologically active components. This results from the fact that they can be used to replace synthetic antioxidants commonly used in food. Murtilla (Ugni molinae Turcz) is a native berry grown in Chile, and in the present study, the phenolic composition and antioxidant activity of its fruits were studied. Hydroalcoholic extracts of dehydrated fruits from two genotypes of murtilla (Ugni molinae Turcz.) were produced. Extracts of wild murtilla and 14-4 genotype fruits had 19.35 and 40.28mg GAE/g for Total Phenolic Compounds, 76.48, and 134.35μmol TEAC/g for DPPH, and 157.04 and 293.99 μmol TEAC/g for ABTS, respectively. Components such as quercetin, epicatechin, and gallic, benzoic and hydrocaffeic acids were identified by CG/MS analysis. All of them showed antioxidant activity. Therefore, it is possible to say that the hydroalcoholic extracts of murtilla have antioxidant potential to be used in lipidic food.

Emission of polycyclic aromatic hydrocarbons from gasohol and ethanol vehicles

The exhaust emission of the polycyclic aromatic hydrocarbons (PAHs) considered toxic to human health were investigated on two spark ignition light duty vehicles, one being gasohol (Gasohol, in Brazil, is the generic denomination for mixtures of pure gasoline plus 20-25% of anhydrous ethyl alcohol fuel (AEAF).)-fuelled and the other a flexible-fuel vehicle fuelled with hydrated ethanol. The influence of fuel type and quality, aged lubricant oil type and use of fuel additives on the formation of these compounds was tested using standardized tests identical to US FTP-75 cycle. PAH sampling and chemical analysis followed the basic recommendations of method TO-13 (United States. Environmental Protection Agency, 1999. Compendium Method TO-13A - Determination of polycyclic Aromatic hydrocarbons (PAH) in Ambient Air Using Gas Chromatography/Mass Spectrometry (CG/MS). Center for environmental research information, Cincinnati, p. 78), with the necessary modification for this particular application. Results showed that the total PAH emission factor varied from 41.9 mu g km(-1) to 612 mu g km(-1) in the gasohol vehicle, and from 11.7 mu g km(-1) to 27.4 mu g km(-1) in the ethanol-fuelled vehicle, a significant difference in favor of the ethanol vehicle. Generally, emission of light molecular weight PAHs was predominant, while high molecular weights PAHs were not detected. In terms of benzo(a)pyrene toxicity equivalence, emission factors varied from 0.00984 mu g TEQ km(-1) to 4.61 mu g TEQ km(-1) for the gasohol vehicle and from 0.0117 mu g TEQ km(-1) to 0.0218 mu g TEQ km(-1) in the ethanol vehicle. For the gasohol vehicle, results showed that the use of fuel additive causes a significant increase in the emission of naphthalene and phenanthrene at a confidence level of 90% or higher; the use of rubber solvent on gasohol showed a reduction in the emission of naphthalene and phenanthrene at the same confidence level; the use of synthetic oil instead of mineral oil also contributed significantly to a decrease in the emission of naphthalene and fluorene. In relation to the ethanol vehicle, the same factors were tested and showed no statistically significant influence on PAH emission. (c) 2008 Elsevier Ltd. All rights reserved.

Desenvolvimento de uma unidade laboratorial para quantificação de BTX como poluentes atmosféricos, usando microextração em fase sólida

This dissertation aims the development of an experimental device to determine quantitatively the content of benzene, toluene and xylenes (BTX) in the atmosphere. BTX are extremely volatile solvents, and therefore play an important role in atmospheric chemistry, being precursors in the tropospheric ozone formation. In this work a BTX new standard gas was produced in nitrogen for stagnant systems. The aim of this dissertation is to develop a new method, simple and cheaper, to quantify and monitor BTX in air using solid phase microextraction/ gas chromatography/mass spectrometry (SPME/CG/MS). The features of the calibration method proposed are presented in this dissertation. SPME sampling was carried out under non-equilibrium conditions using a Carboxen/PDMS fiber exposed for 10 min standard gas mixtures. It is observed that the main parameters that affect the extraction process are sampling time and concentration. The results of the BTX multicomponent system studied have shown a linear and a nonlinear range. In the non-linear range, it is remarkable the effect of competition by selective adsorption with the following affinity order p-xylene > toluene > benzene. This behavior represents a limitation of the method, however being in accordance with the literature. Furthermore, this behavior does not prevent the application of the technique out of the non-linear region to quantify the BTX contents in the atmosphere.

Estudo dos principais fatores que influenciam na solubilização dos hpas em águas

Polycyclic aromatic hydrocarbons (PAHs) constitute a family of compounds characterized by having two or more condensed aromatic rings and for being a class of substances that are widely distributed in the environment as a complex mixture, being very persistent in the environment due to its low solubility in water. The application of chemometric methods to analytical chemistry has provided excellent results in studying the solubility of PAHs in aqueous media in order to understand the mechanisms involved in environmental contamination. The method consists in analyzing the solubilization of PAHs from diesel oil in water varying parameters such as stirring time, volume of oil added and pH, using a full factorial design of two levels and three factors. PAHs were extracted with n-hexane and analyzed by fluorescence spectroscopy because they have molecular characteristics fluorescent due to the large number of condensed rings and links, and gas chromatography coupled to a mass spectrometer (GC-MS). The results of fluorescence analysis showed that only the stirring time and pH influenced the solubility of PAHs in diesel fuel. How is a non-selective technique for the study of fluorescence was performed on form and semi-quantitative. And for the chromatographic analysis the results showed that the solubility of the different PAHs is influenced differently so that you can classify them into groups by the results of the effects