3-Hydroxy-4, 5-dimethyl-2 (5 H)-furanone levels in fortified Madeira wines: Relationship to sugar content

The maturation of Madeira wines usually involves exposure to relatively high temperatures and humidity levels >70%, which affect the aroma and flavor composition and lead to the formation of the typical and characteristic bouquet of these wines. To estimate the levels of sotolon [3-hydroxy4,5-dimethyl-2(5 H )-furanone] and their behavior over time, 86 aged Madeira wines samples (1-25 years old), with different sugar concentrations, respectively, 90 g L-1 for Boal, 110 g L-1 for Malvazia, 25 g L -1 for Sercial, and 65 g L-1 for Verdelho varieties, were analyzed. Isolation was performed by liquid-liquid extraction with dichloromethane followed by chromatographic analysis by GC-MS. The reproducibility of the method was found to be 4.9%. The detection and quantification limits were 1.2 and 2.0 µgL-1, respectively. The levels of sotolon found ranged from not detected to 2000 µgL-1 for wines between 1 and 25 years old. It was observed that during aging, the concentration of sotolon increased with time in a linear fashion ( r ) 0.917). The highest concentration of sotolon was found in wines with the highest residual sugar contents, considering the same time of storage. The results show that there is a strong correlation between sotolon and sugar derivatives: furfural, 5-methylfurfural, 5-hydroxymethylfurfural, and 5-ethoxymethylfurfural. These compounds are also well correlated with wine aging. These findings indicate that the kinetics of sotolon formation is closely related with residual sugar contents, suggesting that this molecule may come from a component like sugar.

Estabelecimento do perfil metabolómico volátil da urina e saliva, como estratégia não-invasiva, para a deteção de potenciais biomarcadores de diferentes tipos de cancro

Com este trabalho pretendeu-se estabelecer o perfil metabolómico volátil de amostras de fluidos biológicos, nomeadamente saliva e urina, de pacientes com cancro da mama e do pulmão e de indivíduos saudáveis (grupo controlo), utilizando a Microextração em Fase Sólida em modo headspace (HS-SPME) seguida de Cromatografia Gasosa acoplada à Espectrometria de Massa (GC-MS). Efetuou-se a comparação entre os perfis voláteis dos grupos estudados com o objetivo de identificar metabolitos que possam ser considerados como potenciais biomarcadores dos tipos de cancro em estudo. De modo a otimizar a metodologia extrativa, HS-SPME, foram avaliados os diferentes parâmetros experimentais com influência no processo extrativo. Os melhores resultados foram obtidos com a fibra CAR/PDMS, usando um volume de 2 mL de saliva acidificada, 10% NaCl (m/v) e 45 minutos de extração a uma temperatura de 37±1°C. Para a urina foi utilizada a mesma fibra, 4 mL de urina acidificada, 20% NaCl (m/v) e 60 minutos de extração a 50±1°C. Nas amostras de saliva e urina, foram identificados 243 e 500 metabolitos voláteis respetivamente, sendo estes pertencentes a diferentes famílias químicas. Posteriormente, utilizou-se a análise discriminante por mínimos quadrados parciais (PLS-DA) que permitiu observar uma boa separação entre os grupos controlo e oncológicos. Nas amostras salivares o grupo de pacientes com cancro da mama foi maioritariamente caracterizado pelo metabolito ácido benzeno carboxílico e o grupo de pacientes com cancro do pulmão pelo ácido hexanóico. Na urina o grupo de pacientes com cancro da mama foi maioritariamente caracterizado pelo metabolito 1-[2-(Isobutiriloxi)-1-metiletil]-2,2-dimetilpropil 2-metilpropanoato e o grupo de pacientes com cancro do pulmão pelo o-cimeno. Além da metodologia PLS-DA foi realizada a validação cruzada de monte carlo (MCCV) tendo-se obtido uma elevada taxa de classificação, sensibilidade e especificidade o que demonstra a robustez dos dados obtidos.

Impact of forced-aging process on Madeira Wine flavor

The aim of this study was to determine the optimal temperature and baking time to obtain a Madeira wine considered typical by an expert panel. For this purpose simultaneous descriptive analyses of typical Madeira wines were performed, and seven descriptors were selected: “dried fruit”, “nutty”, “musty”, “baked”, “oak”, “mushroom”, and “brown sugar”. Up to 10 odor-active zones were the most frequently cited by the members of the GC-olfactometry panel as corresponding to the panel’s descriptors. The odor importance of each of the zones reported by the GC-O analysis was ranked by AEDA. Three odor zones were identified as common to both Malvasia and Sercial wines and had retention indices (RI) of 1993 (“brown sugar” and “toasted”), 2151 (“brown sugar”), and 2174 (“nutty”, “driedfruits”);sotolonwasidentifiedasresponsibleforthislastaroma.Severalmoleculeswereselected to be quantified on baked wines on the basis of AEDA results and expected Maillard volatiles, such as sotolon, furfural, 5-methylfurfural, 5-ethoximethylfurfural, methional, and phenylacetaldehyde. It was observed that typicity scores were positively correlated with the concentrations of sotolon and sugar and baking time and negatively with the fermentation length.

Preparação e caracterização de catalisadores à base de titânio suportado em MCM-41 para produção de compostos oxigenados através da pirólise catalítica do capim elefante

In recent years, the area of advanced materials has been considerably, especially when it comes to materials for industrial use, such as is the case with structured porosity of catalysts suitable for catalytic processes. The use of catalysts combined with the fast pyrolysis process is an alternative to the oxygenate production of high added value, because, in addition to increasing the yield and quality of products, allows you to manipulate the selectivity to a product of interest, and therefore allows greater control over the characteristics of the final product. Based on these arguments, in this work were prepared titanium catalysts supported on MCM-41 for use in catalytic pyrolysis of biomass, called elephant grass. The reactions of pyrolysis of biomass were performed in a micro pyrolyzer, Py-5200, coupled to GC / MS, the company CDS Corporation, headquartered in the United States. The catalysts Ti-MCM-41 in different molar ratios were characterized by XRD, TG / DTG, FT-IR, SEM, XRF, UV-visible adsorption of nitrogen and the distribution of particle diameter and specific surface area measurement by the BET method. From the catalytic tests it was observed that the catalysts synthesized showed good results for the pyrolysis reaction.The main products were obtained a higher yield of aldehydes, ketones and furan. It was observed that the best reactivity is a direct function of the ratio Si/Ti, nature and concentration of the active species on mesoporous supports. Among the catalysts Ti-MCM-41 (molar ratio Si / Ti = 25 and 50), the ratio Si / Ti = 25 (400 ° C and 600 ° C) favored the cracking of oxygenates such as acids , aldehydes, ketones, furans and esters. Already the sample ratio Si / Ti = 50 had the highest yield of aromatic oxygenates

Hidrocarbonetos policíclicos aromáticos em sedimentos de fundo do estuário do rio Potengi, região da grande Natal (RN): implicações ambientais

Estuaries are environments prone to the input of chemical pollutants of various kinds and origins, including polycyclic aromatic hydrocarbons (PAHs). Anthropogenic PAHs may have two possible sources: pyrolytic (with four or more aromatic rings and low degree of alkylation) and petrogenic (with two and three aromatic rings and high degree of alkylation). This study aimed to evaluate the levels, distribution and possible sources of polycyclic aromatic hydrocarbons in the estuary of the Potengi river, Natal, Brazil. Samples of bottom sediments were collected in the final 12 km of the estuary until its mouth to the sea, where the urbanization of the Great Natal is more concentrated. Sampling was performed on 12 cross sections, with three stations each, totaling 36 samples, identified as T1 to T36. The non alkylated and alkylated PAHs were analyzed by gas chromatography coupled to mass spectrometry (GC / MS). PAHs were detected in all 36 stations with total concentration on each varying 174-109407 ng g-1. These values are comparable to those of several estuarine regions worldwide with high anthropogenic influence, suggesting the record of diffuse contamination installed in the estuary. PAHs profiles were similar for most stations. In 32 of the 36 stations, low molecular weight PAHs (with 2 and 3 ring: naphthalene, phenanthrene and their alkylated homologues) prevailed, which ranged from 54% to 100% of the total PAH, indicating that leaks, spills and combustion fuels are the dominant source of PAH pollution in the estuary. The level of contamination by PAHs in most stations suggests that there is potential risk of occasional adverse biological effects, but in some stations adverse impacts on the biota may occur frequently. The diagnostic ratios could differentiate sources of PAHs in sediments of the estuary, which were divided into three groups: petrogenic, pyrolytic and mixing of sources. The urban concentration of the Great Natal and the various industrial activities associated with it can be blamed as potential sources of PAHs in bottom sediments of the estuary studied. The data presented highlight the need to control the causes of existing pollution in the estuary

Pirólise rápida catalítica do capim elefante utilizando materiais mesoporosos e óxidos metálicos para deoxigenação em bio-óleo

The fast pyrolysis of lignocellulosic biomass is a thermochemical conversion process for production energy which have been very atratactive due to energetic use of its products: gas (CO, CO2, H2, CH4, etc.), liquid (bio-oil) and charcoal. The bio-oil is the main product of fast pyrolysis, and its final composition and characteristics is intrinsically related to quality of biomass (ash disposal, moisture, content of cellulose, hemicellulose and lignin) and efficiency removal of oxygen compounds that cause undesirable features such as increased viscosity, instability, corrosiveness and low calorific value. The oxygenates are originated in the conventional process of biomass pyrolysis, where the use of solid catalysts allows minimization of these products by improving the bio-oil quality. The present study aims to evaluate the products of catalytic pyrolysis of elephant grass (Pennisetum purpureum Schum) using solid catalysts as tungsten oxides, supported or not in mesoporous materials like MCM-41, derived silica from rice husk ash, aimed to reduce oxygenates produced in pyrolysis. The biomasss treatment by washing with heated water (CEL) or washing with acid solution (CELix) and application of tungsten catalysts on vapors from the pyrolysis process was designed to improve the pyrolysis products quality. Conventional and catalytic pyrolysis of biomass was performed in a micro-pyrolyzer, Py-5200, coupled to GC/MS. The synthesized catalysts were characterized by X ray diffraction, infrared spectroscopy, X ray fluorescence, temperature programmed reduction and thermogravimetric analysis. Kinetic studies applying the Flynn and Wall model were performed in order to evaluate the apparent activation energy of holoceluloce thermal decomposition on samples elephant grass (CE, CEL and CELix). The results show the effectiveness of the treatment process, reducing the ash content, and were also observed decrease in the apparent activation energy of these samples. The catalytic pyrolysis process converted most of the oxygenate componds in aromatics such as benzene, toluene, ethylbenzene, etc

Pirólise de borras oleosas de petroleo utilizando nanomateriais

The oily sludge is a complex mix of hydrocarbons, organic impurities, inorganic and water. One of the major problems currently found in petroleum industry is management (packaging, storage, transport and fate) of waste. The nanomaterials (catalysts) mesoporous and microporous are considered promising for refining and adsorbents process for environment protection. The aim of this work was to study the oily sludge from primary processing (raw and treated) and vacuum residue, with application of thermal analyses technique (pyrolysis), thermal and catalytic pyrolysis with nanomaterials, aiming at production petroleum derived. The sludge and vacuum residue were analyzed using a soxhlet extraction system, elemental analysis, thin layer chromatography, thermogravimetry and pyrolysis coupled in gas chromatography/mass spectrometry (Py GC MS). The catalysts AlMCM-41, AlSBA-15.1 e AlSBA-15.2 were synthesized with molar ratio silicon aluminum of 50 (Si/Al = 50), using tetraethylorthosilicante as source of silicon and pseudobuhemita (AlOOH) as source of aluminum. The analyzes of the catalysts indicate that materials showed hexagonal structure and surface area (783,6 m2/g for AlMCM-41, 600 m2/g for AlSBA-15.1, 377 m2/g for AlSBA-15.2). The extracted oily sludge showed a range 65 to 95% for organic components (oil), 5 to 35% for inorganic components (salts and oxides) and compositions different of derivatives. The AlSBA-15 catalysts showed better performance in analyzes for production petroleum derived, 20% increase in production of kerosene and light gas oil. The energy potential of sludge was high and it can be used as fuel in other cargo processed in refinery

Volatile Oil of Psidium cattleianum Sabine from the Brazilian Atlantic Forest

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Triterpene benzoates from the bark of Picramnia teapensis (Simaroubaceae)

Two new benzoic acid esters of triterpene alcohols [lup-20 (29)-en-28-oic acid 3 alpha, 7 beta -dibenzoate and 3 alpha -hydroxy-lup-20(29)-en-28-ic acid 7 beta -benzoate] were isolated from the stem bark of Picramnia teapensis Tul. The structures of these compounds were established on the basis of spectral analyses. Other known compounds, beta -sitosterol, estigmasterol, lupeol and epilupeol, were identified in mixture by GC-MS. The triterpene esters have not shown in-vitro inhibitory effect on the growth of Leucoagaricus gongylophorus (Fisher), referred also as Leucocoprinus gongylophorus (Heim), syn Rozites gongylophora (Moller), the symbiotic fungus cultivated by the leaf-cutting ant Atta sexdens L.

Chemical composition and fumigant effect of essentialoil of Lippia sidoides Cham. and monoterpenes against Tenebrio molitor (L.) (coleoptera: tenebrionidae)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Sesquiterpenos do caule de Pilocarpus riedelianus e atividades sobre microorganismos

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Avaliação da atividade antimicrobiana de sistemas emulsionados contendo óleos naturais para o tratamento de infecções cutâneas

Natural oils have shown a scientific importance due to its pharmacological activity and renewable character. The copaiba (Copaifera langsdorffii) and Bullfrog (Rana catesbeiana Shaw) oils are used in folk medicine particularly because the anti-inflammatory and antimicrobial activities. Emulsion could be eligible systems to improve the palatability and fragrance, enhance the pharmacological activities and reduce the toxicological effects of these oils. The aim of this work was to investigate the antimicrobial activity of emulsions based on copaiba (resin-oil and essential-oil) and bullfrog oils against fungi and bacteria which cause skin diseases. Firstly, the essential oil was extracted from copaiba oil-resin and the oils were characterized by gas chromatography coupled to a mass spectrometry (GC-MS). Secondly, emulsion systems were produced. A microbiological screening test with all products was performed followed (the minimum inhibitory concentration, the bioautography method and the antibiofilm determination). Staphylococcus aureus, S. epidermidis, Pseudomonas aeruginosa, Candida albicans, C. parapsilosis, C. glabrata, C. krusei and C. tropicalis American Type Culture Collection (ATCC) and clinical samples were used. The emulsions based on copaiba oil-resin and essential oil improved the antimicrobial activity of the pure oils, especially against Staphylococcus e Candida resistant to azoles. The bullfrog oil emulsion and the pure bullfrog oil showed a lower effect on the microorganisms when compared to the copaiba samples. All the emulsions showed a significant antibiofilm activity by inhibiting the cell adhesion. Thus, it may be concluded that emulsions based on copaiba and bullfrog oils are promising candidates to treatment of fungal and bacterial skin infections

Um algoritmo para estimação de estado em alimentadores de distribuição de energia elétrica com base no método da soma de potências

Most algorithms for state estimation based on the classical model are just adequate for use in transmission networks. Few algorithms were developed specifically for distribution systems, probably because of the little amount of data available in real time. Most overhead feeders possess just current and voltage measurements at the middle voltage bus-bar at the substation. In this way, classical algorithms are of difficult implementation, even considering off-line acquired data as pseudo-measurements. However, the necessity of automating the operation of distribution networks, mainly in regard to the selectivity of protection systems, as well to implement possibilities of load transfer maneuvers, is changing the network planning policy. In this way, some equipments incorporating telemetry and command modules have been installed in order to improve operational features, and so increasing the amount of measurement data available in real-time in the System Operation Center (SOC). This encourages the development of a state estimator model, involving real-time information and pseudo-measurements of loads, that are built from typical power factors and utilization factors (demand factors) of distribution transformers. This work reports about the development of a new state estimation method, specific for radial distribution systems. The main algorithm of the method is based on the power summation load flow. The estimation is carried out piecewise, section by section of the feeder, going from the substation to the terminal nodes. For each section, a measurement model is built, resulting in a nonlinear overdetermined equations set, whose solution is achieved by the Gaussian normal equation. The estimated variables of a section are used as pseudo-measurements for the next section. In general, a measurement set for a generic section consists of pseudo-measurements of power flows and nodal voltages obtained from the previous section or measurements in real-time, if they exist -, besides pseudomeasurements of injected powers for the power summations, whose functions are the load flow equations, assuming that the network can be represented by its single-phase equivalent. The great advantage of the algorithm is its simplicity and low computational effort. Moreover, the algorithm is very efficient, in regard to the accuracy of the estimated values. Besides the power summation state estimator, this work shows how other algorithms could be adapted to provide state estimation of middle voltage substations and networks, namely Schweppes method and an algorithm based on current proportionality, that is usually adopted for network planning tasks. Both estimators were implemented not only as alternatives for the proposed method, but also looking for getting results that give support for its validation. Once in most cases no power measurement is performed at beginning of the feeder and this is required for implementing the power summation estimations method, a new algorithm for estimating the network variables at the middle voltage bus-bar was also developed

Sistema de supervisão aérea baseado em navegação visual para detecção de anomalias em instalações de petróleo e gás

This work deals with the development of a prototype of a helicopter quadrotor for monitoring applications in oil facilities. Anomaly detection problems can be resolved through monitoringmissions performed by a suitably instrumented quadrotor, i.e. infrared thermosensors should be embedded. The proposed monitoring system aims to reduce accidents as well as to make possible the use of non-destructive techniques for detection and location of leaks caused by corrosion. To this end, the implementation of a prototype, its stabilization and a navigation strategy have been proposed. The control strategy is based on dividing the problem into two control hierarchical levels: the lower level stabilizes the angles and the altitude of the vehicle at the desired values, while the higher one provide appropriate references signals to the lower level in order the quadrotor performs the desired movements. The navigation strategy for helicopter quadrotor is made using information provided by a acquisition image system (monocular camera) embedded onto the helicopter. Considering that the low-level control has been solved, the proposed vision-based navigation technique treats the problem as high level control strategies, such as, relative position control, trajectory generation and trajectory tracking. For the position control we use a control technique for visual servoing based on image features. The trajectory generation is done in a offline step, which is a visual trajectory composed of a sequence of images. For the trajectory tracking problem is proposed a control strategy by continuous servovision, thus enabling a navigation strategy without metric maps. Simulation and experimental results are presented to validate the proposal

Calibração cega de receptores cinco-portas baseada em separação cega de fontes

The exponential growth in the applications of radio frequency (RF) is accompanied by great challenges as more efficient use of spectrum as in the design of new architectures for multi-standard receivers or software defined radio (SDR) . The key challenge in designing architecture of the software defined radio is the implementation of a wide-band receiver, reconfigurable, low cost, low power consumption, higher level of integration and flexibility. As a new solution of SDR design, a direct demodulator architecture, based on fiveport technology, or multi-port demodulator, has been proposed. However, the use of the five-port as a direct-conversion receiver requires an I/Q calibration (or regeneration) procedure in order to generate the in-phase (I) and quadrature (Q) components of the transmitted baseband signal. In this work, we propose to evaluate the performance of a blind calibration technique without additional knowledge about training or pilot sequences of the transmitted signal based on independent component analysis for the regeneration of I/Q five-port downconversion, by exploiting the information on the statistical properties of the three output signals