Influência de diferentes sistemas de solvente água-etanol sobre as propriedades físico-químicas e espectroscópicas dos compostos macrocíclicos feofitina e clorofila α

This work focus on the influence of solvent on the photophysical properties of chlorophyll α and pheophytin. Both compounds are related to the photosynthesis process and are considered prototypes of photosensitizers in Photodynamic Therapy. Fluorescence measurements were developed using water/ethanol mixtures at different compositions, since both solvents could be employed in biological applications. The spectroscopic properties of these compounds undergo profound changes depending on water content in the ethanol due to auto-aggregation processes. The major hydrophobicity and the lower dielectric constant of ethanol when compared with water precluded significantly the auto-aggregation process of these compounds.

Bonding agent underneath sealant: shear bond strength to oil-contaminated

This study evaluated in vitro the shear bond strength of a resin-based pit-and-fissure sealant (Fluroshield - F) associated with either an ethanol-based (Adper Single Bond 2 - SB) or an acetone-based (Prime & Bond - PB) adhesive system under conditions of oil contamination. Mesial and distal enamel surfaces from 30 sound third molars were randomly assigned to 2 groups (n=30): I - no oil contamination; II - oil contamination. Contamination (0.25 mL during 10 s) was performed after 37% phosphoric acid etching with an air/oil spray. The specimens were randomly assigned to subgroups, according to the bonding protocol adopted: subgroup A - F was applied to enamel without an intermediate bonding agent layer; In subgroups B and C, SB and PB, respectively, were applied, light-cured, and then F was applied and light-cured. Shear bond strength was tested at a crosshead speed of 0.5 mm/min in a universal testing machine. Means (± SD) in MPa were: IA-11.28 (±1.84); IIA-12.02 (±1.15); IB-9.73 (±2.38); IIB-9.62 (±2.29); IC-28.30 (±1.63); and IIC-25.50 (±1.91). It may be concluded that the oil contamination affected negatively the sealant bonding to enamel and the acetone-based adhesive system (PB) layer applied underneath the sealant was able to prevent its deleterious effects to adhesion.

Successful transplant of mesenchymal stem cells in induced osteonecrosis of the ovine femoral head: preliminary results

PURPOSE: Evaluate the bone tissue recovery following transplantation of ovine mesenchymal stem cells (MSC) from bone marrow and human immature dental-pulp stem cells (hIDPSC) in ovine model of induced osteonecrosis of femoral head (ONFH). METHODS: Eight sheep were divided in three experimental groups. First group was composed by four animals with ONFH induced by ethanol through central decompression (CD), for control group without any treatment. The second and third group were compose by two animals, six weeks after ONFH induction received transplantation of heterologous ovine MSC (CD + oMSC), and hIDPSC (CD + hIDPSC), respectively. In both experiments the cells were transplanted without application of any type of immunosupression protocol. RESULTS: Our data indicate that both cell types used in experiments were able to proliferate within injured site providing bone tissue recovery. The histological results obtained from CD+hIDPSC suggested that the bone regeneration in such animals was better than that observed in CD animals. CONCLUSION: Mesenchymal stem cell transplant in induced ovine osteonecrosis of femoral head by central decompression technique is safe, and apparently favors bone regeneration of damaged tissues.

Nutritional reserves of Vochysiaceae seeds: chemical diversity and potential economic uses

Contents of proteins, carbohydrates and oil of seeds of 57 individuals of Vochysiaceae, involving one species of Callisthene, six of Qualea, one of Salvertia and eight of Vochysia were determined. The main nutritional reserves of Vochysiaceae seeds are proteins (20% in average) and oils (21. 6%). Mean of carbohydrate contents was 5. 8%. Callisthene showed the lowest protein content (16. 9%), while Q. cordata was the species with the highest content (30% in average). The contents of ethanol soluble carbohydrates were much higher than those of water soluble carbohydrates. Oil contents lay above 20% for most species (30. 4% in V. pygmaea and V. pyramidalis seeds). The predominant fatty acids are lauric (Q. grandiflora), oleic (Qualea and Salvertia) or acids with longer carbon chains (Salvertia and a group of Vochysia species). The distribution of Vochysiaceae fatty acids suggests for seeds of some species an exploitation as food sources (predominance of oleic acid), for other species an alternative to cocoa butter (high contents or predominance of stearic acid) or the production of lubricants, surfactants, detergents, cosmetics and plastic (predominance of acids with C20 or C22 chains) or biodiesel (predominance of monounsaturated acids). The possibility of exploitation of Vochysiaceae products in a cultivation regimen and in extractive reserves is discussed.

Unusual 1,6-diphenyl-1,3,5-hexatriene (DPH) spectrophotometric behavior in water/ethanol and water/DMSO mixtures

The absorption spectra of DPH at fixed concentration do not change with water content in organic solvents. It exhibits monomer bands, such as those obtained in ethanol. The absorption did not change for solutions up to 54 and 46% of water in ethanol and DMSO, respectively, for [DPH] = 5.0 × 10-6 mol L-1 at 30 °C. However, at the same experimental conditions, a gradual sharp decay of the DPH fluorescence is observed. It is proposed that water molecules below these water concentration limits act as quenchers of the excited states of DPH. Stern-Volmer quenching constants by intensities measurements are 7.4 × 10-2 (water/ethanol) and 2.6 × 10-2 L mol-1 (water/DMSO). DPH lifetime measurements in the absence and presence of water resulted in 7.1 × 10-2 L mol-1 in water/ethanol, which pointed out that the process is a dynamic quenching by water molecules. For experiments using DPH as probe, this process can affect data, leading to misunderstanding interpretation.

Ethanol electrooxidation on Pt-Sn and Pt-Sn-W bulk alloys

Ethanol oxidation has been studied on Pt-Sn and Pt-Sn-W electrodes prepared in an arc-melting furnace. Different electrochemical techniques like cyclic voltammetry and chronoamperometry were used to evaluate the catalytic activity of these materials. The electro-oxidation process was also investigated by in situ infrared reflectance spectroscopy in order to determine adsorbed intermediates and reaction products. Experimental results indicated that Pt-Sn and Pt-Sn-W alloys are able to oxidize ethanol mainly to acetaldehyde and acetic acid. Adsorbed CO was also detected, demonstrating the viability of splitting the C-C bond in the ethanol molecule during the oxidation process. The adsorbed CO was further oxidized to CO2.This reaction product was clearly detected by SNIFTIRS. Pt-Sn-W catalyst showed a better electrochemical performance than Pt-Sn that, in it turn, is better than Pt-alone.

Metallochlorophylls of magnesium, copper and zinc: evaluation of the influence of the first coordination sphere on their solvatochromism and aggregation properties

In this study the role of different metal centers (magnesium, zinc and copper) on the enhancement of the hydrophilic character of metallochlorophylls, was evaluated. The solvatochromism as well as the aggregation process for these compounds in water/ethanol mixtures at different volume ratios were evaluated using Fluorescence, and Resonant Light Scattering (RLS) measurements, aiming to characterize the behavior of these compounds. Independently on the studied metallochlorophyll, the presence of at least 60% of water results in a considerable increase in the fluorescence emission, probably a direct consequence of a lower aggregation of these compounds, which is confirmed by the results from RLS measurements. Additionally, the results suggest that magnesium and zinc chlorophyll should be promising phototherapeutic agents for Photodynamic Therapy.

A novel disposable electrochemical microcell: construction and characterization

An alternative technique for the fabrication of disposable electrochemical microcells containing working, reference and auxiliary electrodes on a single device is reported. The procedure is based on thermal-transfer of toner masks onto CD-R (recordable compact discs) gold surfaces to define the layout of the electrodes (contour). In a subsequent step, the layout is manually painted with a permanent marker pen. The unprotected gold surface is conveniently etched (chemical corrosion) and the ink is then easily removed with ethanol, generating gold surfaces without contamination. The final and reproducible area of the electrodes is defined by heat transference of a second toner mask. Silver epoxy is deposited on one of the gold bands which is the satisfactorily used as reference electrode. These microcells were electrochemically characterized by cyclic, linear, and square wave voltammetry, and several electroactive species were used as model systems. The area reproducibility of the electrodes for different microcells was studied and a relative standard deviation better than 1,0% (n = 10) was obtained. Disposable electrochemical microcells were successfully used in analysis of liquid samples with volumes lower than 200 µL and good stability and reproducibility (RSD less than 2.0%) were achieved. These microcells were also evaluated for quantification of paracetamol and dipyrone in pharmaceutical formulations.

Consumo abusivo e dependência de álcool em população adulta no Estado de São Paulo, Brasil

OBJETIVO: Descrever as prevalências de consumo abusivo e dependência de álcool em população adulta de 20 a 59 anos no Estado de São Paulo, e suas associações com variáveis demográficas e socioeconômicas. MÉTODOS: Inquérito domiciliar do tipo transversal (ISA-SP), em quatro áreas do Estado de São Paulo: a) Região Sudoeste da Grande São Paulo, constituída pelos Municípios de Taboão da Serra, Itapecerica da Serra e Embu; b) Distrito do Butantã, no Município de São Paulo; c) Município de Campinas e; d) Município de Botucatu. Foi considerado consumo abusivo de álcool a ingestão em dia típico de 30 gramas ou mais de etanol para os homens, e 24 gramas ou mais para as mulheres. A dependência de álcool foi caracterizada pelo questionário CAGE. Análises bivariadas e multivariadas dos dados foram realizadas a partir de Modelos de Regressão de Poisson. Todas as análises foram estratificadas por sexo. RESULTADOS: Em 1.646 adultos entrevistados, a prevalência de consumo abusivo de álcool foi de 52,9% no sexo masculino e 26,8% no sexo feminino. Quanto à dependência de álcool, foram observadas duas ou mais respostas positivas no teste CAGE em 14,8% dos homens e em 5,4% das mulheres que relataram consumir álcool. Isto corresponde a uma prevalência populacional de dependência de 10,4% nos homens e 2,6% nas mulheres. O consumo abusivo de álcool no sexo masculino apresentou associação inversa à faixa etária e associação direta à escolaridade e ao tabagismo. No sexo feminino, observou-se associação direta do consumo abusivo de álcool com a escolaridade e o tabagismo, e com as situações conjugais sem companheiro. A dependência de álcool no sexo masculino associou-se a não exercer atividade de trabalho e à baixa escolaridade. No sexo feminino não houve associação do CAGE com nenhuma das variáveis estudadas. CONCLUSÕES: Pela alta prevalência de consumidores e dependentes, é essencial a identificação dos segmentos sociodemográficos mais vulneráveis ao consumo abusivo e dependência de álcool. As associações entre a dependência/abuso e não estar exercendo atividade de trabalho, no sexo masculino, e a maior prevalência em mulheres de escolaridade universitária, sugerem componentes para programas de intervenção e controle.

Effect of the kappa-casein gene polymorphism, breed and seasonality on physicochemical characteristics, composition and stability of bovine milk

The objective of this study was to evaluate the effect of genetic polymorphism of kappa-casein, breed and seasonality on the physicochemical characteristics, composition and stability of milk in commercial dairy herds. A total of 879 milk and blood samples were collected from 603 Holstein and 276 Girolando cows, obtained during rainy and dry seasons. Milk samples were analyzed to determine the physicochemical characteristics, composition and ethanol stability, while blood samples were subjected to polymerase chain reaction to identify the kappa-casein genotype. The frequencies of genotypes AA, AB and BB of k-casein were respectively, 66.83, 31.84 and 1.33% for Holstein, and 71.38, 27.90 and 0.72% for the Girolando cows, respectively. The A allele was more frequent than the B allele, both for Holstein (0.827 and 0.173) and Girolando cows (0.853 and 0.147), respectively. Cows of AB and BB genotypes showed a higher milk fat content compared to the AA genotype. There was an interaction between breed and seasonality on the concentration of milk urea with higher values for Holstein and Girolando cows in the rainy and dry season, respectively. The levels of lactose, total solids, crude protein, true protein, casein and the casein:true protein ratio were higher during the dry season, while during the rainy season, the somatic cell count and milk urea concentration were higher. There was no association between milk stability and k-casein genotypes, but Holstein cows showed higher milk stability than Girolando cows, and milk was more stable during the rainy season than during the dry season.

Efeitos do teor de carboidratos solúveis sobre as características da silagem de cana-de-açúcar

Objetivou-se quantificar na cana-de-açúcar o teor de carboidratos solúveis (CHOs) que anula a produção de etanol e avaliar os efeitos desses carboidratos sobre o valor nutritivo e outras características fermentativas da silagem de cana-de-açúcar. Utilizou-se o delineamento inteiramente casualizado com três tratamentos, cada um com quatro repetições. Os tratamentos consistiram da retirada total do caldo da cana-de-açúcar, por meio de prensagem, e de sua reconstituição (0, 50 ou 100%) à cana. No nível de 50% de reconstituição, o caldo foi adicionado à cana juntamente com 50% de água e, no nível 0%, adicionou-se 100% de água à cana. A restituição resultou em concentrações de 41,6; 34,0 e 23,0% de carboidratos solúveis na matéria seca (MS). O material foi ensilado em 12 silos experimentais confeccionados a partir de baldes plásticos. A abertura dos silos foi realizada 85 dias após a ensilagem, quando foram determinados os teores dos ácidos orgânicos e a composição química das silagens. A retirada de carboidratos solúveis da cana-de-açúcar teve efeito linear decrescente sobre os teores de matéria seca, o teor de carboidratos solúveis e a digestibilidade in vitro da matéria seca (DIVMS) das silagens, no entanto, ocasionou aumento dos teores de fibra detergente ácido (FDA), fibra detergente neutro (FDN) e lignina. Observou-se efeito linear decrescente da retirada dos carboidratos solúveis sobre os teores de etanol e ácidos lático e butírico e as perdas de matéria seca das silagens. Não se observaram efeitos de tratamentos sobre os dados de estabilidade aeróbia. A produção de etanol seria nula se a cana-de-açúcar contivesse apenas 12,4% de CHOs com base na matéria seca (MS).

Efeito do processamento na atividade antioxidante do grão de amaranto (Amaranthus cruentus L. BRS-Alegria)

As características nutricionais, funcionais e agrícolas do amaranto são responsáveis pelo aumento do interesse por este alimento nas últimas décadas. O grão pode ser cozido, estourado, torrado, extrusado ou moído para ser consumido. Foi avaliado o efeito destes processamentos na atividade antioxidante do grão de amaranto, através das determinações do teor de fenólicos totais e da atividade antioxidante in vitro por dois métodos: inibição da oxidação lipídica pelo sistema \03B2-caroteno/ácido linoléico e índice de atividade antioxidante pelo aparelho Rancimat®. Os processamentos reduziram em média o teor de fenólicos totais do grão de amaranto de 31,7 para 22,0 mg de equivalentes de ácido gálico/g de resíduo seco. Observou-se que o extrato obtido por etanol do grão torrado foi o único a apresentar menor índice de atividade antioxidante (IAA) em relação ao grão cru (1,3 v 1,7). Os processos de extrusão, torração e explosão não alteraram a capacidade de inibição da oxidação lipídica (IOL) do amaranto (55 por cento). Já o cozimento aumentou o IOL (79 por cento), o que pode ter ocorrido devido ao maior tempo de processamento sob alta temperatura (100ºC/10min). Os métodos mais comuns de processamento do grão de amaranto ocasionaram redução do teor de fenólicos totais, no entanto a atividade antioxidante do estourado e do extrusado, avaliada pelos dois métodos, foi semelhante ao do grão cru. O grão de amaranto tanto cru como processado apresenta potencial antioxidante. Polifenóis, antocianinas, flavonóides, tocoferóis, vitamina C e compostos gerados na reação de Maillard podem estar relacionados à atividade antioxidante deste grão