Preferential location of lidocaine and etidocaine in lecithin bilayers as determined by EPR, fluorescence and H-2 NMR

We have examined the effect of the uncharged species of lidocaine (LDC) and etidocaine (EDC) on the acyl chain moiety of egg phosphatidylcholine liposomes. Changes in membrane organization caused by both anesthetics were detected through the use of EPR spin labels (5, 7 and 12 doxyl stearic acid methyl ester) or fluorescence probes (4, 6, 10, 16 pyrene-fatty acids). The disturbance caused by the LA was greater when the probes were inserted in more external positions of the acyl chain and decreased towards the hydrophobic core of the membrane. The results indicate a preferential insertion of LDC at the polar interface of the bilayer and in the first half of the acyl chain, for EDC. Additionally, 2 H NMR spectra of multilamellar liposomes composed by acyl chain-perdeutero DMPC and EPC (1:4 mol%) allowed the determination of the segmental order (S-mol) and dynamics (T-1) of the acyl chain region. In accordance to the fluorescence and EPR results, changes in molecular orientation and dynamics are more prominent if the LA preferential location is more superficial, as for LDC while EDC seems to organize the acyl chain region between carbons 2-8, which is indicative of its positioning. We propose that the preferential location of LDC and EDC inside the bilayers creates a "transient site", which is related to the anesthetic potency since it could modulate the access of these molecules to their binding site(s) in the voltage-gated sodium channel. (C) 2007 Elsevier B.V. All rights reserved.

Avaliação cinética e potencial do Nb2O5 obtido a partir de um complexo de nióbio para formação do oleato de metila através da reação de esterificação do ácido oleico

Among the heterogeneous catalysts materials made from niobium show up as an alternative to meet the demand of catalysts for biodiesel production. This study aims to evaluate the potential of a heterogeneous catalyst derived from a complex of niobium in the reaction of methyl esterification of oleic acid. The catalyst was synthesized after calcination at different temperatures of a niobium complex ((NH4)3[NbO(C2O4)3].H2O) generating a niobium oxide nanostructure with a different commercial niobium oxide used to synthesize the complex. The commercial niobium oxide, the complex niobium and niobium catalyst were characterized by thermogravimetry (TG and DTA), surface area analysis (BET), scanning electron microscopy (SEM) and X-ray diffraction (XRD), showing the catalyst has researched morphological and crystallographic indicating a catalytic potential higher than that of commercial niobium oxide characteristics. Factorial with central composite design point, with three factors (calcination temperature, molar ratio of alcohol/oleic acid and mass percentage of catalyst) was performed. Noting that the optimal experimental point was given by the complex calcination temperature of 600°C, a molar ratio alcohol/oleic acid of 3.007/1 and the catalyst mass percentage of 7.998%, with a conversion of 22.44% oleic acid in methyl oleate to 60 min of reaction. We performed a composite linear and quadratic regression to determine an optimal statistical point of the reaction, the temperature of calcination of the complex at 450°C, the molar ratio of alcohol/oleic acid 3.3408/1 and mass percentage of catalyst of 7.6833% . Kinetic modeling to estimate parameters for heterogeneous catalysis it set well the experimental results with a final conversion of 85.01% with 42.38% of catalyst and without catalyst at 240 min reaction was performed. Allowing to evaluate the catalyst catalytic studied has the potential to be used in biodiesel production

Hidróxidos duplos lamelares aplicados à obtenção de biodiesel

In this paper, the Layered Double Hydroxides (LDH s) type hydrotalcite were synthesized, characterized and tested as basic heterogeneous catalysts for the production of biodiesel by transesterification of sunflower oil with methanol. The synthesis of materials Layered Double Hydroxides (LDH s) by co-precipitation method from nitrates of magnesium and aluminum, and sodium carbonate. The materials were submitted to the variation in chemical composition, which is the amount of Mg2+ ions replaced by Al3+. This variation affects the characteristic physico-chemical and reaction the solid. The molar ratio varied in the range of 1:1 and 3:1 magnesium / aluminum, and their values between 0.2 and 0.33. This study aims to evaluate the influence of variation of molar ratio of mixed oxides derived from LDH s and the influence of impregnation of a material with catalytic activity, the KI, the rate of conversion of sunflower oil into methyl esters (biodiesel) through transesterification by heterogeneous catalysis. .The catalysts were calcined at 550 ° C and characterized by X-ray diffraction (XRD), scanning electron microscopy and energy dispersive spectroscopy of X-ray (SEM / EDS), thermogravimetric analysis (TG) and test basicity. The transesterification reaction was performed for reflux is a mixture of sunflower oil and methanol with a molar ratio of 15:1, a reaction time of 4h and a catalyst concentration of 2% by weight. The physical-chemical characterization of sunflower oil and biodiesel obtained by the route methyl submitted according NBR, EN, ASTM. Subsequently, it was with the chromatographic and thermogravimetric characterizations of oils. The results of chromatographic analysis showed that the catalysts were effective in converting vegetable oil into biodiesel, in particular the type hydrotalcite KI-HDL-R1, with a conversion of 99.2%, indicating the strong influence of the chemical composition of the material, in special due to presence of potassium in the structure of the catalyst

Obtenção de biodiesel através da transesterificação do óleo de farelo de arroz utilizando KI/Al2O3

This study proposes to find a biodiesel through transesterification of rice bran oil with KI/Al2O3 checking the influence of two types of alumina (Amorphous and Crystalline) for conversion into methyl esters. The catalyst was synthesized by the wet impregnation method. Adding 30 mL of 35% KI(aq.) in 10 g of alumina, under stirring at 80 °C for 3 hours. The reaction conditions used in this study were optimized, with a molar ratio methanol:oil of 15:1, 8 h of reaction time and reflux temperature. The catalyst amount was varied in the range of 1 to 5 % wt. The solid catalysts materials were analyzed by: x-ray diffraction (XRD), thermogravimetry (TG), N2 adsorption/desorption, scanning electron microscopy (SEM) and basicity, for the identification of its structure and composition, verifying the presence of basic sites. The results showed that Al2O3(A) presents an amorphous structure, high surface area and a better catalytic activity, in relation to the catalyst synthesized with Al2O3(C) support that proved to have a more crystalline structure, having as well, a lesser surface area, enabling difficulties for the incorporation of active sites. The obtained biodiesel with 5% wt. KI/Al2O3(A) presented physicochemical properties within the standards specified by the Resolution No 7/2008 ANP and obtained the best reaction yield with 95.2%, according to quantitative measurement from the TG, which showed 96.2% conversion into methyl esters. It was furthermore found that with the increasing amount of the quantity of the catalyst in the reaction, there was also an increase in the ester content obtained. The specific mass and the kinematic viscosity were reduced with the increase of the amount of quantity of the catalyst, indicating an increase in the conversion of triglycerides

Síntese e caracterização de óxidos de zinco e de magnésio suportados em A1SBA-15 para produção de biodiesel

To overcome the challenge of meeting growing energy demand in a sustainable way, biodiesel has shown very promising as alternative energy can replace fossil fuels, even partially. Industrially, the biodiesel is produced by homogeneous transesterification reaction of vegetable oils in the presence of basic species used as catalysts. However, this process is the need for purification of the esters obtained and the removal of glycerin formed after the reaction. This context, the alternative catalysts have that can improve the process of biodiesel production, aiming to reduce costs and facilitate its production. In this study, the AlSBA-15 support with Si / Al ratio = 50 was synthesized, as like as the heterogeneous catalysts of zinc oxide and magnesium supported on mesoporous AlSBA-15 silica, in the concentrations of 5, 10, 15 and 30 %, relative to the support. The textural properties and structural characterization of catalysts and supports were determined by techniques: X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) coupled to the chemical analyzer, adsorption / desorption of N2, thermal analysis (TG / DTG), absorption spectroscopy in the infrared (FTIR) and X-ray photoelectron spectroscopy (XPS). Characterization results indicated that the support AlSBA-15 retained the hexagonal ordered after the incorporation of zinc oxide and magnesium oxide in the holder. For heterogeneous catalysts, ZnO-AlSBA-15, that was observed the presence of zinc oxide nanoparticles dispersed in the surface and interior channels of the mesoporous and microporous support. The catalytic activity was evaluated by the transesterification reaction of sunflower oil via methylic route, and some reaction parameters were optimized with the most active catalyst in biodiesel production by sunflower oil. For the series of heterogeneous catalysts, the sample with 30 % ZnO supported on AlSBA-15 showed a better conversion of triglyceride to methyl esters, about 95.41 % of reaction conditions: temperature 175 °C, with molar ratio of 42:1, stirring at 200 rpm and under a pressure of 14 bar for 6 h. The catalyst MgO-AlSBA-15 showed no catalytic activity in the studied reactions

Studies on anti-allergic constituents in the leaves and stems of Anchietia salutaris var. martiana (Violaceae)

The anti-allergic active fractionation of hexane extracts of the leaves and stems of Anchietia salutaris,ar. martiana (family Violaceae) nas performed by monitoring their activities with an in vitro bioassay system measuring the inhibitory effects on induced histamine release from guinea pig lung cells. Three known pentacyclic triterpenes (friedelin, alpha-amyrin, beta-amyrin) were isolated, but these compounds were inactive. Aliphatic hydrocarbons and methyl esters of fatty acids (palmitic, oleic, linoleic, linolenic acids) were detected in active fractions. All compounds isolated were detected for the first time in this medicinal plant.

Synergistic effect in the catalytic activity of lipase Rhizomucor miehei immobilized on zeolites for the production of biodiesel

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

Metodologia experimental para avaliação de custos de produção e utilização de biodiesel: estudo de caso de quatro ésteres metílicos e óleo diesel comercial

Considerando que o Brasil detém uma vasta gama de matérias-primas para produção de biodiesel, e também que há a possibilidade de produção em pequena escala, prima-se por estudos de cunho econômico a partir de metodologias de fácil execução. O objetivo do trabalho foi demonstrar uma metodologia e sua aplicação para avaliação dos custos inseridos dentro do processo produtivo e de utilização do biodiesel. A metodologia foi aplicada a biodieseis originários de óleo de soja, girassol, frango e sebo bovino, dos quais se avaliaram economicamente os custos fixos e variáveis para conversão química dos óleos e gorduras em ésteres metílicos, em uma planta de produção experimental. Os custos de produção para cada uma das quatro citadas são distintos em função do valor inicial por litro de cada uma. Também fora avaliado o custo específico e o consumo específico de cada um dos biodieseis, a fim de determinar a diferença em relação ao óleo diesel comercial. No estudo de caso, os resultados mostraram vantagens para o óleo diesel, tanto no custo quanto no consumo. Comparando-se os biodieseis, o de sebo bovino apresentou-se com o menor custo de produção e o menor consumo.

Sterolic and triterpenoidic constituents of stem bark of Drypetes gossweileri

Four compounds have been identified from the stem bark of Drypetes gossweileri by means of H-1- and C-13-NMR spectroscopy, stearic acid, methyl putranjate, and two new compounds: stigmasterol stearate and beta-sitosterol stearate.

Similar anxiolytic-like effects following intra-amygdala infusions of benzodiazepine receptor agonist and antagonist: Evidence for the release of an endogenous benzodiazepine inverse agonist in mice exposed to elevated plus-maze test

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Clerodane diterpenes from Aristolochia species

The investigation of Aristolochia brasiliensis and A. esperanzae afforded 12 clerodane derivatives, including the following six novel ones: rel (5S, 8R, 9S, 10R)-2-oxo-ent-3-cleroden-15-oic acid, rel (5S, 8R, 9S, 10R)-2-oxo-ent-clerod-3,13-dien-15-oic acid methyl ester, (5R, 8R, 9S, 10R)-ent-3-cleroden-15-oic acid, rel (5S, 8R, 9S, 10R)-ent-clerod-3,13-dien-15-oic acid, (2S, 5R, 8R, 9S, 10R)-2-hydroperoxy-ent-3-cleroden-15-oic acid methyl ester and (2S, 5R, 8R, 9S, 10R)-2-hydroperoxy-ent-clerod-3,13-dien-15-oic acid methyl ester. The structures were assigned on the basis of spectral data and derivatization by chemical reactions. The occurrence of this type of diterpene has not previously been reported in Aristolochiaceae. © 1987.

Effect of Surface Treatments on the Bond Strength between Composite Resin and Acrylic Resin Denture Teeth

Purpose: This investigation studied the effects of 3 surface treatments on the shear bond strength of a light-activated composite resin bonded to acrylic resin denture teeth. Materials and Methods: The occlusal surfaces of 30 acrylic resin denture teeth were ground flat with up to 400-grit silicon carbide paper. Three different surface treatments were evaluated: (1) the flat ground surfaces were primed with methyl methacrylate (MMA) monomer for 180 seconds; (2) light-cured adhesive resin was applied and light polymerized according to the manufacturer's instructions; and (3) treatment 1 followed by treatment 2. The composite resin was packed on the prepared surfaces using a split mold. The interface between tooth and composite was loaded at a cross-head speed of 0.5 mm/min until failure. Results: Analysis of variance indicated significant differences between the surface treatments. Results of mean comparisons using Tukey's test showed that significantly higher shear bond strengths were developed by bonding composite resin to the surfaces that were previously treated with MMA and then with the bonding agent when compared to the other treatments. Conclusion: Combined surface treatment of MMA monomer followed by application of light-cured adhesive resin provided the highest shear bond strength between composite resin and acrylic resin denture teeth.

Anesthesia of fish with benzocaine does not interfere with comet assay results

Fish blood erythrocytes are frequently used as sentinels in biomonitoring studies. Usually, fish blood is collected by painful cardiac or caudal vein punctures. Previous anesthesia could decrease animal suffering but it is not known at present whether anesthesia can cause confounding effects. Therefore, using the alkaline single cell gel (SCG)/comet assay with blood erythrocytes of the cichlid fish Nile tilapia, we tested for a possible modulation of induced DNA damage (methyl methanesulfonate; MMS) by the anesthetic benzocaine administered by bath exposure (80mg/l for ∼10min). Furthermore, benzocaine (80-600mg/l) was tested for its genotoxic potential on fish erythrocytes in vitro and for potential interactions with two known genotoxins (MMS and hydrogen peroxide). Our results did neither indicate a significant increase in the amount of DNA damage (even after a 48h follow-up), nor indicated interactions with MMS-induced DNA damage when fish were exposed to benzocaine in vivo. There was also no increase in DNA damage after in vitro exposure of fish erythrocytes to benzocaine. Clear concentration-related effects were observed for the two genotoxins in vitro, which were not significantly altered by the presence of benzocaine. These results suggest that anesthesia of fish does not confound comet assay results and the use of blood samples from anesthetized fish can be recommended with regard to animal welfare. © 2002 Elsevier Science B.V. All rights reserved.

Iridoid glucosides from Randia spinosa (Rubiaceae)

An iridoid glucoside: randinoside, along with five known iridoids: galioside, deacetylasperulosidic acid methyl ester, scandoside methyl ester, geniposide and gardenoside, were isolated from the stems of Randia spinosa. The structures were determined by spectroscopic analysis, including 2D NMR techniques. © 2003 Elsevier Science Ltd. All rights reserved.

Effects of dentin collagen removal on microleakage of bonded restorations

Purpose: To evaluate the effects of removing dentin collagen exposed by acid etching on the microleakage of bonded restorations with and without flowable composite application and submitted to thermocycling and long-term water storage. Materials and Methods: Standardized Class V cavities were prepared in 180 bovine incisors. They were randomly assigned to three groups according to the adhesive technique used. Conventional group (C): Single Bond was applied according to the manufacturer's instructions and Z250 composite was placed. Hypochlorite group (H): After acid etching a 10% NaOCl aqueous solution was applied for 1 min, then Single Bond and Z250 were applied. Hypochlorite and Flowable group (HF): Similar to group H, but following adhesive application, a thin layer of Natural Flow flowable composite was applied before the Z250. Each group was divided into three subgroups (0, 6, 12), which remained immersed in distilled water for 24 h or 6 or 12 months and underwent 500, 1500 or 2500 thermal cycles, respectively. At the end of each storage time, the specimes were stained with silver nitrate, decalcified, immersed in methyl salicylate for clearing and observed under a stereomicroscope to determine microleakage (scores 0 to 4). The data were analyzed using the Kruskal-Wallis and the Multiple Comparison Tests (α = 0.05). Results: After 12 months, every group showed significant increases in microleakage. There was no significant difference between Groups H and HF for the three different periods of time, but they showed statistically less microleakage than Group C. Conclusion: The removal of dentinal collagen reduced the marginal microleakage when compared to the conventional technique. The use of the flowable composite did not produce significant effects. No technique was completely effective in preventing microleakage.