Solvent assisted decomposition of the tetrahedral intermediate of the transesterification reaction to biodiesel production. A density functional study

B3LYP/6-31 + G(d) calculations were employed to investigate the mechanism of the transesterification reaction between a model monoglyceride and the methoxide and ethoxide anions. The gas-phase results reveal that both reactions have essentially the same activation energy (5.9 kcal mol(-1)) for decomposition of the key tetrahedral intermediate. Solvent effects were included by means of both microsolvation and the polarizable continuum solvation model CPCM. Both solvent approaches reduce the activation energy, however, only the microsolvation model is able to introduce some differentiation between methanol and ethanol, yielding a lower activation energy for decomposition of the tetrahedral intermediate in the reaction with methanol (1.1 kcal mol(-1)) than for the corresponding reaction with ethanol (2.8 kcal mol(-1)), in line with experimental evidences. Analysis of the individual energy components within the CPCM approach reveals that electrostatic interactions are the main contribution to stabilization of the transition state. (C) 2009 Elsevier Ltd. All rights reserved.

Evaluation of the counterimmunoelectrophoresis reaction as a serodiagnosis test for swine leptospirosis

Avaliou-se a reação de contraimunoeletroforese (CIE) como teste gênero-específico para diagnóstico da leptospirose suína, usando-se três extratos solúveis de Leptospira sp, sorovares pomona, icterohaemorrhagiae e patoc, obtidos pelo tratamento com Triton X-100 a quente e aplicados a amostras de soro de suínos subdivididos em três grupos: Grupo 1, 10 suínos experimentalmente infectados com estirpe Pomona; Grupo 2, 50 suínos naturalmente infectados e Grupo 3, controle. As amostras de soros foram submetidas à reação de CIE e os resultados comparados aos da Soroaglutinação Microscópica (SAM), técnica de referência pela WHO. Os Grupos 1 e 3 foram monitorados por 93 dias após a inoculação (p.i.). Pela SAM a soroconversão do Grupo 1 ocorreu por volta do 10º dia p.i., enquanto pela CIE, empregando-se qualquer extrato antigênico, foi anterior à SAM. Quando a CIE foi realizada frente a antigeno homólogo à infecção, seus resultados foram equivalentes aos da SAM, não se verificando o mesmo frente aos antígenos heterólogos. Neste aspecto, os Grupos 1 e 3 mostraram comportamento diferente pois não houve diferença significativa entre os resultados da CIE frente aos três antígenos, o que poderia significar serem independentes do sorovar responsável pelo surto ou infectante. Embora a CIE seja segura, rápida, de fácil execução, de baixo custo e ideal para análise em grande escala de amostras, revelou-se de limitada capacidade gênero-específica, o que não é desejavel para testes de triagem de campo; mas poderia ser útil na detecção precoce de resposta sorológica em relação à SAM.

Induction of the acrosome reaction test to in vitro estimate embryo production in Nelore cattle

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

Evaluation of the Tissue Reaction to Fast Endodontic Cement (CER) and Angelus MTA

Introduction: A new cement (CER; Cimento Endodontico Rapido or fast endodontic cement) has been developed to improve handling properties. It is a formulation that has Portland cement in gel. However, there had not yet been any study evaluating its biologic properties. The purpose of this study was to evaluate the rat subcutaneous tissue response to CER and Angelus MTA. Methods: The materials were placed in polyethylene tubes and implanted into dorsal connective tissue of Wistar rats for 7, 30, and 60 days. The specimens were prepared to be stained with hematoxylin-eosin or von Kossa or not stained for polarized light. The presence of inflammation, predominant cell type, calcification, and thickness of fibrous connective tissue were recorded. Scores were defined as follows: 0, none or few inflammatory cells, no reaction; 1, <25 cells, mild reaction; 2, 25-125 cells, moderate reaction; 3, >125 cells, severe reaction. Fibrous capsule was categorized as thin when thickness was <150 mu m and thick at >150 mu m. Necrosis and formation of calcification were both recorded. Results: Both materials Angelus MTA and CER caused moderate reactions at 7 days, which decreased with time. The response was similar to the control at 30 and 60 days with Angelus MTA and CER, characterized by organized connective tissue and presence of some chronic inflammatory cells. Mineralization and granulations birefringent to polarized light were observed with both materials. Conclusions: It was possible to conclude that CER was biocompatible and stimulated mineralization. (J Endod 2009,35:1377-1380)

Revisiting the addition reaction of TeCl4 to alkynes: the crystal structure and docking studies of 1-chloro-2-trichlorotelluro-3-phenyl-propen-2-ol

Tellurium tetrachloride adds to alkynes via two pathways: a concerted syn addition, that yields Z-tri- and tetra-substituted alkenes or by an anti addition that yields E-alkenes. The mechanistic aspects of these divergent pathways have been reevaluated at the light of crystallographic data. The molecules, of the title compound, in the crystal, are associated in a helical fashion with a Te...Te pitch of 6.3492(6) angstrom. As it exhibits inhibitory activity for cathepsin B and in order to gain more insight of the inhibition mechanism, a docking study was undertaken providing insight on why organic telluranes are more efficient inhibitors than inorganic ones as AS-101. (c) 2006 Elsevier B.V. All rights reserved.

Correlation among immune response, morphogenesis of the granulomatous reaction and spleen lymphoid structure in murine experimental paracoccidioidomycosis

We studied the correlation among cellular immune response, the pattern of lung granulomatous lesions and alterations in spleen lymphoid structure in Swiss mice inoculated intravenously with Paracoccidioides brasiliensis strain 18. The animals were evaluated at 24, 48 and 96 h after infection and further studied weekly for 18 weeks by: (i) the macrophage migration inhibition test with phytohemagglutinin (PHA) and P. brasiliensis antigen (PbAg); and (ii) histopathology of the lung and spleen lesions. One group of animals was gamma -irradiated (8 Gy), infected under the same conditions and evaluated for the pattern of lung granulomatous lesions and spleen lymphoid structure at 24, 48 and 96 h after infection. During the first week of infection, the non-irradiated animals presented a positive response to PHA and PbAg, compact granulomas in the lungs and a typical hyperplasia of the spleen white pulp. However, from weeks 2 to 5, a depression of the cell-mediated immunity (CMI) response to PHA and PbAg was observed in association with granulomas presenting only large mononuclear cells and lacking both giant cells and a peripheral halo of small mononuclear cells. This pattern of granuloma formation was similar to that seen in gamma -irradiated animals, whose cells involved in CMI were absent. After week 7, the non-irradiated animals showed granulomas characterized by the presence of giant cells and a peripheral halo of small mononuclear cells. This type of granuloma was formed concomitantly with recovery of the CMI and of the lymphoid structure of the spleen. The results showed a correlation among granulomas composed of large mononuclear cells, hypoplasia of the splenic tissue and impaired CMI. This correlation indicated that although granuloma morphogenesis per se does not depend on the activation of CMI, this response is important at later stages during modulation of the cellular composition of the granulomas.

Analysis of the inflammatory reaction induced by the catfish (Cathorops spixii) venoms

Cathorops spixii is one of the most abundant venomous fish of the southeastern coast of the State of São Paulo, and consequently causes a great part of the accidents seen there. The accidents affect mainly fishermen, swimmers and tourists and are characterized by punctiform or wide wounds, erythema, edema, pain, sudoresis, indisposition, fever, nausea, vomiting and secondary infection. The objective of this work was to characterize the inflammatory response induced in mice by both venoms (mucus and sting) of the catfish C spixii. Our results demonstrated that both venoms induced a great number of rolling and adherent leukocytes in the post-capillary venules of cremaster muscle of mice, and an increase in the vascular permeability in peritoneal cavity. Mucus induced the recruitment of neutrophils immediately after injection followed later by macrophage infiltration. In contrast, the cellular infiltration elicited by sting venom was rapidly resolved. The peritonitis reaction provoked by venoms was characterized by cytokine (IL-6), chemokines (MCP-1 and KC) or lipid mediator (LTB4) production in the peritoneal cavity. The macrophages from 7-day mucus venom-induced exudates upon in vitro mucus venom stimulation, expressed CD1 Ic x MHC class II and release bioactive IL-12p70. on the other hand, sting venom-elicited peritoneal macrophages lost the ability to differentiate into dendritic cells, following re-stimulation in vitro with sting venom, they do not express CD11c, nor do they exhibit sufficient levels of MHC class II. In conclusion, both types of venoms (mucus or sting) promote inflammatory reaction with different profiles, and the inflammatory reaction induced by the first was characterized by antigen persistence in peritoneal cavity that allowed the activation of phagocytic cells with capacity of antigenic presentation. (C) 2007 Elsevier Ltd. All rights reserved.

Optimization of the Transesterification Reaction in Biodiesel Production and Determination of Density and Viscosity of Biodiesel/Diesel Blends at Several Temperatures

Waste frying oil has been used to optimize the production of biodiesel. Biodiesel was prepared through sodium ethoxide catalyzed methanolysis from the transesterification of recycled waste frying oil. Optimization of the transesterification reaction for biodiesel production was carried out by means of statistical analyses using ANOVA. The optimum conditions for reaction were the following: a oil methanol mole ratio of 1:9, temperature of 50 degrees C, catalyst mass fraction of 0.9 %, and reaction time of 40 min, which enabled a yield of 98.7 % determined by gas chromatography/mass spectrometry (GC/MS) analysis. The density and viscosity of biodiesel/diesel blends have been determined as a function of composition at several temperatures.

Characterization of glycerol kinase from baker's yeast: Response surface modeling of the enzymatic reaction

The present study describes a methodology of dosage of glycerol kinase (GK) from baker's yeast. The standardization of the activity of the glycerol kinase from baker's yeast was accomplished using the diluted enzymatic preparation containing glycerol phosphate oxidase (GPO) and glycerol kinase. The mixture was incubated at 60 degrees C by 15 min and the reaction was stopped by the SDS solution addition. A first set of experiments was carried out in order to investigate the individual effect of temperature (7), pH and substrate concentration (S), on GK activity and stability. The pH and temperature stability tests showed that the enzyme presented a high stability to pH 6.0-8.0 and the thermal stability were completely maintained up to 50 degrees C during 1 h. The K(m) of the enzyme for glycerol was calculated to be 2 mM and V(max) to be 1.15 U/mL. In addition, modeling and optimization of reaction conditions was attempted by response surface methodology (RSM). Higher activity values will be attained at temperatures between 52 and 56 degrees C, pH around 10.2-10.5 and substrate concentrations from 150 to 170 mM.This low cost method for glycerol kinase dosage in a sequence of reactions is of great importance for many industries, like food, sugar and alcohol. RSM showed to be an adequate approach for modeling the reaction and optimization of reaction conditions to maximize glycerol kinase activity. (C) 2007 Elsevier B.V. All rights reserved.

Investigation of the pore blockage of a Brazilian dolomite during the sulfation reaction

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

Sulfur-containing palladacycles as catalyst precursors for the heck reaction

(formula presented) The air, water, and highly thermally stable sulfur-containing palladacycles, mainly derived from the ortho-palladation of benzylic thioethers, are exceptional catalyst precursors for the Heck reaction. The reaction can be performed with aryl iodides, bromides, and chlorides, with acrylic esters and styrene, leading to turnover numbers up to 1 850 000.

Interference of inorganic ions on phenol degradation by the Fenton reaction

The addition of Cu2+ ions to the classical Fenton reaction (Fe2+ plus H2O2 at pH 3) is found to accelerate the degradation of organic compounds. This synergic effect causes an approximately 15 % additional reduction of the total organic carbon (TOC), representing an overall improvement of the efficiency of the mineralization of phenol. Although Fe2+ exhibits a high initial rate of degradation, the degradation is not complete due to the formation of compounds refractory to the hydroxyl radical. The interference of copper ions on the degradation of phenol by the Fenton reaction was investigated. In the presence of Cu2+, the degradation is slower, but results in a greater reduction of TOC at the end of the reaction (t = 120 min). In the final stages of the reaction, when the Fe3+ in the solution is complexed in the form of ferrioxalate, the copper ions assume the role of the main catalyst of the degradation.

Mechanistic Implications of Zinc(II) Ions on the Degradation of Phenol by the Fenton Reaction

A study of the interference of Zn2+ ions on phenol degradation by Fenton reaction (Fe2+/Fe3(+) + H2O2) is reported. One of the first intermediates formed in the reaction, catechol, can reduce Fe3+ to Fe2+ and, in the presence of H2O2 initiates an efficient catalytic redox cycle. In the initial stages of the reaction, this catechol-mediated cycle becomes the principal route of thermal degradation of phenol and its oxidation products. The Zn2+ ion addition enhances the persistence time of catechol, probably by stabilization of the corresponding semiquinone radical via complexation.

Risk assessment behaviors associated with corticosterone trigger the defense reaction to social isolation in rats: Role of the anterior cingulate cortex

The extent to which the hypothalamic-pituitary-adrenal axis is activated by short-term and long-term consequences of stress is still open to investigation. This study aimed to determine (i) the correlation between plasma corticosterone and exploratory behavior exhibited by rats subjected to the elevated plus maze (EPM) following different periods of social isolation, (ii) the effects of the corticosterone synthesis blocker, metyrapone, on the behavioral consequences of isolation, and (iii) whether corticosterone produces its effects through an action on the anterior cingulate cortex, area 1 (Cg1). Rats were subjected to 30-min, 2-h, 24-h, or 7-day isolation periods before EPM exposure and plasma corticosterone assessments. Isolation for longer periods of time produced greater anxiogenic-like effects on the EPM. However, stretched attend posture (SAP) and plasma corticosterone concentrations were increased significantly after 30 min of isolation. Among all of the behavioral categories measured in the EPM, only SAP positively correlated with plasma corticosterone. Metyrapone injected prior to the 24 h isolation period reversed the anxiogenic effects of isolation. Moreover, corticosterone injected into the Cg1 produced a selective increase in SAP. These findings indicate that risk assessment behavior induced by the action of corticosterone on Cg1 neurons initiates a cascade of defensive responses during exposure to stressors.

Behavioral characterization of the alarm reaction and anxiolytic-like effect of acute treatment with fluoxetine in piaucu fish

In Ostariophysan fish, the detection of the alarm substance liberated into the water as a consequence of an attack by a predator elicits an alarm reaction or anti-predatory behavior. In this study, experiments were performed to: (i) describe and quantitatively characterize the behavioral and ventilatory responses in piaucu fish (Leporinus macrocephalus), individually and as part of a school, to conspecific alarm substance (CAS) and; (ii) test the effect of acute fluoxetine treatment on alarm reaction. Histological analysis revealed the presence of club cells in the intermediate and superficial layers of the epidermis. The predominant behavioral response to CAS was freezing for fish held individually, characterized by the cessation of the swimming activity as the animal settles to a bottom corner of the aquarium. Fish exposed to CAS showed decrease in the mean ventilatory frequency (approximately 13%) relative to control. In schools, CAS elicited a biphasic response that was characterized by erratic movements followed by increased school cohesion and immobility, reflected as an increased school cohesion (65.5% vs. -5.8% for controls) and in the number of animals near the bottom of the aquarium (42.0% vs. 6.5% for controls). Animals treated with single i.p. injections of fluoxetine (10 mu g/g b.w.) did not exhibit alarm behavior following CAS stimulation. These results show that an alarm pheromone system is present in piaucu fish, evidenced by the presence of epidermal club cells and an alarm reaction induced by CAS and consequently of a chemosensory system to transmit the appropriate information to neural structures responsible for initiating anti-predator behavioral responses. In addition, fluoxetine treatment caused an anxiolytic-like effect following CAS exposure. Thus, the alarm reaction in piaucu can be a useful model for neuroethological and pharmacological studies of anxiety-related states. (C) 2011 Elsevier Inc. All rights reserved.