Atividade antiinflamatória de uma heterofucana da alga marrom Padina gymnospora

Fucans, sulfated polysaccharides extracted from brown algae and some echinoderms, have been extensively studied for its diverse biological activities and because of its interference with molecular mechanisms of cell to cell recognition, including leukocyte trafficking from blood vessels into sites of inflammation mediated by selectin, a family of adhesion molecules. In the present study, we examined structural features of a heterofucan extracted from brown algae Padina gymnospora and its effect on the leukocyte migration to the peritoneum. The sulfated polysaccharides were extracted from the brown seaweed by proteolysis with the proteolytic enzyme maxatase. The presence of protein and uronic acid contamination was detected in the crude polysaccharide extract. Fractionation of the crude extract with growing concentrations of acetone produced five fractions with different concentrations of fucose, xylose, uronic acid, galactose, glucose and sulfate. The fraction precipitated with 1.5 volumes of acetone was characterized by infrared and nuclear magnetic resonance, through which can be observed the presence of sulfate groups in the C4 of -L-fucose. The anti-inflammatory action of this composite was assessed by a sodium thioglycollate-induced peritonitis assay and through nitric oxide production by the peritoneal macrophages using Griess reagent. Fraction F1.5 was efficient in reducing leukocyte influx into the peritoneal cavity when 10 mg/kg and 25mg/kg were used, resulting in a decrease of 56 and 39%, respectively. A decrease of nitric oxide production occurred when high concentrations of fucana were used. The cytotoxicity of the composite was also assessed using the reduction of 3-(4,5 dimethylthiazol-2-yl) 2,5-diphenyltetrazolium bromide (MTT). Fraction F1.5 had no cytotoxicity when 500 μg/mL of the fraction was used. This study suggests the use of fraction F1.5 (heterofucan) as an anti-inflammatory

Avaliação de uma fração polissacaridica da alga Lobophora variegata (Lamouroux) em modelo de artrite induzida em ratos por Zymosan

Fucans seaweed Lobophora variegata estructures are known for their chemical and biological properties. In this study, we analyzed, the action of fucans L. variegata and the fractions purified with acetone in Zymosan-induced arthritis. After differential fractionation with acetone, six fractions were obtained and named F0.3, F0.5, F0.8, F1, F1.5 and F2. The results showed that the fraction F1 showed high yield (51.9%) and was chosen for studies of antioxidant activity and induced arthritis. Nuclear magnetic resonance (NMR) of 13C showed signals at 103.3 and 15.78 ppm that are assigned to links β13 galactose and of the C6 methyl fucose, respectively. The infrared (IR) showed absorbance at 1238 and 850 cm-1 which are attributed to sulfate. The fraction F1 showed antioxidant activities in vitro. For analysis of inflammatory parameters chosen the polysaccharide was administered in different doses (25, 50 and 75 mg / kg ip, per body weight) and diclofenac sodium (5 mg / kg ip) and L-NAME (25 mg / kg ip) in groups of animals (n = 6). After 6 h, were analyzed for cellular influx and levels of nitrite. In experiment five days, were made analysis of swelling and serum TNF-α. Histopathological analysis were performed for confirmation of results. The fraction F1 (25, 50 and 75 mg / kg ip) reduced the cellular influx (52.1 to 96.7%) and nitric oxide levels (27.2 - 39%) compared to control group. The reduction of edema (63.4 - 100%) and serum TNF-α (p <0.001) were observed when the polysaccharide F1 administered at a dose (50 mg / kg) These results suggest that these heterofucanas of Lobophora variegata have besides the activity antioxidant and potential anti-inflammatory activity in arthritis induced by zymosan

Imunoterapia de úlceras venosas com ß-(1-3) glucana insolúvel

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior

Análise estrutural e avaliação do efeito condroitim sulfato extraído de tilápia (Oreochromis niloticus) em modelo de peritonite aguda

Chondroitin sulfate (CS) is a naturally glycosaminoglycan found in the extracellular matrix of connective tissues and it may be extracted and purified those tissues. CS is involved in various biological functions, which may be related to the having structural variability, despite the simplicity of the linear chain structure from this molecule. Researches in biotechnology and pharmaceutical field with wastes from aquaculture has been developed in Brazil. In recent decades, tilapia (Oreochromis niloticus), native fish from Africa, has been one of the most cultivated species in various regions of the world, including Brazil. The tilapia farming is a cost-effective activity, however, it generates large amount of wastes that are discarded by producers. It is understood that waste from tilapia can be used in research as a source of molecules with important biotechnological applications, which also helps in reducing environmental impacts and promote the development of an ecofriendly activity. Thus, nile tilapia viscera were subjected to proteolysis, then the glycosaminoglycans were complexed with ion exchange resin (Lewatit), it was fractionated with increasing volumes of acetone and purified by ion exchange chromatography DEAE-Sephacel. Further, the fraction was analyzed by agarose gel electrophoresis and nuclear magnetic resonance (NMR). The electrophoretic profile of the compound together the analysis of 1H NMR spectra and the HSQC correlation allow to affirm that the compound corresponds to a molecule like chondroitin sulfate. MTT assay was used to assess cell viability in the presence of CS tilapia isolated and showed that the compound is not cytotoxic to normal cells such as cells from the mouse embryo fibroblast (3T3). Then, this compound was tested for the ability to reduce the influx of leukocytes in model of acute peritonitis (in vivo) induced by sodium thioglycolate. In this context, it was done total and differential leukocytes counting in the blood and peritoneal fluid collected respectively from vena cava and the peritoneal cavity of the animals subjected to the experiment. The chondroitin sulfate for the first time isolated from tilapia (CST ) was able to reduce the migration of leukocytes to the peritoneal cavity of inflamed mice until 80.4 per cent at a dose 10µg/kg. The results also show that there was a significant reduction (p<0.001) of the population of polymorphonuclear leukocytes from peritoneal cavity in the three tested doses (0.1µg/kg; 1µg/kg and 10µg/kg) when it was compared to the positive control (just thioglycolate). Therefore, since the CST structure and mechanism of action has been completely elucidated, this compound may have potential for therapeutic use in inflammatory diseases

Alquilação de tolueno com propeno, através de complexo ferro (II) ᵦ- diimina homogêneo e heterogeneizado em MCM-41, Al-MCM-41 e SBA-15

This work describes the synthesis and aplication of homogeneous and heterogenized iron catalysts in the alkylation reaction of toluene with propene, empolying experimental design. The homogenous complex was obtained trough the synthesis of the organic ligand folowed by the complexation of the iron(II) chloride. As to the heterogenized complexes, first were synthetized the inorganic supports (SBA-15, MCM-41 and Al-MCM-41). Then, it was synthetized the ligand again, that through funcionalization with chloropropyltrimethoxysilane (CPTMS), was anchored on the support previously calcinated. To these anchored ligands, was complexed the iron(II) chloride, previously solubilizated in tetrahydrofuran (THF). The organic ligand characterization was accomplished trough nuclear magnetic resonance (NMR) and Infrared spectroscopy (IV). The supports were characterized with x-ray diffraction (DRX), texture analysis with nitrogen adsorption/desorption (before and after the anchoring), termogravimetric analysis (TG) and infrared (IV). The metalic content was quantified trough the atomic absorption spectrophotometry (AAS). The complexes were tested in catalytic reactions emolying ethylaluminium sesquichloride (EASC) as co-catalyst in steel reactor, under mecanic stirring. The reaction conditions ranged from 4 to 36 ◦C, with many aluminum/iron ratios. The catalysts were actives in homogeneous and heterogenized ways. The homogenous catalytic complex showed a maximum turnover frequency (TOF) of 8.63 ×103 · h −1 , while, in some conditions, the anchored complexes showed better results, with TOF of until 8.08 ×103 · h −1 . Aditionally, it was possible to determine an equation, to the homogenous catalyst, that describes the product quantity in function of reacional temperature and aluminum/iron ratio.

Desenvolvimento e avaliação tribológica de emulsão O/A a partir de óleo vegetal epoxidado para aplicação em fluídos de corte

The cutting fluids are lubricants used in machining processes, because they present many benefits for different processes. They have many functions, such as lubrication, cooling, improvement in surface finishing, besides they decreases the tool wear and protect it against corrosion. Therefore due to new environment laws and demand to green products, new cutting fluids must be development. These shall be biodegradable, non-toxic, safety for environment and operator healthy. Thus, vegetable oils are a good option to solve this problem, replacing the mineral oils. In this context, this work aimed to develop an emulsion cutting fluid from epoxidized vegetable oil, promoting better lubrication and cooling in machining processes, besides being environment friendly. The methodology was divided in five steps: first one was the biolubricant synthesis by epoxidation reaction. Following this, the biolubricant was characterized in terms of density, acidity, iodo index, oxirane index, viscosity, thermal stability and chemical composition. The third step was to develop an emulsion O/A with different oil concentration (10, 20 and 25%) and surfactant concentration (1, 2.5 and 5%). Also, emulsion stability was studied. The emulsion tribological performance were carried out in HFRR (High Frequency Reciprocating Rig), it consists in ball-disc contact. Results showed that the vegetable based lubricant may be synthesized by epoxidationreaction, the spectra showed that there was 100% conversion of the epoxy rings unsaturations. In regard the tribological assessment is observed that the percentage of oil present in the emulsion directly influenced the film formation and coefficient of friction for higher concentrations the film formation process is slow and unstable, and the coefficient of friction. The high concentrations of surfactants have not improved the emulsions tribological performance. The best performance in friction reduction was observed to emulsion with 10% of oil and 5% of surfactant, its average wear scar was 202 μm.

Síntese de zeólitas utilizando cátions orgânicos a base de um anel imidazólio como agentes direcionadores de estruturas em meio fluorídrico

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES

Tensoativo derivado do ácido cítrico: síntese e aplicação em fluidos de perfuração de emulsão inversa

This work describes the synthesis and study of the application of a new surfactant (Triester Lipophilic – TEL) obtained by citric acid with octanol. It is reaction was followed by thin layer chromatography (TLC) and after purification the product was characterized by proton and 13 – carbon nuclear magnetic resonance spectroscopy ( H and 13C NMR), thermogravimetric analysis (TGA) and surface tension analysis of oil-in-water emulsions. The TEL performance as surfactant in ester, n-paraffin and biodiesel based drilling fluids on the 70/30 and 60/40 water- oil rations (WOR) was evaluated by comparative tests of two commercial products used in the fields. These drilling fluids were aged in roller oven at 200 0 F during 16 h. The rheological and electric stability measurements were carried out at 135 ºF, the phase separation was evaluated after seven days at rest and the filtrate volume of drilling fluids was determined at high temperature and high pressure. The rheological behavior of the drilling fluids was evaluated by the flow curves. The results showed that the drilling fluids studied here presented Binghamian behavior as well as the used in the oil fields. The laboratory tests showed that the TEL reduced the filtrate volume and promoted the enhance of the thermal and mechanical stabilities.

Interações da trancinolona com ciclodextrinas em sistemas multicomponentes

Triamcinolone is a relevant anti-inflammatory costicosteroid drug, used mainly by injectable suspensions due its poor water solubility. The association of triamcinolone with cyclodextrins and co-solvents (triethanolamine TEA and N-methylpirrolidone NMP) was held to solubilize the drug and explain the involved interactions. Phase-solubility diagrams showed that triamcinolone was solubilized forming incredible stable complexes with cyclodextrins, in which bests results were observed applying randomyl-methylated-beta-cyclodextrin (RMβCD) (161 fold on increased solubility). The co-solvents TEA and NMP also enhanced drug solubility 1.4 and 6.7 fold, respectively. The association of both co-solvents with CDs seems decreased complexation stability, but enables higher amount of uncomplexed drug. Experimental magnetic resonance 2D-ROESY and theoretical molecular modeling studies demonstrated TRI-CDs interactions and elucidated the structure of formed complex, which occurred due to the inclusion of ring A of TRI on CDs cavity. Physicochemical aspects of solid binary and ternary complexes prepared by spray drying were assessed by using FTIR, X-ray diffraction and SEM photographs. Dissolution studies showed that binary and ternary associations presented higher dissolution efficacy in detrimental to pure drug system. In addition, the ternary complex containing TEA and RMβCD allowed drug dissolution faster than binary complex with RMβCD. Therefore, given the higher solubility and drug dissolution rate, binary and ternary complexes are new raw materials with great potential for pharmaceuticals containing triamcinolone.

Catalisadores bifuncionais à base de silicoaluminofosfato e fosfatos de nióbio para emprego em reações de hidroisomerização e hidrocraqueamento do n-hexadecano

Lubricants and cutting middle distillates typically have large amounts of n-paraffins to increase its freezing point and fluidity. Accordingly, the removal of n-paraffins of long chain lubricants oils and diesel is essential to get a product with good cold flow properties. The development of new catalysts, which exhibit thermal stability and catalytic activity for the hydroisomerization reaction is still a challenge. Thus, silicoaluminophosphates (SAPO) were synthesized by different routes. Have been used also post-synthesis treatment for obtaining hybrid structures and others synthesis have been carried out with mesoporous template (soft and hard-template). Therefore, SAPO have been impregnated with H2PtCl6 solution by the incipient wetness method. Then assessments of catalytic activities in hydroisomerization and hydrocracking reactions of hexadecane have been held. Besides SAPO, niobium phosphate - NbP - were also impregnated with platinum and evaluated in the same reaction. After impregnation, these catalysts have been characterized by X-ray diffraction (XRD), nitrogen adsorption, infrared spectroscopy with adsorbed pyridine (IV-PY), scanning electron microscopy (SEM) and resonance nuclear magnetic 29Si (29Si-NMR). The characterization results by XRD have shown that it has been possible to obtain mesoporous SAPOs. However, for the syntheses with soft template there was collapse of the structure after removal of the organic template. Even so, these catalysts have been actives. It was possible to obtain hybrid materials through the synthesis of SAPO-11 made with hard templates and by means of post-synthesis treatments samples of SAPO-11. Moreover, NbP has shown characteristic XRD of amorphous materials, with high acidity and were active in the conversion of hexadecane.

Catalisadores bifuncionais à base de silicoaluminofosfato e fosfatos de nióbio para emprego em reações de hidroisomerização e hidrocraqueamento do n-hexadecano

Lubricants and cutting middle distillates typically have large amounts of n-paraffins to increase its freezing point and fluidity. Accordingly, the removal of n-paraffins of long chain lubricants oils and diesel is essential to get a product with good cold flow properties. The development of new catalysts, which exhibit thermal stability and catalytic activity for the hydroisomerization reaction is still a challenge. Thus, silicoaluminophosphates (SAPO) were synthesized by different routes. Have been used also post-synthesis treatment for obtaining hybrid structures and others synthesis have been carried out with mesoporous template (soft and hard-template). Therefore, SAPO have been impregnated with H2PtCl6 solution by the incipient wetness method. Then assessments of catalytic activities in hydroisomerization and hydrocracking reactions of hexadecane have been held. Besides SAPO, niobium phosphate - NbP - were also impregnated with platinum and evaluated in the same reaction. After impregnation, these catalysts have been characterized by X-ray diffraction (XRD), nitrogen adsorption, infrared spectroscopy with adsorbed pyridine (IV-PY), scanning electron microscopy (SEM) and resonance nuclear magnetic 29Si (29Si-NMR). The characterization results by XRD have shown that it has been possible to obtain mesoporous SAPOs. However, for the syntheses with soft template there was collapse of the structure after removal of the organic template. Even so, these catalysts have been actives. It was possible to obtain hybrid materials through the synthesis of SAPO-11 made with hard templates and by means of post-synthesis treatments samples of SAPO-11. Moreover, NbP has shown characteristic XRD of amorphous materials, with high acidity and were active in the conversion of hexadecane.

Elucidação molecular e micelar dos superagregados de anfotericina B

A Anfotericina B (AmB) é amplamente utilizada no tratamento de infecções fúngicas sistêmicas. No entanto, a sua utilização é limitada devido a sua elevada toxicidade aguda e crônica. Os superagregados de AmB (H-AmB) obtido pelo processo de aquecimento controlado apresentam um potencial reduzido de toxicidade quando comparados à Anfotericina B micelar não aquecida (M-AmB). Diante do exposto, o objetivo deste estudo foi avaliar as características físico-químicas do processo de formação dos superagregados após a liofilização do H-AmB, por meio de técnicas tais como a calorimetria de exploratória diferencial (DSC), termogravimetria (TG) e análise térmica diferencial (DTG), ressonância magnética nuclear (RMN), espalhamento dinâmico de luz (DLS) e difração de raios X (DRX). Os dados de DLS indicaram um tamanho de aproximadamente 260 nm deste novo sistema, sendo este tamanho compatível e viável para administração intravenosa. A análise de DRX demonstrou a formação de um novo estado cristalino do sistema micelar, podendo este estar relacionado a presença de grande proporção de desoxicolato de sódio (NaDC) na formulação. O aquecimento do NaDC resulta na formação de uma estrutura helicoidal intermolecular, promovendo desta forma o aumento da agregação micelar e consequentemente aumento de seu tamanho. Os estudos das análises térmicas demonstraram que o processo de aquecimento não influência no comportamento das amostras. Os dados de RMN da H-AmB demonstraram a presença de ácido desoxicólico além do NaDC. O ácido desoxicólico é formado após o processo de aquecimento e sugere-se que o equilíbrio entre ambas as moléculas seja responsável pela redução da toxicidade da AmB. Os resultados aqui apresentados sugerem que o processo de aquecimento controlado altera a organização estrutural das micelas, resultando na diminuição da toxicidade, na melhoria da estabilidade térmica e na manutenção da atividade.

Elucidação molecular e micelar dos superagregados de anfotericina B

A Anfotericina B (AmB) é amplamente utilizada no tratamento de infecções fúngicas sistêmicas. No entanto, a sua utilização é limitada devido a sua elevada toxicidade aguda e crônica. Os superagregados de AmB (H-AmB) obtido pelo processo de aquecimento controlado apresentam um potencial reduzido de toxicidade quando comparados à Anfotericina B micelar não aquecida (M-AmB). Diante do exposto, o objetivo deste estudo foi avaliar as características físico-químicas do processo de formação dos superagregados após a liofilização do H-AmB, por meio de técnicas tais como a calorimetria de exploratória diferencial (DSC), termogravimetria (TG) e análise térmica diferencial (DTG), ressonância magnética nuclear (RMN), espalhamento dinâmico de luz (DLS) e difração de raios X (DRX). Os dados de DLS indicaram um tamanho de aproximadamente 260 nm deste novo sistema, sendo este tamanho compatível e viável para administração intravenosa. A análise de DRX demonstrou a formação de um novo estado cristalino do sistema micelar, podendo este estar relacionado a presença de grande proporção de desoxicolato de sódio (NaDC) na formulação. O aquecimento do NaDC resulta na formação de uma estrutura helicoidal intermolecular, promovendo desta forma o aumento da agregação micelar e consequentemente aumento de seu tamanho. Os estudos das análises térmicas demonstraram que o processo de aquecimento não influência no comportamento das amostras. Os dados de RMN da H-AmB demonstraram a presença de ácido desoxicólico além do NaDC. O ácido desoxicólico é formado após o processo de aquecimento e sugere-se que o equilíbrio entre ambas as moléculas seja responsável pela redução da toxicidade da AmB. Os resultados aqui apresentados sugerem que o processo de aquecimento controlado altera a organização estrutural das micelas, resultando na diminuição da toxicidade, na melhoria da estabilidade térmica e na manutenção da atividade.

Avaliação do extrato do fungo caripia montagnei e de agonistas de PPAR - α no processo inflamatório

The mushrooms have been object of intense research in view of its potential raising of application in different sectors of the pharmacology and alimentary industry. Among diverse bioactive composites of polyssacharides nature that exist in the fungus the glucans are much searched. These are polymers of glucose and classified as the type of glicosidic linking [α, β]. Peroxisome proliferator-activated receptors (PPARs), ranscription factors belonging to the family of nuclear receptors that bind themselves o specific agonists, have shown their importance in controlling the inflammatory process. The aim of this study was to perform a chemical characterization of extract rom the mushroom Caripia montagnei, assess its antiinflammatory and antibacterial effect and determine if this effect occurs via PPAR. This mushroom is composed of carbohydrates (63.3±4.1%), lipids (21.4l±0.9%) and proteins (2.2± 0.3%). The aqueous solution resulting from the fractionation contained carbohydrates (98.7±3.3%) and protein (1.3±0.25%). Analyses of infrared spectrophotometry and of nuclear magnetic esonance demonstrated that the extract of mushroom C. montagnei is rich in β-glucans. In hioglycolate-induced peritonitis, the C. montagnei glucans (50 mg/kg) educed the inflammatory process in 65.5±5.2% and agonists, pharmacological igands, for PPAR: Wy-14643 (49.3±6.1%), PFOA (48.9±3.8%) and clofibrate in 45.2±3.2%. Sodium diclofenac showed a reduction of 81.65±0.6%. In the plantar edema, the glucans from C. montagnei (50 mg/kg) and L-NAME reduced the edema to a similar degree 91.4±0.3% and 92.8±0,5 %, respectively. In all the groups tested, nitric oxide (NO), an inflammation mediator, showed a significant reduction in the nitrate/nitrite levels when compared to the positive control (P<0.001). The C. montagnei glucans did not show cytotoxicity in the concentrations tested (2.5, 5.0, 10.0, 20.0 and 40.0 µg/100 µL). Antibacterial activity demonstrated that, unlike total extract, there was no inhibition of bacterial growth. The C. montagnei glucans show great potential for antiinflammatory applications. This effect suggests that it is mediated by PPAR activation and by COX and iNOS inhibition

Análises estruturais e atividades biológicas de exopolissacarídeo extraído do fungo comestível pleurotus Sajor-Caju e de seu derivado sulfatado quimicamente.

The exopolysaccharides are extracellular compounds produced by some species of fungi and bacteria. It is suggested that these molecules, even when in the form of complex polysaccharide-peptide, are the main bioactive molecules of many fungus. Some of the biological activities displayed by these compounds can be accentuated and others may arise when you add chemically polar or nonpolar groups to polysaccharides. The fruiting body of Pleurotus sajor-caju produces a heteropolysaccharide with antineoplastic and antimicrobial activity, but other biological activities of this polymer have not been evaluated. In this work the exopolysaccharide of Pleurotus sajor-caju was sulfated chemically and structurally characterized. We also evaluated the antiproliferative, antioxidant and anticoagulant activities from native exopolysaccharide (PN) and its sulfated derivated (PS). Polyacrylamide gel electrophoresis, infrared spectroscopy and nuclear magnetic resonance (¹³C) proved successful in sulfation of PN to obtain PS. Analysis by gas chromatography-mass spectroscopy showed that PN and PS are composed of mannose, galactose, 3-O-methyl-galactose and glucose in proportion percentage of 44,9:16,3:19,8:19 and 49, 7:14,4:17,7:18,2, respectively. The percentage of sulfate found in PS was 22.5%. Antioxidants assays revealed that the sulfation procedure affects differently the activities of exopolysaccharides, while the total antioxidant capacity, the scavenging activity of superoxide radical and ferric chelating were not affected by sulfation, on the other hand the chemical modification of PN enhanced the scavenging activity of hydroxyl radical and reducing power. PS also showed anticoagulant activity in a dose-dependent manner and clotting time was 3.0 times higher than the baseline value in APTT at 2 mg/mL. The exopolysaccharide not presented antiproliferative activity against HeLa tumor cells, but PS affects the cellular proliferation in a time-dependent manner. After 72 h, the inhibition rate of PS (2.0 mg/mL) on HeLa cells was about 60%. The results showed that PN sulfation increase some of their activities.