Quintosana e seus derivados conjugados com ácido gálico: avaliação de seu potencial antioxidante e de interferência na formação de cristais de oxalato de cálcio

Chitin is the second most abundant polysaccharide in nature and its derivative chitosan has been widely studied due to its unique chemical and pharmacological properties. However, studies show that when this molecule is used as food, drug, etc. it tends to accumulate in renal tissue and promotes an increase in calcium excretion. Nevertheless, the effect of chitosan on the formation of calcium oxalate (OxCa) crystals has never been evaluated. The formation of kidney stones (urolithiasis) is the disease that most often affects the kidneys and the urinary system. In addition, this is a disease with high prevalence and recurrence. Many molecules with antioxidant activity have been shown to decrease the potential for in vitro OxCa crystals formation. Thus, the aim of this study was to evaluate the effect of low molecular weight chitosan and its derivatives conjugated to gallic acid (AG) as antioxidant and inhibitor of OxCa crystals formation. The physico-chemical analysis confirmed the identity of chitosan. This molecule was subjected to five antioxidant tests and showed an excellent copper chelating activity. However, chitosan did not show other significant antioxidant activity. When chitosan was subjected to in vitro crystal formation tests, it increased the number of OxCa monohydrate crystals, modified the morphology of the crystals, modified the proportions between populations of crystals in solution and increased the zeta potential of these crystals formed. Four molecules of chitosan conjugated with GA were obtained. The physico-chemical analysis confirmed that chitosan and AG were covalently bonded. However, the amount of GA liked to chitosan did not increase even when 10 times more GA was used in experiment. When these derivatives were subjected to antioxidant tests, all chitosan conjugates showed higher antioxidant potential than their precursors. However, they showed different activity between them, which indicating that the position where AG is conjugated is an important factor for chitosan-GA activity. When conjugated chitosans were submitted to in vitro crystal formation tests, a reduction in the crystals number was observed when compared with those formed in the presence of unconjugated chitosan. Chitosan has a strong capacity for inducing OxCa monohydrate crystal formation, as well as modify their morphology and zeta potential. Over all, the process of conjugating AG to chitosan led to an increase in antioxidant potential of this molecule and was also able to decrease its capacity of inducing in vitro crystal formation

Síntese e caracterização de compostos de coordenação do Ácido 4-cloro-2-(2- furilmetilamino)-5- sulfamoil-benzóico com os íons níquel, cobalto e zinco

This work aimed to promote the synthesis, characterization and propose a plausible molecular structure for coordination compounds involving furosemide (4-Chloro-2-(2- furylmethylamino)-5-sulfamoyl-benzoic acid) with the metal ions Ni+2, Zn+2 and Co+2. The compounds were obtained in methanoic medium by evaporation of the solvent after the synthesis procedure. For characterization of coordination compounds determining the levels of metals by EDTA complexometry, infrared spectroscopy (FTIR), solubility of compounds in various solvents, thermogravimetry (TG), differential scanning calorimetry (DSC), differential thermal analysis were made (DTA), determination of the carbon , hydrogen and nitrogen (CHN). The results of infrared spectroscopy in the region suggest that the organic ligand is coordinated in a bidentate fashion to the metal ions, the metal center interactions to occur by the coordination of the nitrogen atom of the amino group and the oxygen atom of the carboxylic acid of the structure of furosemide. With the results of the levels of metal, elemental analysis (CHN) and thermal analysis has been possible to propose the structure of the ligand. The values of the molar conductivity of the complex in acetonitrile behavior suggest the non acetonitrile electrolyte solution. With the solubility tests it was found that the compounds have high solubility in methanol and acetonitrile, as are partially insoluble in water. From the results of thermal analysis (TG, DSC, DTA), it was possible to obtain the thermal behavior of the compounds as stages of dehydration, thermal stability, decomposition and the energies involved.

Efeito do ácido ascórbico sobre a espermatogênese de camundongos com distrofia muscular de Duchenne

The objective was to evaluate spermatogenesis alterations caused by DMD and the effect of the treatment using ascorbic acid in preventing those injuries. Twenty four mice were used, 12 from the C57BL/10 lineage (non-dystrophic) and 12 from the C57BL/10Mdx (dystrophic). The sample was divided in six groups containing 4 animals each, as: C30 = 30 days control; D30 = Dystrophic with 30 days; C60 = 60 days control; D60 = Distrophic with 60 days; CS60 = 60 days control supplemented with ascorbic acid and DS60 = Dystrophic with 60 days supplemented with ascorbic acid. The ascorbic acid supplementation was given in the water, 0,005 mg/day. After euthanasia, the testicles (right and left) were collected, weighted and cross sectioned. The material was fixed in the Karnovsky solution for 24 hours, included in resin for histological studies (morphological and morphometric analyzes) submitted to ultrastructural analysis and immunohistochemistry for caspase-3. There was a significant increase in the tunica propria percentage in D30 compared to C30 and D60. The ultrastructural analysis showed mitochondrial apoptosis evidence of Sertoli cells that can reduce sperm efficiency in CS60 and DS60. A higher volume density of apoptotic cells postivas to Caspase-3 in C30 and D30 versus DS60 compared to CS60. There was severe hypertrophy of the Leydig cells between D30 and D60. However, with supplementation was observed reversal of this change in DS60. The ultrastructure of Leydig cells to early presence of lipid vesicles was observed in the group pre-pubertal dystrophic (D30). Thus, the DMD affect the organization of the seminiferous tubules and intertubule, however, the ascorbic acid supplementation used for the treatment of DMD has been just enough to reduce the hypertrophy of the Leydig cells.

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.

Nanopartículas catiônicas de poli (ácido lático) para liberação modificada de peptídios da peçonha do escorpião Tityus serrulatus

Reported accidents involving the poisoning scorpions are still frequent in Brazil, mainly caused by Tityus serrulatus, known as yellow scorpion. Although antivenom sera are produced routinely by various government laboratories, the effectiveness of its use depends on how quickly treatment is initiated and efficiency in the production of antibodies by the immunized animals. In this study, the development of cationic polymeric nanoparticles of poly(lactic acid) aimed to create a modified delivery system for peptides and proteins of T. serrulatus venom, able to enhance the production of serum antibodies against the scorpion toxins. The cationic nanoparticles were obtained by a low energy nanoprecipitation, after study of the parameters’ variations effects over the physicochemical properties of the particles. The surface functionalization of the nanoparticles with the hyperbranched polyethyleneimine was proved by zeta potential analysis and enabled the adsorption by electrostatic interaction of different types of proteins. The protein loading efficiency of 40-80 % to bovine serum albumin (BSA) and 100 % to scorpion venom peptides evaluated by spectrophotometry and polyacrylamide gel electrophoresis confirmed the success of the selected parameters established for obtainment of nanoparticles, produced with size between 100 to 250 nm. The atomic force microscopy analysis and in vitro release showed that the spherical nanoparticles provided a sustained release profile of proteins by diffusion mechanism, demonstrating the potential for application of the nanoparticles in vivo.

Nanopartículas catiônicas de poli (ácido lático) para liberação modificada de peptídios da peçonha do escorpião Tityus serrulatus

Reported accidents involving the poisoning scorpions are still frequent in Brazil, mainly caused by Tityus serrulatus, known as yellow scorpion. Although antivenom sera are produced routinely by various government laboratories, the effectiveness of its use depends on how quickly treatment is initiated and efficiency in the production of antibodies by the immunized animals. In this study, the development of cationic polymeric nanoparticles of poly(lactic acid) aimed to create a modified delivery system for peptides and proteins of T. serrulatus venom, able to enhance the production of serum antibodies against the scorpion toxins. The cationic nanoparticles were obtained by a low energy nanoprecipitation, after study of the parameters’ variations effects over the physicochemical properties of the particles. The surface functionalization of the nanoparticles with the hyperbranched polyethyleneimine was proved by zeta potential analysis and enabled the adsorption by electrostatic interaction of different types of proteins. The protein loading efficiency of 40-80 % to bovine serum albumin (BSA) and 100 % to scorpion venom peptides evaluated by spectrophotometry and polyacrylamide gel electrophoresis confirmed the success of the selected parameters established for obtainment of nanoparticles, produced with size between 100 to 250 nm. The atomic force microscopy analysis and in vitro release showed that the spherical nanoparticles provided a sustained release profile of proteins by diffusion mechanism, demonstrating the potential for application of the nanoparticles in vivo.

Efeito anti-inflamatório e antioxidante do extrato hidroalcóolico de Turnera subulata na colite ulcerativa induzida por ácido acético em ratos

Inflammatory bowel diseases is composed by a set of chronic and inflammatory disorders, among them is ulcerative colitis (UC). UC treatment is based on anti-inflammatory administration; however, this group of drugs clearly leads to development of undesirable side effects, what stimulate the search for new therapies alternatives. The aim of this study was to evaluate the effect of hydroalcholic Turnera subulata extract on acetic acid-induced acute UC in rats. UC was induced by 1 mL injection of 4% acetic acid via rectal in Wistar mouse. 42 animals were distributed among 6 experimental groups: Control, UC, Sulfasalazine 500 mg/Kg/day (SSZ), T. subulata 50mg/Kg/day (TS 50), T. subulata 100mg/Kg/day (TS 100), T. subulata 200mg/Kg/day (TS 200). Throughout the experiment, body weight, food and water ingestion was daily evaluated. At the end of the experiment, the animals were euthanized and a colon fragment was observed by macroscopic analysis. Colon fragments were also collected for microscopic analysis and oxidative stress evaluation. The means from each group was compared by ANOVA test with a significance level of 5% (p<0.05) using GraphPad Prism Software. As results, we can clearly observe that SSZ group had the greater body weight decrease among the groups throughout the experiments, 14.78%, as well as, the lowest food intake, 6.23 g of food/day. The animals treated with T. subulata extracts showed no important body weight loss when compared to control. UC group showed the highest tissue damage macroscope score, 6.5, while TS 50 showed the lowest tissue damage score: 1. Microscope evaluation showed the presence of edema, haemorraghia and ulceration in all group of animals, except for Control. Nevertheless, TS 50 showed the lowest inflammatory damage among all groups. Oxidative stress analysis revealed that T. subulata treatment modulate catalase and superoxide dismutase activity, we also observed a decrease in protein and lipid peroxidation in response to extract administration. Taken together, these results shows that T. subulata extract exerts anti-inflammatory and anti-oxidant effects on experimental UC.

Efeito anti-inflamatório e antioxidante do extrato hidroalcóolico de Turnera subulata na colite ulcerativa induzida por ácido acético em ratos

Inflammatory bowel diseases is composed by a set of chronic and inflammatory disorders, among them is ulcerative colitis (UC). UC treatment is based on anti-inflammatory administration; however, this group of drugs clearly leads to development of undesirable side effects, what stimulate the search for new therapies alternatives. The aim of this study was to evaluate the effect of hydroalcholic Turnera subulata extract on acetic acid-induced acute UC in rats. UC was induced by 1 mL injection of 4% acetic acid via rectal in Wistar mouse. 42 animals were distributed among 6 experimental groups: Control, UC, Sulfasalazine 500 mg/Kg/day (SSZ), T. subulata 50mg/Kg/day (TS 50), T. subulata 100mg/Kg/day (TS 100), T. subulata 200mg/Kg/day (TS 200). Throughout the experiment, body weight, food and water ingestion was daily evaluated. At the end of the experiment, the animals were euthanized and a colon fragment was observed by macroscopic analysis. Colon fragments were also collected for microscopic analysis and oxidative stress evaluation. The means from each group was compared by ANOVA test with a significance level of 5% (p<0.05) using GraphPad Prism Software. As results, we can clearly observe that SSZ group had the greater body weight decrease among the groups throughout the experiments, 14.78%, as well as, the lowest food intake, 6.23 g of food/day. The animals treated with T. subulata extracts showed no important body weight loss when compared to control. UC group showed the highest tissue damage macroscope score, 6.5, while TS 50 showed the lowest tissue damage score: 1. Microscope evaluation showed the presence of edema, haemorraghia and ulceration in all group of animals, except for Control. Nevertheless, TS 50 showed the lowest inflammatory damage among all groups. Oxidative stress analysis revealed that T. subulata treatment modulate catalase and superoxide dismutase activity, we also observed a decrease in protein and lipid peroxidation in response to extract administration. Taken together, these results shows that T. subulata extract exerts anti-inflammatory and anti-oxidant effects on experimental UC.

Avaliação da influência de surfactantes químico e biológico na hidrólise enzimática de casca de coco verde após pré-tratamento ácido/alcalino e com peróxido de hidrogênio alcalino

In Brazil many types of bioproducts and agroindustrial waste are generated currently, such as cacashew apple bagasse and coconut husk, for example. The final disposal of these wastes causes serious environmental issues. In this sense, waste lignocellulosic content, as the shell of the coconut is a renewable and abundant raw material in which its use has an increased interest mainly for the 2nd generation ethanol production. The hydrolysis of cellulose to reducing sugars such as glucose and xylose is catalysed by a group of enzymes called cellulases. However, the main bottleneck in the enzymatic hydrolysis of cellulose is the significant deactivation of the enzyme that shows irreversible adsorption mechanism leading to reduction of the cellulose adsorption onto cellulose. Studies have shown that the use of surfactants can modify the surface property of the cellulose therefore minimizing the irreversible binding. The main objective of the present study was to evaluate the influence of chemical and biological surfactants during the hydrolysis of coconut husk which was subjected to two pre-treatment in order to improve the accessibility of the enzymes to the cellulose, removing this way, part of the lignin and hemicellulose present in the structure of the material. The pre-treatments applied to coconut bagasse were: Acid/Alkaline using 0.6M H2SO4 followed by 1M NaOH, and the one with Alkaline Hydrogen Peroxide at a concentration of 7.35% (v/v) and pH 11.5. Both the material no treatment and pretreated were characterized using analysis of diffraction X-ray (XRD), Scanning Electron Microscopy (SEM) and methods established by NREL. The influence of both surfactants, chemical and biological, was used at concentrations below the critical micelle concentration (CMC), and the concentrations equal to the CMC. The application of pre-treatment with coconut residue was efficient for the conversion to glucose, as well as for the production of total reducing sugars, it was possible to observe that the pretreatment fragmented the structure as well as disordered the fibers. Regarding XRD analysis, a significant increase in crystallinity index was observed for pretreated bagasse acid/alkali (51.1%) compared to the no treatment (31.7%), while that for that treated with PHA, the crystallinity index was slightly lower, around 29%. In terms of total reducing sugars it was not possible to observe a significant difference between the hydrolysis carried out without the use of surfactant compared to the addition of Triton and rhamnolipid. However, by observing the conversions achieved during the hydrolysis, it was noted that the best conversion was using the rhamnolipíd for the husk pretreated with acid/alkali, reaching a value of 33%, whereas using Triton the higher conversion was 23.8%. The coconut husk is a residue which can present a high potential to the 2nd generation ethanol production, being the rhamonolipid a very efficient biosurfactant for use as an adjuvant in the enzymatic process in order to act on the material structure reducing its recalcitrance and therefore improving the conditions of access for enzymes to the substrate increasing thus the conversion of cellulose to glucose.

Avaliação da influência de surfactantes químico e biológico na hidrólise enzimática de casca de coco verde após pré-tratamento ácido/alcalino e com peróxido de hidrogênio alcalino

In Brazil many types of bioproducts and agroindustrial waste are generated currently, such as cacashew apple bagasse and coconut husk, for example. The final disposal of these wastes causes serious environmental issues. In this sense, waste lignocellulosic content, as the shell of the coconut is a renewable and abundant raw material in which its use has an increased interest mainly for the 2nd generation ethanol production. The hydrolysis of cellulose to reducing sugars such as glucose and xylose is catalysed by a group of enzymes called cellulases. However, the main bottleneck in the enzymatic hydrolysis of cellulose is the significant deactivation of the enzyme that shows irreversible adsorption mechanism leading to reduction of the cellulose adsorption onto cellulose. Studies have shown that the use of surfactants can modify the surface property of the cellulose therefore minimizing the irreversible binding. The main objective of the present study was to evaluate the influence of chemical and biological surfactants during the hydrolysis of coconut husk which was subjected to two pre-treatment in order to improve the accessibility of the enzymes to the cellulose, removing this way, part of the lignin and hemicellulose present in the structure of the material. The pre-treatments applied to coconut bagasse were: Acid/Alkaline using 0.6M H2SO4 followed by 1M NaOH, and the one with Alkaline Hydrogen Peroxide at a concentration of 7.35% (v/v) and pH 11.5. Both the material no treatment and pretreated were characterized using analysis of diffraction X-ray (XRD), Scanning Electron Microscopy (SEM) and methods established by NREL. The influence of both surfactants, chemical and biological, was used at concentrations below the critical micelle concentration (CMC), and the concentrations equal to the CMC. The application of pre-treatment with coconut residue was efficient for the conversion to glucose, as well as for the production of total reducing sugars, it was possible to observe that the pretreatment fragmented the structure as well as disordered the fibers. Regarding XRD analysis, a significant increase in crystallinity index was observed for pretreated bagasse acid/alkali (51.1%) compared to the no treatment (31.7%), while that for that treated with PHA, the crystallinity index was slightly lower, around 29%. In terms of total reducing sugars it was not possible to observe a significant difference between the hydrolysis carried out without the use of surfactant compared to the addition of Triton and rhamnolipid. However, by observing the conversions achieved during the hydrolysis, it was noted that the best conversion was using the rhamnolipíd for the husk pretreated with acid/alkali, reaching a value of 33%, whereas using Triton the higher conversion was 23.8%. The coconut husk is a residue which can present a high potential to the 2nd generation ethanol production, being the rhamonolipid a very efficient biosurfactant for use as an adjuvant in the enzymatic process in order to act on the material structure reducing its recalcitrance and therefore improving the conditions of access for enzymes to the substrate increasing thus the conversion of cellulose to glucose.

Estudos de Durabilidade Frente ao Ataque Ácido de Compósitos Portland-Polímero para Cimentação de Poços de Petróleo

Portland-polymers composites are promising candidates to be used as cementing material in Northeastern oil wells of Brazil containing heavy oils submitted to steam injection. In this way, it is necessary to evaluate its degradation in the commonly acidizind agents. In addition, to identify how aggressive are the different hostile environments it is an important contribution on the decision of the acidic systems to be used in. It was investigated the performance of the Portland-polymer composites using powdered polyurethane, aqueous polyurethane, rubber tire residues and a biopolymer, those were reinforced with polished carbon steel SAE 1045 to make the electrochemical measurements. HCl 15,0 %, HCl 6,0 % + HF 1,5 % (soft mud acid), HCl 12,0 % + HF 3,0 % (regular mud acid) and HAc 10 % + HF 1,5 % were used as degrading environment and electrolytes. The more aggressive acid solution to the plain Portland hardened cement paste was the regular mud acid, that showed loss of weight around 23.0 %, followed by the soft mud acid, the showed 11.0 %, 15.0 % HCl with 7,0 % and, at last the 10.0 % HAc plus HF 1.5 % with just 1.0 %. The powdered polyurethane-composite and the aqueous polyurethane one showed larger durability, with reduction around 87.0 % on the loss of weight in regular mud acid. The acid attack is superficial and it occurs as an action layer, where the degraded layer is responsible for the decrease on the kinetic of the degrading process. This behavior can be seen mainly on the Portland- aqueous polyurethane composite, because the degraded layer is impregnated with chemically modified polymer. The fact of the acid attack does not have influence on the compressive strength or fratography of the samples, in a general way, confirms that theory. The mechanism of the efficiency of the Portland-polymers composites subjected to acid attack is due to decreased porosity and permeability related with the plain Portland paste, minor quantity of Ca+2, element preferentially leached to the acidic solution, wave effect and to substitute part of the degrading bulk for the polymeric one. The electrolyte HAc 10 % + HF 1,5 % was the least aggressive one to the external corrosion of the casing, showing open circuit potentials around +250 mV compared to -130 mV to the simulated pore solution to the first 24 hours immersion. This behavior has been performed for two months at least. Similar corrosion rates were showed between both of the electrolytes, around 0.01 μA.cm-2. Total impedance values, insipient arcs and big polarization resistance capacitive arcs on the Nyquist plots, indicating passivity process, confirm its efficiency. In this way, Portlandpolymers composites are possible solutions to be succeed applied to oilwell cementing concomitant submitted to steam injection and acidizing operation and the HAc 10,0 % + HF 1,5 % is the less aggressive solution to the external corrosion of the casing