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.

Atividades Biológicas De Xilana De Sabugo De Milho

The corn cob is an agricultural by-product still little used, this in part due to the low knowledge of the biotechnological potential of their molecules. Xylan from corn cobs (XSM) is a polysaccharide present in greater quantity in the structure of plant and its biotechnology potential is little known. This study aimed to the extraction, chemical characterization and evaluation of biological activities of xylan from corn cobs. To this end, corncobs were cleaned, cut, dried and crushed, resulting in flour. This was subjected to a methodology that combines the use of alkaline conditions with waves of ultrasound. After methanol precipitation, centrifugation and drying was obtained a yield of 40% (g/g flour). Chemical analysis indicated a high percentage of polysaccharides in the sample (60%) and low contamination by protein (0.4%) and phenolic compounds (> 0.01%). Analysis of monosaccharide composition indicated the presence of xylose:glucose:arabinose:galactose:mannose:glucuronic acid in a molar ratio 50:20:15:10:2.5:2.5. The presence of xylan in the sample was confirmed by nuclear magnetic resonance (¹H and ¹³C) and infrared spectroscopy (IR). Tests were conducted to evaluate the antioxidant potential of XSM. This showed a total antioxidant capacity of 48.45 EAA/g sample. However, did not show scavenging activity of superoxide and hydroxyl radical and also reducing power. But, showing a high capacity chelating iron ions with 70% with about 2 mg/mL. The ability to XSM to influence cell proliferation in culture was also evaluated. This polymer did not influence the proliferation of normal fibroblast cells (3T3), however, decreased the rate of proliferation of tumor cells (HeLa) in a dose-dependent, reaching an inhibition of about 50% with a concentration around 2 mg/mL. Analyzing proteins related to cell death, by immunoblotting, XSM increases the amount of Bax, Bcl-2 decrease, increase cytochrome c and AIF, and reduce pro-caspase-3, indicating the induction of cell death induced apoptosis dependent and independent of caspase. XSM did not show anticoagulant activity in the PT test. However, the test of activated partial thromboplastin time (aPTT), XSM increased clotting time at about 5 times with 600 μg of sample compared with the negative control. The presence of sulfate on the XSM was discarded by agarose gel electrophoresis and IR. After carboxyl-reduction of XSM the anticoagulant activity decreased dramatically. The data of this study demonstrate that XSM has potential as antioxidant, antiproliferative and anticoagulant compound. Future studies to characterize these activities of XSM will help to increase knowledge about this molecule extracted from corn and allow their use in functional foods, pharmaceuticals and chemical industries.

Efeito de glucanas do fungo Caripia montagnei em modelo de inflamação intestinal induzida por tnbs em ratos Wistar e em células de carcinoma de cólon humano HT-29

Compounds derived from fungi has been the subject of many studies in order to broaden the knowledge of their bioactive potential. Polysaccharides from Caripia montagnei have been described to possess anti-inflammatory and antioxidant properties. In this study, glucans extracted from Caripia montagnei mushroom were chemically characterized and their effects evaluated at different doses and intervals of treatment. It was also described their action on colonic injury in the model of colitis induced by 2,4,6-trinitrobenzene sulfonic acid (TNBS), and its action on cells of the human colon carcinoma (HT-29). Compounds extracted of C. montagnei contain high level of carbohydrates (96%), low content of phenolic compounds (1.5%) and low contamination with proteins (2.5%). The (FT-IR) and (NMR) analysis showed that polysaccharides from this species of mushroom are composed of α- and β-glucans. The colonic damage was evaluated by macroscopic, histological, biochemical and immunologic analyses. The results showed a reduction of colonic lesions in all groups treated with the glucans of Caripia montagnei (GCM). GCM significantly reduced the levels of IL-6 (50 and 75 mg/kg, p < 0.05), a major inflammatory cytokine. Biochemical analyses showed that such glucans acted on reducing levels of alkaline phosphatase (75 mg/kg, p < 0.01), nitric oxide (p < 0.001), and myeloperoxidase (p < 0.001). These results were confirmed microscopically by the reduction of cellular infiltration. The increase of catalase activity suggest a protective effect of GCM on colonic tissue, confirming their anti-inflammatory potential. GCM displayed cytostatic activity against HT-29 cells, causing accumulation of cells in G1 phase, blocking the cycle cell progression. Those glucans also showed ability to modulate the adhesion of HT-29 cells to Matrigel® and reduced the oxidative stress. The antiproliferative activity against HT-29 cells displayed by GCM (p <0.001) can be attributed to its cytostatic activity and induction of apoptosis by GCM

Síntese e caracterização do líquido iônico tetrafluoroborato de 1-metil-3-(2,6-(S)-dimetiloct-2-eno)-imidazol como eletrólito para produção de hidrogênio via eletrólise da água

Ionic liquids (ILs) are organic compounds liquid at room temperature, good electrical conductors, with the potential to form as a means for electrolyte on electrolysis of water, in which the electrodes would not be subjected to such extreme conditions demanding chemistry [1]. This paper describes the synthesis, characterization and study of the feasibility of ionic liquid ionic liquid 1-methyl-3(2,6-(S)-dimethyloct-2-ene)-imidazole tetrafluoroborate (MDI-BF4) as electrolyte to produce hydrogen through electrolysis of water. The MDI-BF4 synthesized was characterized by thermal methods of analysis (Thermogravimetric Analysis - TG and Differential Scanning Calorimetry - DSC), mid-infrared spectroscopy with Fourier transform by method of attenuated total reflectance (FTIR-ATR), nuclear magnetic resonance spectroscopy of hydrogen (NMR 1H) and cyclic voltammetry (CV). Where thermal methods were used to calculate the yield of the synthesis of MDI-BF4 which was 88.84%, characterized infrared spectroscopy functional groups of the compound and the binding B-F 1053 cm-1; the NMR 1H analyzed and compared with literature data defines the structure of MDI-BF4 and the current density achieved by MDI-BF4 in the voltammogram shows that the LI can conduct electrical current indicating that the MDI-BF4 is a good electrolyte, and that their behavior does not change with the increasing concentration of water

Analise estrutural do galactano acidico dos ovos de pomacea lineata e avaliacao de suas atividades proliferativa e antiinflamatoria

The acidic galactan (AG) was obtained by extraction and proteolysis by acetone precipitation of the eggs of the mollusc Pomacea lineata. Its structure was elucidated by a combination of chemical analysis, the intrinsic viscosity and NMR spectroscopy 1D and 2D. Biological aspects of AG were evaluated by in vivo testing of healing and peritonitis induced (anti-inflammatory activity) and in vitro assays of cytotoxicity (MTT). This polymer showed a simple structure without the presence of sulfate and uronic acids in its structure. Its intrinsic viscosity and relative were evaluated at 0.44 ± 0.05 and 1.744± 0.07 dl.g-1. Spectroscopy showed that the AG has a constitution composed predominantly of β-D-galactosis, and β-D-glucosamine-NAcetil that comes in a smaller proportion in chain. The character of this acidic polysaccharide is given by the presence of pyruvate in the molecule, forming a cyclic acetal of six states, located in β-D-galactosis. The involvement of AG in the healing process was evaluated and the histological analysis revealed that there was so early in the process of healing, a great stimulation of macrophages with granuloma formation. Suggesting that AG may have promoted the advance of biological events required for tissue healing. In the trial of the GA-induced peritonitis showed dose dependent, demonstrating the anti-inflammatory effect at concentrations above 20 mg/kg, and confirming its inflammatory character and the concentration of 1mg/kg. In vitro tests used in the GA concentration of 1000 μg/mL showed proliferative activity by stimulating the growth of 3T3 cells, corroborating the findings in vivo and demonstrating the absence of cytotoxic activity

Preparação e carcterização de complexos multicomponentes contendo ciclodextrinas e benznidazol

The benznidazole (BNZ) is the only alternative for Chagas disease treatment in Brazil. This drug has low solubility, which restricts its dissolution rate. Thus, the present work aimed to study the BNZ interactions in binary systems with beta cyclodextrin (β-CD) and hydroxypropyl-beta cyclodextrin (HP-β-CD), in order to increase the apparent aqueous solubility of drug. The influence of seven hydrophilic polymers, triethanolamine (TEA) and 1-methyl-2- pyrrolidone (NMP) in benznidazole apparent aqueous solubility, as well as the formation of inclusion complexes was also investigated. The interactions in solution were predicted and investigated using phase solubility diagram methodology, nuclear magnetic resonance of protons (RMN) and molecular modeling. Complexes were obtained in solid phase by spray drying and physicochemical characterization included the UV-Vis spectrophotometric spectroscopy in the infrared region, scanning electron microscopy, X-ray diffraction and dissolution drug test from the different systems. The increment on apparent aqueous solubility of drug was achieved with a linear type (AL) in presence of both cyclodextrins at different pH values. The hydrophilic polymers and 1-methyl-2-pyrrolidone contributes to the formation of inclusion complexes, while the triethanolamine decreased the complex stability constant (Kc). The log-linear model applied for solubility diagrams revealed that both triethanolamine and 1-methyl-2-pyrrolidone showed an action cosolvent (both solvents) and complexing (1-methyl-2-pyrrolidone). The best results were obtained with complexes involving 1-methyl-2-pyrrolidone and hydroxypropylbeta- cyclodextrin, with an increased of benznidazole solubility in 27.9 and 9.4 times, respectively. The complexes effectiveness was proven by dissolution tests, in which the ternary complexes and physical mixtures involving 1-methyl- 2-pyrrolidone and both cyclodextrins investigated showed better results, showing the potential use as novel pharmaceutical ingredient, that leads to increased benznidazole bioavailability

Avaliação do comportamento termoanalítico e oxidativo do biodiesel de mamona

In this work biodiesel was gotten through the transesterification reaction using the oil of castor as source of triglycerides and using the methylic route for obtaining of esters. For the characterization of biodiesel and its mixtures with mineral diesel oil, physical chemical parameters and several analytical techniques had been used, as well as: gas chromatography (GC), nuclear magnetic resonance of proton (1H NMR), infrared spectroscopy (IR) and thermal analysis. The chromatography confirmed the complete reaction of esters in biodiesel presenting a 97,08% conversion. The 1H - NMR presented singlet in 3,6 ppm corresponding to the hydrogen of the group ester RCOO CH3. The infrared presented a strong band in 1741 cm-1 referring to stretching C=O of ester and an average band in 1175 cm-1 referring C O deformation. With the data of thermal analysis it was possible to observe the thermal and oxidative stability of the samples changing the atmospheres of synthetic air and nitrogen, where stages of the thermal decomposition had been verified and had been attributed to the volatilization and/or decomposition of the triacylglycerides. The thermal degradation of the samples was carried through 150 and 210°C during 1, 12, 24 and 48 hours and was observed change in the thermogravimetric profile, therefore an increase in the number of stages of the thermal decomposition also occurred indicating characteristic intermediate composites of polymerization, being this confirmed through the rheological study that presented brusque increase of viscosity. The kinetic study showed that the activation energy has the following order: biodiesel > mineral diesel oil > mixtures biodiesel/diesel

Alquilação redutiva da quitosana a partir do glutaraldeído e 3-amino-1-pr

Chitosan derivatives were prepared by reductive alkylation using glutaraldehyde and 3-amino-1-propanol. The reducing agent used was the sodium borohydride. Tests of solubility, stability and viscosity were performed in order to evaluate these parameters effects in the reaction conditions (molar ratio of the reactants and presence of nitrogen in the reaction system). The molecular structure of commercial chitosan was determined by infrared (IR) and hydrogen nuclear magnetic resonance spectroscopy (1H NMR). The intrinsic viscosity and average molecular weight of the chitosan were determined by viscosimetry in 0.3 M acetic acid aqueous solution 0.2 M sodium acetate at 25 ºC. The derivatives of chitosan soluble in aqueous acidic medium were characterized by 1H NMR. The rheological behavior of the chitosan and of the derivative of chitosan (sample QV), which presented the largest viscosity, were studied as a function of polymer concentration, temperature and ionic strength of the medium. The results of characterization of the commercial chitosan (the degree of deacetylation obtained equal 78.45 %) used in this work confirmed a sample of low molar weight (Mv = 3.57 x 104 g/mol) and low viscosity (intrinsic viscosity = 213.56 mL/g). The chemical modification of the chitosan resulted in derivatives with thickening action. The spectra of 1H NMR of the soluble derivatives in acid aqueous medium suggested the presence of hydrophobic groups grafted into chitosan in function of the chemical modification. The solubility of the derivatives of chitosan in 0.25 M acetic acid aqueous solution decreased with increase of the molar ratio of the glutaraldehyde and 3-amino-1-propanol in relation to the chitosan. The presence of nitrogen and larger amount of reducing agent in reaction system contributed to the increase of the solubility, the stability and the viscosity of the systems. The viscosity of the polymeric suspensions in function of the shear rate increased significantly with polymer concentration, suggesting the formation of strong intermolecular associations. The chitosan presented pseudoplastic behavior with the increase in polymer concentration at a low shear rate. The derivative QV presented pseudoplastic behavior at all concentrations used and in a large range of shear rate. The viscosity of chitosan in solution decreased with an increase of the temperature and with the presence of salt. However, there was an increase of the viscosity of the chitosan solution at higher temperature (65 ºC) and ionic strength of the medium which were promoted by hydrophobic associating of the acetamide groups. The solutions of the chitosan derivatives (sample QV) were significantly more viscous than chitosan solution and showed higher thermal stability in the presence of salt as a function of the hydrophobic groups grafted into chitosan backbone

Preparação de resinas de poliuretana à base de óleo de mamona e dietanolamina

The aim of this work was the preparation of polyols from reactions between castor oil and dietanolamine to increase the hydroxyl content and the network degree in the products to application in electronic devices. The polyols and the mixtures obtained were characterized by nuclear magnetic ressonance. Castor oil (CO) is a natural triglyceride - based polyol possessing hydroxyl groups, which allow several reactions that produce many different products. Among them are the polyurethanes (PU), which have been considered an ideal product for the covering of electricelectronic circuits, due to their excellent electrical, shock-absorbing, solvents resistance and hydrolytic stability properties. About 90% of the fatty acids present in the castor oil are ricinoleic acid (12-hydroxyoleic acid), while the remaining 10% correspond to non-hydroxylated fatty acids, mainly linoleic and oleic acids. The chemical analysis of castor oil indicates a hydroxyl number of 2.7. In this work, a polyol was obtained by the reaction of the CO with diethanolamine (DEA), in order to elevate the hydroxyl value from 160 to 230 or to 280 mgKOH/g, and characterized by nuclear magnetic resonance (NMR) 1H and 13C (Mercury 200). The polyadition of the resulting polyol with isophorone diisocianate (IPDI) was carried out at 60°C, and the reaction kinetics was followed by rheological measurements in a Haake RS150 rheometer. The electrical properties were determined in a HP LCR Meter 4262A, at 1.0 Hz and 10.0 KHz. The chemical analysis showed that the polyols obtained presented hydroxyl number from 230 to 280 mgKOH/g. The polyadition reaction with IPDI produced polyurethane resins with the following properties: hardness in the range from 45 shore A to 65 shore D (ASTM D2240); a dielectric constant of 3.0, at 25°C (ASTM D150). Those results indicate that the obtained resins present compatible properties to the similar products of fossil origin, which are used nowadays for covering electric-electronic circuits. Therefore, the PUs from castor oil can be considered as alternative materials of renewable source, free from the highly harmful petroleum - derived solvents

Hidrólise e caracterização de poliacrilamida hidrofobicamente modificada: avaliação da aplicabilidade na recuperação de petróleo

The hydrolysis reaction in alkaline conditions of the commercial polymer poly(acrylamide-co-metacrylate of 3,5,5-trimethyl-hexane) called HAPAM, containing 0.75 % of hydrophobic groups, was carried out in 0.1 M NaCl and 0.25M NaOH solutions, varying the temperature and reaction time. The polymers were characterized by 1H and 13C Nuclear Magnetic Resonance (NMR), Elemental Analysis and Size Exclusion Chromatography (SEC). The values of the hydrolysis degree were obtained by 13C NMR. The viscosity of HAPAM and HAPAM-10N-R solutions was evaluated as a function of shear rate, ionic strength and temperature. At high polymer concentration (Cp), the viscosity of HAPAM solutions increased with the ionic strength and decreased with the temperature. The viscosity of HAPAM-10N-R solutions increased significantly in distilled water, due to repulsions between the carboxylate groups. At high Cp, with the increase of ionic strength and temperature, occurred a decrease of viscosity, due to mainly the high hydrolysis degree and the low amount of hydrophobic groups. These results indicated that the studied polymers have properties more suitable for the application in Enhanced Oil Recovery (EOR) in low salinity and moderate temperature reservoirs

Síntese e caracterização de poliacrilamidas modificadas para utilização na indústria do petróleo

Modified polyacrylamides with ≅ 0.2 mol % of N,N-dihexylacrylamide and hydrolysis degree from 0 to 25 % were synthesized by micellar copolymerization. The hydrophobic monomer was obtained by the reaction between acryloyl chloride and N,Ndihexylamine and characterized by infrared (IR) and proton nuclear magnetic resonance (1H NMR) spectroscopy. The polymer molecular structures were determined through 1H and 13C NMR spectroscopy and the polymers were studied in dilute and semi-dilute regimes by viscometry, rheometry, static light scattering and photon correlation spectroscopy, at the temperature range from 25 to 55 ºC. The data obtained by viscometry showed that the intrinsic viscosity from the hydrolyzed polymers is larger than the precursor polymers at the same ionic strength. The comparison between the charged polymers showed that the polymer with higher hydrolysis degree has a more compact structure in formation water (AFS). The increase of temperature led to an enhanced reduced viscosity to the polymers in Milli-Q water (AMQ), although, in brine, only the unhydrolyzed polymer had an increase in the reduced viscosity with the temperature, and the hydrolyzed derivatives had a decrease in the reduced viscosity. The static light scattering (SLS) analyses in salt solutions evidenced a decrease of weight-average molecular weight (⎯Mw) with the increase of the hydrolysis degree, due to the reduction of the thermodynamic interactions between polymer and solvent, which was evidenced by the decrease of the second virial coefficient (A2). The polymers showed more than one relaxation mode in solution, when analyzed by photon correlation spectroscopy, and these modes were attributed to isolated coils and aggregates of several sizes. The aggregation behavior depended strongly on the ionic strength, and also on the temperature, although in a lower extension. The polymers showed large aggregates in all studied conditions, however, their solutions did not displayed a good increase in water viscosity to be used in enhanced oil recovery (EOR) processes

Bioprospecção química da esponja callyspongia vaginalis (Callyspongiidae)

Recently, marine organisms have attracted attention because of the complexity and potent biological activity from your secondary metabolites. Our planet has 80% it surface covered by oceans and seas, therefore, housing a wide number of different forms of life, among them, the sponges. These sessile and filtrating animals, according to numerous researches, come showing like true chemistry factories. The substances from these animals, sometimes show as news targets to therapeutics agents, and some countries has already use them for treatment of some diseases. Further of the secondary metabolites, the polysaccharides of marine origin also have been target of studies, because the presence of the sulfates groups in its molecules. Polysaccharides with differents biological activities have been related in a large number of researches. Actually, many studies show the sponges as source of promising medicine. These studies inspire new researches, because the few number of sponges species studied until now. Because of that, the present work shows the chemistry prospection of the sponge Callyspongia vaginalis. Chromatographic methods in silica gel allowed the isolations of two secondary metabolites: the known β- sitosterol and a ceramide, no reported in the genus Callyspongia, previously. The analysis of the their lipid extracts show different kinds of fatty acids with a variety of chain length (saponifiable fraction), and others metabolites like Lupenone and stigmasterol, also unprecedented in the genus. The Polysaccharide characterization and the elucidation of the secondary metabolites acquired through of chromatography analysis (CC, molecular exclusion) and spectrometric (NMR 1H and 13C, mass, IR), respectively and comparison with literature data

Síntese, caracterização e estudo fotofísico de complexos de 4,4- diaminoestilbeno-2,2-dissulfonato com íons lantanídeos

This is a work involving fundamental studies of chemistry where the synthesis and structural characterization, as well as a possible future application of these new compounds as luminescent sensors or sunscreen agents, complexes with 4,4 diaminostilbene-2,2-disulfonic (DSD) and trivalent lanthanide ions La3+, Nd3+, Eu3+, Gd3+ and Yb3+, were synthesized in the ratio of 3 mmol: 1 mmol (DSD: lanthanides). The complexes obtained with these ions were present in powder form and were characterized by complexometric titration with EDTA CHN Elemental analysis, molecular absorption spectroscopy in the ultraviolet region, the absorption spectroscopy in the infrared, thermal analysis (TG / DTG), Nuclear Magnetic Resonance - NMR 1H and Luminescence Spectroscopy. The complexometric titration and CHN analysis, confirmed the TG / DTG which suggest that these complexes have the following general chemical formulas: [La2(C14H12S2O6N2)2(H2O)2Cl2].7H2O,[Nd2(C14H12S2O6N2)2(H2O)2Cl2].6H2O,[Eu2(C14 H12S2O6N2)2(H2O)2Cl2].7H2O,[Gd2(C14H12S2O6N2)2(H2O)2Cl2].4H2O e [Yb2(C14H12S2O6N2)2(H2O)2].6H2O. The disappearance of the bands in the infrared spectrum at 2921 cm-1 and 2623 cm-1 and the displacement of the bands in the spectra of the amine complex indicate that the lanthanide ion is coordinated to the oxygen atoms and the sulfonate groups of the nitrogens amines, suggesting the formation of the dimer. The disappearance of the signal and the displacement signal SO3H amines in the 1H NMR spectrum of this complex are also indicative coordination and dimer formation. The Thermogravimetry indicates that the DSD is thermally stable in the range of 40º to 385°C and their complexes with lanthanide ions exhibit weight loss between 4 and 5 stages. The Uv-visible spectra indicated that the DSD and complexes exhibit cis isomers. The analysis of luminescence indicates that the complexes do not exhibit emission in the region of the lanthanides but an intense emission part of the binder. This is related to the triplet states of the ligand, which are in the lowest energy state emitting lanthanide ions, and also the formation of the dimer that suppress the luminescence of ion Eu3+. The formation of dimer was also confirmed by calculating the europium complex structure using the model Hamiltonian PM6 and Sparkle

Obtenção de polímeros graftizados de quitosana e estudo das propriedades físico-químicas para aplicação na indústria do petróleo

Chitosan is a biopolymer derived from the shells of crustaceans, biodegradable, inexpensive and renewable with important physical and chemical properties. Moreover, the different modifications possible in its chemical structure generate new properties, making it an attractive polysaccharide owing to its range of potential applications. Polymers have been used in oil production operations. However, growing concern over environmental constraints has prompted oil industry to search for environmentally sustainable materials. As such, this study sought to obtain chitosan derivatives grafted with hydrophilic (poly(ethylene glycol), mPEG) and/or hydrophobic groups (n-dodecyl) via a simple (one-pot) method and evaluate their physicochemical properties as a function of varying pH using rheology, small-angle Xray scattering (SAXS), dynamic light scattering (DLS) and zeta potential. The chitosan derivatives were prepared using reductive alkylation under mild reaction conditions and the chemical structure of the polymers was characterized by nuclear magnetic resonance (1H NMR) and CHN elemental analysis. Considering a constant mPEG/Chitosan molar ratio on modification of chitosan, the solubility of the polymer across a wide pH range (acidic, neutral and basic) could only be improved when some of the amino groups were submitted to reacetylation using the one-pot method. Under these conditions, solubility is maintained even with the simultaneous insertion of n-dodecyl. On the other hand, the solubility of derivatives obtained only through mPEG incorporation using the traditional methodology, or with the ndodecyl group, was similar to that of its precursor. The hydrophilic group promoted decreased viscosity of the polymer solutions at 10 g/L in acid medium. However, at basic pH, both viscosity and thermal stability increased, as well as exhibited a pronounced pseudoplastic behavior, suggesting strong intermolecular associations in the alkaline medium. The SAXS results showed a polyelectrolyte behavior with the decrease in pH for the polymer systems. DLS analyses revealed that although the dilute polymer solutions at 1 g/L and pH 3 exhibited a high density of protonated amino groups along the polymer chain, the high degree of charge contributed significantly to aggregation, promoting increased particle size with the decrease in pH. Furthermore, the hydrophobic group also contributed to increasing the size of aggregates in solution at pH 3, whereas the hydrophilic group helped reduce their size across the entire pH range. Nevertheless, the nature of aggregation was dependent on the pH of the medium. Zeta potential results indicated that its values do not depend solely on the surface charge of the particle, but are also dependent on the net charge of the medium. In this study, water soluble associative polymers exhibit properties that can be of great interest in the petroleum industry