Effects of hydroxyl group distribution on the reactivity, stability and optical properties of fullerenols

We investigate the impact of hydroxyl groups on the properties of C(60)(OH)(n) systems, with n = 1, 2, 3, 4, 8, 10, 16, 18, 24, 32 and 36 by means of first-principles density functional theory calculations. A detailed analysis from the local density of states has shown that adsorbed OH groups can induce dangling bonds in specific carbon atoms around the adsorption site. This increases the tendency to form polyhydroxylated fullerenes (fullerenols). The structural stability is analyzed in terms of the calculated formation enthalpy of each species. Also, a careful examination of the electron density of states for different fullerenols shows the possibility of synthesizing single molecules with tunable optical properties.

Low generation triazine-based dendrimers-synthesis, characterzation and in vitro biological activity

In the present study, two low generation triazine-based dendrimers, G1.0(Cl)4 dendrimer and G1.5(OH)8 dendrimer, were synthesized and their cytotoxicity were tested by using the NIH 3T3 and the A2780 cell lines. In the synthesis process of the G1.0(Cl)4 dendrimer, cyanuric chloride (CAC) which has high reactivity chlorine atom was connected to the terminal of triethylene glycol (TEG) via nucleophilic substitution by controlling temperature. The prepared G1.0(Cl)4 dendrimer was purified by silica gel column chromatography. Then the four chlorine atoms in the G1.0(Cl)4 dendrimer were substituted by diethanolamine (DEA) to give dendrimer with the hydroxyl terminal group G1.5(OH)8. The starting materials, CAC, G1.0(Cl)4 dendrimer and G1.5(OH)8 dendrimer were analyzed by one-dimensional NMR, FTIR and MS techniques. The two dendrimers, G1.0(Cl)4 and G1.5(OH)8, showed perfect stability in the air environment at room temperature. However, G1.0(Cl)4 is not soluble in water while the G1.5(OH)8 dendrimer is a water soluble compound. Furthermore, cell biological evaluation at the studied concentrations showed that the CAC, as well as the prepared G1.0(Cl)4 and G1.5(OH)8 dendrimers, have no cytotoxicity towards the NIH 3T3 and A2780 cell lines.

Caracterização de poliacrilamida parcialmente hidrolisada em regime concentrado

A partially hydrolyzed polyacrylamide (HPAM) is a copolymer composed of acrylamide and sodium acrylate. Due to its wide range of applications there are different methods for its quantification and characterization in solution systems. Evaluation of C* is important to describe the transition from dilute to semi-dilute, behavior, when the solution will have its characteristic viscosity at concentrations above C*. This dissertation describes the determination of the critical concentration of overlap C* by potentiometry of partially hydrolyzed polyacrylamide - HPAM under acidic conditions. Based on the law of mass action and the proper treatment of the constant of aggregate formation, polymer molecular weight, degree of polymerization and hydrolysis were calculated. The inflection point was determined by the intersection of the resulting equation and mathematical development, statistically satisfy the experimental points relating the number of moles of monomers (n), equilibrium constant of formation of the entanglements (K*), pH, C* and acidity constant of the polymer (Ka). The viscometric parameters of C* showed a percentage difference compared to potentiometers. The results for the determination of C*, and degree of copolymerization molar mass proved to be a simple alternative for the characterization of polymers with protonated monomers and water soluble

Obtenção de sistemas microemulsionados e estudo de simulação por dinâmica molecular de sistemas micelares objetivando a veiculação de produtos naturais bioativos

Among the new drugs launched into the market since 1980, up to 30% of them belong to the class of natural products or they have semisynthetic origin. Between 40-70% of the new chemical entities (or lead compounds) possess poor water solubility, which may impair their commercial use. An alternative for administration of poorly water-soluble drugs is their vehiculation into drug delivery systems like micelles, microemulsions, nanoparticles, liposomes, and cyclodextrin systems. In this work, microemulsion-based drug delivery systems were obtained using pharmaceutically acceptable components: a mixture Tween 80 and Span 20 in ratio 3:1 as surfactant, isopropyl mirystate or oleic acid as oil, bidistilled water, and ethanol, in some formulations, as cosurfactants. Self-Microemulsifying Drug Delivery Systems (SMEDDS) were also obtained using propylene glycol or sorbitol as cosurfactant. All formulations were characterized for rheological behavior, droplet size and electrical conductivity. The bioactive natural product trans-dehydrocrotonin, as well some extracts and fractions from Croton cajucara Benth (Euphorbiaceae), Anacardium occidentale L. (Anacardiaceae) e Phyllanthus amarus Schum. & Thonn. (Euphorbiaceae) specimens, were satisfactorily solubilized into microemulsions formulations. Meanwhile, two other natural products from Croton cajucara, trans-crotonin and acetyl aleuritolic acid, showed poor solubility in these formulations. The evaluation of the antioxidant capacity, by DPPH method, of plant extracts loaded into microemulsions evidenced the antioxidant activity of Phyllanthus amarus and Anacardium occidentale extracts. For Phyllanthus amarus extract, the use of microemulsions duplicated its antioxidant efficiency. A hydroalcoholic extract from Croton cajucara incorporated into a SMEDDS formulation showed bacteriostatic activity against colonies of Bacillus cereus and Escherichia coli bacteria. Additionally, Molecular Dynamics simulations were performed using micellar systems, for drug delivery systems, containing sugar-based surfactants, N-dodecylamino-1-deoxylactitol and N-dodecyl-D-lactosylamine. The computational simulations indicated that micellization process for N-dodecylamino-1- deoxylactitol is more favorable than N-dodecyl-D-lactosylamine system.

Estudo da imobilização de proteases para a síntese de oligolisinas

Enzymatic synthesis of peptides using proteases has attracted a great deal of attention in recent years. One key challenge in peptide synthesis is to find supports for protease immobilization capable of working in aqueous medium at high performance, producing watersoluble oligopeptides. At present, few reports have been described using this strategy. Therefore, the aim of this thesis was to immobilize proteases applying different methods (Immobilization by covalent bound, entrapment onto polymeric gels of PVA and immobilization on glycidil metacrylate magnetic nanoparticles) in order to produce water-soluble oligopeptides derived from lysine. Three different proteases were used: trypsin, α-chymotrypsin and bromelain. According to immobilization strategies associated to the type of protease employed, trypsin-resin systems showed the best performance in terms of hydrolytic activity and oligopeptides synthesis. Hydrolytic activities of the free and immobilized enzymes were determined spectrophotometrically based on the absorbance change at 660 nm at 25 °C (Casein method). Calculations of oligolysine yield and average degree of polymerization (DPavg) were monitored by 1H-NMR analysis. Trypsin was covalently immobilized onto four different resins (Amberzyme, Eupergit C, Eupergit CM and Grace 192). Maximum yield of bound protein was 92 mg/g, 82 mg/g and 60 mg/g support for each resin respectively. The effectiveness of these systems (Trypsin-resins) was evaluated by hydrolysis of casein and synthesis of water-soluble oligolysine. Most systems were capable of catalyzing oligopeptide synthesis in aqueous medium, albeit at different efficiencies, namely: 40, 37 and 35% for Amberzyme, Eupergit C and Eupergit CM, respectively, in comparison with free enzyme. These systems produced oligomers in only 1 hour with DPavg higher than free enzyme. Among these systems, the Eupergit C-Trypsin system showed greater efficiency than others in terms of hydrolytic activity and thermal stability. However, this did not occur for oligolysine synthesis. Trypsin-Amberzyme proved to be more successful in oligopeptide synthesis, and exhibited excellent reusability, since it retained 90% of its initial hydrolytic and synthetic activity after 7 reuses. Trypsin hydrophobic interactions with Amberzyme support are responsible for protecting against strong enzyme conformational changes in the medium. In addition, the high concentration of oxirane groups on the surface promoted multi-covalent linking and, consequently, prevented the immobilized enzyme from leaching. The aforementioned results suggest that immobilized Trypsin on the supports evaluated can be efficiently used for oligopeptides synthesis in aqueous media

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

Avaliação das propriedades físico-químicas de sistemas a base de carboximetilcelulose e poli (N-isopropilacrilamida) em soluções aquosas para aplicação na indústria do petróleo

Sustainable development is a major challenge in the oil industry and has aroused growing interest in research to obtain materials from renewable sources. Carboxymethylcellulose (CMC) is a polysaccharide derived from cellulose and becomes attractive because it is water-soluble, renewable, biodegradable and inexpensive, as well as may be chemically modified to gain new properties. Among the derivatives of carboxymethylcellulose, systems have been developed to induce stimuli-responsive properties and extend the applicability of multiple-responsive materials. Although these new materials have been the subject of study, understanding of their physicochemical properties, such as viscosity, solubility and particle size as a function of pH and temperature, is still very limited. This study describes systems of physical blends and copolymers based on carboxymethylcellulose and poly (N-isopropylacrylamide) (PNIPAM), with different feed percentage compositions of the reaction (25CMC, 50CMC e 75CMC), in aqueous solution. The chemical structure of the polymers was investigated by infrared and CHN elementary analysis. The physical blends were analyzed by rheology and the copolymers by UV-visible spectroscopy, small-angle X-ray scattering (SAXS), dynamic light scattering (DLS) and zeta potential. CMC and copolymer were assessed as scale inhibitors of calcium carbonate (CaCO3) using dynamic tube blocking tests and chemical compatibility tests, as well as scanning electron microscopy (SEM). Thermothickening behavior was observed for the 50 % CMC_50 % PNIPAM and 25 % CMC_75 % PNIPAM physical blends in aqueous solution at concentrations of 6 and 2 g/L, respectively, depending on polymer concentration and composition. For the copolymers, the increase in temperature and amount of PNIPAM favored polymer-polymer interactions through hydrophobic groups, resulting in increased turbidity of polymer solutions. Particle size decreased with the rise in copolymer PNIPAM content as a function of pH (3-12), at 25 °C. Larger amounts of CMC result in a stronger effect of pH on particle size, indicating pH-responsive behavior. Thus, 25CMC was not affected by the change in pH, exhibiting similar behavior to PNIPAM. In addition, the presence of acidic or basic additives influenced particle size, which was smaller in the presence of the additives than in distilled water. The results of zeta potential also showed greater variation for polymers in distilled water than in the presence of acids and bases. The lower critical solution temperature (LCST) of PNIPAM determined by DLS corroborated the value obtained by UV-visible spectroscopy. SAXS data for PNIPAM and 50CMC indicated phase transition when the temperature increased from 32 to 34 °C. A reduction in or absence of electrostatic properties was observed as a function of increased PNIPAM in copolymer composition. Assessment of samples as scale inhibitors showed that CMC performed better than the copolymers. This was attributed to the higher charge density present in CMC. The SEM micrographs confirmed morphological changes in the CaCO3 crystals, demonstrating the scale inhibiting potential of these polymers

O Zoledronato no tratamento da osteoporose umeral em ratas: estudo prospectivo e randomizado

OBJETIVO: Investigar as repercussões clínicas, biomecânicas e histomorfométricas do zoledronato no tratamento da osteoporose umeral em ratas osteoporóticas. MÉTODOS: Analisou-se, prospectivamente, 40 ratas (Rattus novergicus albinus). Com 60 dias de vida, foram aleatorizadas em dois grupos de acordo com o procedimento cirúrgico: ooforectomia bilateral (O) (n=20) e pseudo-cirurgia (P) (n=20). Após trinta dias, os animais foram novamente randomizados, de acordo com a administração de 0,1mg/kg de zoledronato (AZ) ou água destilada (AD): OAZ (n=10), OAD (n=10), PAZ (n=10) e PAD (n=10). Após doze meses, os animais foram eutanasiados e seus úmeros retirados. Clinicamente considerou-se o peso dos animais; biomecanicamente foram realizados ensaios compressivos e histomorfometricamente foi determinada a área trabecular óssea. RESULTADOS: Os grupos O tiveram um aumento de peso maior que os grupos P (p=0,005). Os grupos com zoledronato suportaram maior carga máxima que os grupos com água destilada (p=0,02). Nos grupos com zoledronato verificou-se o aumento da área trabecular óssea quando comparados aos grupos com água destilada (p=0,001). Houve correlação positiva entre a área trabecular e a carga máxima (p=0,04; r=0,95). CONCLUSÃO: O zoledronato não influiu no peso dos animais. Os resultados mostraram o aumento da resistência óssea umeral e da área trabecular óssea.

Seroprevalence and risk factors associated with neosporosis in sheep and dogs from farms

This study aimed to establish the seroprevalence and risk factors associated with neosporosis in sheep and dogs from rural properties. 1497 blood samples were collected from sheep and 42 from dogs that cohabited with sheep from 16 farms located in the central region of São Paulo State, Brazil. For the detection of N. caninum antibodies it was performed the indirect fluorescent antibody test (IFAT >= 25). For the epidemiological study it was applied a questionnaire for the owners or responsible from the sheep and dogs regarding informations related to neosporosis. The seroprevalence obtained out of the 1497 sheep sera tested was 8.0% (CI95% = 6.7-9.2%) and out of the 42 dogs 4.8% (CI95% = 0-7.2%). Variables statistically related to seropositivity for N. caninum in sheep were: dams well as water supply (P = 0.0004; OR = 2.15), presence of other domestic canids (P = 0.0013; OR = 2.38) and presence of reproductive problems (P = 0.0031; OR = 1.75). (C) 2011 Elsevier B.V. All rights reserved.

Long-term effect of carbodiimide on dentin matrix and resin-dentin bonds

Objectives: To characterize the interaction of 1-Ethyl-3-[3-dimethylaminopropyl] carbodiimide Hydrochloride (EDC) with dentin matrix and its effect on the resin-dentin bond. Methods: Changes to the stiffness of demineralized dentin fragments treated with EDC/N-hydroxysuccinimide (NHS) in different solutions were evaluated at different time points. The resistance against enzymatic degradation was indirectly evaluated by ultimate tensile strength (UTS) test of demineralized dentin treated or not with EDC/NHS and subjected to collagenase digestion. Short- and long-term evaluations of the strength of resin-dentin interfaces treated with EDC/NHS for 1 h were performed using microtensile bond strength (mu TBS) test. All data (MPa) were individually analyzed using ANOVA and Tukey HSD tests (alpha = 0.05). Results: The different exposure times significantly increased the stiffness of dentin (p < 0.0001, control-5.15 and EDC/NHS-29.50), while no differences were observed among the different solutions of EDC/NHS (p = 0.063). Collagenase challenge did not affect the UTS values of EDC/NHS group (6.08) (p > 0.05), while complete degradation was observed for the control group (p = 0.0008, control-20.84 and EDC/NHS-43.15). EDC/NHS treatment did not significantly increase resin-dentin mu TBS, but the values remained stable after 12 months water storage (p < 0.05). Conclusions: Biomimetic use of EDC/NHS to induce exogenous collagen cross-links resulted in increased mechanical properties and stability of dentin matrix and dentin-resin interfaces. (C) 2010 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 94B: 250-255, 2010.

Exposed collagen in aged resin-dentin bonds produced on sound and caries-affected dentin in the presence of chlorhexidine

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

Interaction Between the Predator Podisus nigrispinus (Hemiptera: Pentatomidae) and the Entomopathogenic Bacteria Bacillus thuringiensis

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Efeitos do tratamento oral com sulfato de vanadila em ratos diabeticos jovens

This work intends to evaluate the effects of oral vanadyl treatment (VOSO 4, 1 mg/mL) in young streptozotocin-diabetic rats during 19 and 29 days. In several times of treatment the rats were monitored to determine body weight, food and water intakes, glycemia, and the urinary excretion of glucose and urea. The animals were killed in the 19(th) and 29(th) days, and the glycemia level was determined again, as well as the weight of pancreas, muscles (Soleus and Extensor digitorum longus - EDL) and adipose tissues (epididymal and retroperitoneal). The results showed that the treatment of young diabetic rats with VOSO 4 promotes the reduction of hyperglycemia (p < 0.01), food (p < 0.01) and water intakes (p < 0.05) and body weight (p < 0.05). Neither the tissues and pancreas weights nor the urinary urea level of the treatment group varied in comparison to the control group. In conclusion, the vanadyl treatment in the studied period is able to reduce the main metabolic alterations often found in diabetes. These data are very useful and important for the future experiments to verify the effects of vanadyl sulfate on muscle protein metabolism in diabetic rats.

Effect of post-polymerization heat treatments on the cytotoxicity of two denture base acrylic resins

Introduction: Most denture base acrylic resins have polymethylmethacrylate in their composition. Several authors have discussed the polymerization process involved in converting monomer into polymer because adequate polymerization is a crucial factor in optimizing the physical properties and biocompatibility of denture base acrylic resins. To ensure the safety of these materials, in vitro cytotoxicity assays have been developed as preliminary screening tests to evaluate material biocompatibility. 3H-thymidine incorporation test, which measures the number of cells synthesizing DNA, is one of the biological assays suggested for cytotoxicity testing. Aim: The purpose of this study was to investigate, using 3H-thymidine incorporation test, the effect of microwave and water-bath post-polymerization heat treatments on the cytotoxicity of two denture base acrylic resins. Materials and Methods: Nine disc-shaped specimens (10 x 1 mm) of each denture base resin (Lucitone 550 and QC 20) were prepared according to the manufacturers' recommendations and stored in distilled water at 37°C for 48 h. The specimens were assigned to 3 groups: 1) post-polymerization in a microwave oven for 3 min at 500 W; 2) post-polymerization in water-bath at 55°C for 60 min; and 3) without post-polymerization. For preparation of eluates, 3 discs were placed into a sterile glass vial with 9 mL of Eagle's medium and incubated at 37°C for 24 h. The cytotoxic effect of the eluates was evaluated by 3H-thymidine incorporation. Results: The results showed that the components leached from the resins were cytotoxic to L929 cells, except for the specimens heat treated in water bath (p<0.05). Compared to the group with no heat treatment, water-bath decreased the cytotoxicity of the denture base acrylic resins. Conclusion: The in vitro cytotoxicity of the tested denture base materials was not influenced by microwave post-polymerization heat treatment.

Study of polypropylene surface modification by air dielectric barrier discharge operated at two different frequencies

In this work, air dielectric barrier discharge (DBD) operating at the line frequency (60 Hz) or at frequency of 17 kHz was used to improve the wetting properties of polypropylene (PP). The changes in the surface hydrophilicity were investigated by contact angle measurements. The plasma-induced chemical modifications of PP surface were studied by X-ray photoelectron spectroscopy (XPS) and Fourier-transformed infrared spectroscopy (FTIR). The polymer surface morphology and roughness before and after the DBD treatment were analyzed by atomic force microscopy (AFM). To compare the plasma treatment effect at different frequencies the variation of the contact angle is presented as a function of the deposited energy density. The results show that both DBD treatments leaded to formation of water-soluble low molecular weight oxidized material (LMWOM), which agglomerated into small mounts on the surface producing a complex globular structure. However, the 60 Hz DBD process produced higher amount of LMWOM on the PP surface comparing to the 17 kHz plasma treatment with the same energy dose. The hydrophilic LMWOM is weakly bounded to the surface and can be easily removed by polar solvents. After washing the DBD-treated samples in de-ionized water their surface roughness and oxygen content were reduced and the PP partially recovered its original wetting characteristics. This suggested that oxidation also occurred at deeper and more permanent levels of the PP samples. Comparing both DBD processes the 17 kHz treatment was found to be more efficient in introducing oxygen moieties on the surface and also in improving the PP wetting properties. © 2012 Elsevier B.V. All rights reserved.