Synthesis Optimization of Hydroxymethylnitrofurazone, an Antichagasic Candidate, Using 3(2) Factorial Design

Hydroxymethylnitrofurazone presents in vitro activity against Trypanosoma cruzi. The optimization of the synthesis of this compound was performed through a 3(2) factorial statistical design. Quadratic model produced the best response surface predicting a maximum yield (82%) close to the center design point with a seven hours reaction and a 1:1.5 (NF:K(2)CO(3)) ratio.

Group 11 (Cu, Ag, Au) promotion of 15%Co/Al(2)O(3) Fischer-Tropsch synthesis catalysts

Co/Al(2)O(3) Fischer-Tropsch synthesis catalysts promoted with different quantities of Group 11 metals (Cu, Ag, Au) were characterized and tested. The presence of relatively small quantities of such metals enhanced Co reducibility and, in the cases of Ag and Au, improved the surface Co metal active site densities. EXAFS experiments with the most loaded catalyst samples show that only Co-Co and Me-Me (Me = Cu, Ag and Au) coordination could be observed. This suggests that the greater fraction of the metals form different phases. However, the reduction promoting effect of the Group 11 metal is severely hampered once the catalyst receives a mild passivation treatment following primary reduction. An explanation in terms of promoter segregation during primary reduction is proposed. At lower promoter levels (0.83%Ag and 1.51%Au) and higher Ag levels (2.76%), significant gains in Co active site densities were achieved resulting in improved CO conversion levels relative to the unpromoted catalyst. Moreover, slight decreases in light product (e.g., CH(4)) selectivity and slight increases in C(5)+ selectivity were achieved. At high Au loading (5.05%), however, too much Au was loaded which, although significantly increasing the fraction of Co reduced, blocked Co surface sites and resulted in decreased Co conversion rates. While Cu facilitated Co reduction, the increased fraction of reduced Co did not translate to improved active site densities. It appears that a fraction of Cu tended to cover the rim of Co clusters, resulting in decreases in CO conversion rates and detrimental increases in light product selectivity. (C) 2009 Elsevier B.V. All rights reserved.

Synthesis and Characterization of Magnetic Composites Based on Cis-Polyisoprene and CoFe(2)O(4) Nanoparticles

CoFe(2)O(4) nanoparticles were obtained by the co-precipitation method. They were further modified by the adsorption of ricinoleic acid (RA). The non-modified and modified CoFe(2)O(4)/RA nanoparticles were characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), Raman, and Fourier transform infrared (FTIR) spectroscopy. The modified particles present a mean diameter < 20 nm. The adsorption of RA on the CoFe(2)O(4) surface is characterized by the IR absorptions of the RA while in the Raman spectrum the predominant signals are those from the CoFe(2)O(4). The cis-polyisoprene (PI) composite was prepared by dissolving PI in cyclohexane followed by the addition of a magnetic fluid based on CoFe(2)O(4)/RA nanoparticles dispersed in cyclohexane. After solvent evaporation a magnetic composite was obtained and characterized by AFM, Raman, and FTIR measurements. AFM images show uniformly CoFe(2)O(4)/RA particles distributed in the PI matrix. Raman spectra obtained for the composites reveal the characteristic Raman peaks of PI and CoFe(2)O(4) nanoparticles.

Synthesis, characterization and adsorption properties of porous mixed valent diruthenium(II,III)-terephthalate and diruthenium(II,III)-adipate polymers

Two porous mixed valent diruthenium(II,III)-dicarboxylate compounds have been prepared and characterized by spectroscopic methods, X-ray diffraction and thermogravimetry. Crystalline solids of [Ru(2)(tere)(2)Cl] center dot 3.5H(2)O (tere=terephthalate) and [Ru(2)(adip)(2)Cl] center dot 1.5H(2)O (adip=adipate) consist of extended chains in which polymeric layers of multiply metal-metal bonded [Ru(2)](5+) cores are bridged by dicarboxylate ligands in paddlewheel type geometries. Units of [Ru(2)(dicarboxylate)(2)](n)(+) are linked by axial bridging chloride ions generating three-dimensional networks. The polymers loose non-bonded water molecules at low temperatures but do not undergo thermal decomposition below 280-300 degrees C. Both of compounds exhibit high BET surface areas, [Ru(2)(tere)(2)Cl]: 235 m(2) g(-1) and [Ru(2)(adip)(2)Cl]: 281 m(2) g(-1), and occlude similar numbers of mol of N(2) per mol of metal. The terephthalate ligand generated an organized structure with supermicropores (total pore size of 0.24 cm(3) g(-1)) while the adipate ligand led to a mesoporous structure (total pore sizes of 0.47 cm(3) g(-1)) for the corresponding diruthenium(II,III)-dicarboxylate polymers. (c) 2008 Elsevier B.V. All rights reserved.

Microwave-Assisted Derivatization of Cellulose in an Ionic Liquid: An Efficient, Expedient Synthesis of Simple and Mixed Carboxylic Esters

Microwave (MW)-assisted cellulose dissolution in ionic liquids (ILs) has routinely led either to incomplete biopolymer solubilization, or its degradation. We show that these problems can be avoided by use of low-energy MW heating, coupled with efficient stirring. Dissolution of microcrystalline cellulose in the IL 1-allyl-3-methylimidazolium chloride has been achieved without changing its degree of polymerization; regenerated cellulose showed pronounced changes in its index of crystallinity, surface area, and morphology. MW-assisted functionalization of MCC by ethanoic, propanoic, butanoic, pentanoic, and hexanoic anhydrides has been studied. Compared with conventional heating, MW irradiation has resulted in considerable decrease in dissolution and reaction times. The value of the degree of substitution (DS) was found to be DS(ethanoate) > DS(propanoate) > DS(butanoate). The values of DS(pentanoate) and DS(hexanoate) were found to be slightly higher than DS(ethanoate). This surprising dependence on the chain length of the acylating agent has been reported before, but not rationalized. On the basis of the rate constants and activation parameters of the hydrolysis of ethanoic, butanoic, and hexanoic anhydrides in aqueous acetonitrile (a model acyl transfer reaction), we suggest that this result may be attributed to the balance between two opposing effects, namely, steric crowding and (cooperative) hydrophobic interactions between the anhydride and the cellulosic surface, whose lipophilicity has increased, due to its partial acylation. Four ethanoate-based mixed esters were synthesized by the reaction with a mixture of the two anhydrides; the ethanoate moiety predominated in all products. The DS is reproducible and the IL is easily recycled. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 134-143, 2010

Synthesis of NiO-MgO-ZrO(2) catalysts and their performance in reforming of model biogas

Catalysts containing NiO/MgO/ZrO(2) mixtures were synthesized by the polymerization method in a single step. They were characterized by X-ray diffraction (XRD), temperature programmed reduction (TPR) and physisorption of N(2) (BET) and then tested in the reforming of a model biogas (1.5CH4:1CO(2)) in the presence of air (1.5CH(4) + 1CO(2) + 0.25O(2)) at 750 degrees C for 6h. It was observed that the catalyst Ni20MZ performed better in catalytic processes than the well known catalysts, Ni/ZrO(2) and Ni/MgO, synthesized under the same conditions. The formation of solid solutions, MgO-ZrO(2) and NiO-MgO, increased the rate of conversion of reactants (CH(4) and CO(2)) into synthesis gas (H(2) + CO). The formation of oxygen vacancies (in samples containing ZrO(2) and MgO) seems to promote removal of the coke deposited on the nickel surface. The values of the H(2)/CO ratio were generally found to be slightly lower than stoichiometric, owing to the reverse water gas shift reaction occurring in parallel. (C) 2011 Elsevier B.V. All rights reserved.

Selective Synthesis of Oxacalix[6]arenes and Mixed Oxacalix[4]arenes

Calixarenesare macrocycles composed of benzene rings meta linked to each other by one carbon atom. These exotic compounds can be used for a variety of purposes including metalleaching for environmental cleanup, surface technology, luminescent probes, nuclear waste treatment, among others. A variety of calixarenesexist, including azacalix[n]arenesthiocalix[n]arenes(where n = the number of benzene rings) and oxacalix[n]arenes; these macrocycles use nitrogen, sulfur and oxygen, respectively, as the atom whichlinks the benzene rings together. My research has focused on synthesizing oxacalix[6]arenes (“hexamer”) in high yield, which is a synthetic challenge because it is generally accepted that oxacalix[n>4]arenes will thermodynamically decompose to the oxacalix[4]arene (“tetramer”); i.e. heating the reaction mixture will yield the tetramer, not the hexamer. To generate the hexamer, “trimer”precursors have been synthesized, in the hopes of facilitating hexamer ring closure.

Synthesis and characterization of hybrids derived from vermiculite chloropropyl and aliphatic diamines

ALVES, Ana Paula de Melo et al. Synthesis and characterization of hybrids derived from vermiculite chloropropyl and aliphatic diamines. Journal of Thermal Analysis and Calorimetry, v.87, n. 3, p.771–774, 2007.

Synthesis of poly(styrene-co-methyl methacrylate)-based ionomers and their Langmuir and Langmuir-Blodgett (LB) film formation

Poly(styrene-co-methyl methacrylate) (PS-PMMA) ionomers with several degrees of sulfonation were synthesized and characterized by infrared, UV-vis, and NMR spectroscopies, elemental analysis, and differential scanning calorimetry (DSC). Stable Langmuir films could be produced with PS-PMMA with 3 and 6 mol % of sulfonation, while PS-PMMA 8% exhibited material loss to the water subphase, probably due to its higher solubility. Surface pressure and surface potential isotherms with PS-PMMA 3% spread onto salt-containing subphases pointed to a film behavior characteristic of the polyelectrolyte effect, where charge repulsion governs the film properties. The Langmuir-Blodgett films of this ionomer were successfully transferred onto various substrates, as confirmed by UV-vis and FTIR spectroscopies. Using cycling voltammetry, we show that LB films from PS-PMMA 3% can be applied in selective sensing of dopamine, even in the presence of interferents such as ascorbic acid.

Structural and electrochemical properties of LiCoO2 prepared by combustion synthesis

LiCoO2 powders were prepared by combustion synthesis, using metallic nitrates as the oxidant and metal sources and urea as fuel. A small amount of the LiCoO2 phase was obtained directly from the combustion reaction, however, a heat treatment was necessary for the phase crystallization. The heat treatment was performed at the temperature range from 400 up to 700 degreesC for 12 h. The powders were characterized by X-ray diffraction (XRD), X ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and specific surface area values were obtained by BET isotherms. Composite electrodes were prepared using a mixture of LiCoO2, carbon black and poly(vinylidene fluoride) (PVDF) in the 85:10:5% w/w ratio. The electrochemical behavior of these composites was evaluated in ethylene carbonate/dimethylcarbonate solution, using lithium perchlorate as supporting electrolyte. Cyclic voltammograms showed one reversible redox process at 4.0/3.85 V and one irreversible redox process at 3.3 V for the LiCoO2 obtained after a post-heat treatment at 400 and 500 degreesC.Raman spectroscopy showed the possible presence of LiCoO2 with cubic structure for the material obtained at 400 and 500 degreesC. This result is in agreement with X-ray data with structural refinement for the LiCoO2 powders obtained at different temperatures using the Rietveld method. Data from this method showed the coexistence of cubic LiCoO2 (spinel) and rhombohedral (layered) structures when LiCoO2 was obtained at lower temperatures (400 and 500 degreesC). The single rhombohedral structure for LiCoO2 was obtained after post-heat treatment at 600 degreesC. The maximum energy capacity in the first discharge was 136 mA g(-1) for the composite electrode based on LiCoO2 obtained after heat treatment at 700 degreesC. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Defensive-like behaviors and antinociception induced by NMDA injection into the periaqueductal gray of mice depend on nitric oxide synthesis

Glutamate NMDA receptor activation within the periaqueductal gray (PAG) leads to antinociceptive, autonomic and behavioral responses characterized as the fear reaction. Considering that NMDA receptor triggers activation of neuronal nitric oxide synthase (nNOS), enzyme that produces nitric oxide (NO), this study investigated the effects of intra-PAG infusions of NPLA (N omega-propyl-L-arginine), an nNOS inhibitor, on behavioral and antinociceptive responses induced by local injection of NMDA receptor agonist in mice. The behaviors measured were frequency of jumping and rearing as well as duration (in seconds) of running and freezing. Nociception was assessed during the second phase of the formalin test (injection of 50 mu l of formalin 2.5% into the dorsal surface of the right hind paw). Five to seven days after stereotaxic surgery for intracerebral cannula implantation, mice were injected with formalin into the paw, and 10 min later, they received intra-dPAG injection of NPLA (0, 0.2, or 0.4 nmol/0.1 mu l). Ten minutes later, they were injected with NMDA (N-methyl-D-aspartate: 0 or 0.04 nmol/0.1 mu l) into the same midbrain site and were immediately placed in glass holding cage for recording the defensive behavior and the time spent on licking the injected paw with formalin during a period of 10 min. Microinjections of NMDA significantly decreased nociception response and produced jumping, running, and freezing reactions. Intra-dPAG injections of NPLA (0.4 nmol) completely blocked the NMDA effects without affecting either behavioral or nociceptive responses in intra-dPAG saline-injected animals, except for the rearing frequency that was increased by the nNOS inhibitor. These results strongly suggest the involvement of NO within the PAG in the antinociceptive and defensive reactions induced by local glutamate NMDA receptor activation in this midbrain structure. (c) 2006 Elsevier B.V. All rights reserved.

Polymeric precursor method to the synthesis of XWO(4) (X = Ca and Sr) thin films-Structural, microstructural and spectroscopic investigations

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

Ferrocene adsorbed into the porous octakis(hydridodimethylsiloxy) silsesquioxane after thermolysis in tetrahydrofuran media: An applied surface for ascorbic acid determination

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

Adsorption and electropolymerization of toluidine blue on the nano structured octakis(hydridodimethylsiloxy)-octasilsesquioxane surface

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

Synthesis, characterization, and application of modified silica in the removal and preconcentration of lead ions from natural river water

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