Synthesis and characterization of nanostructured TiO2-SnO2 composite

Nanostructured composites based on titanium dioxide have been studied in order to improve optical and photo-catalytic properties, as well as their performance in gas sensors. In this work, titanium and tin dioxides were simultaneously synthesized by the polyol method resulting in TiO2 platelet coated with SnO2 nanoparticles as was observed by scanning electron microscopy. The thermal analysis showed that the combined synthesis promotes more easily the crystallization of the TiO2 rutile phase. The composite obtained after heat treatment at 500 °C showed to be formed of almost only rutile phases of both oxides. The optical properties analyzed by UV-Vis spectroscopy showed that the combined oxides have higher absorbance, which reinforces a model found in the literature based on the flow of photo-generated electrons to the conduction band of SnO2 delaying the recombination of charges.

O desenvolvimento de nanopartículas de intermetálicos ordenados de ouro e estudo da atividade eletroquímica da reação de oxidação do glicerol

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Filmes de Langmuir-Blodgett de nanopartículas de prata

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

O efeito da ordenação e estrutura geométrica dos materiais PtSn/C e PdSn/C na eletrooxidação do glicerol em meio alcalino

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Electrocatalytic performance of environmentally friendly synthesized gold nanoparticles towards the borohydride electro-oxidation reaction

In this paper we report a simple and environmentally friendly synthesis of gold nanoparticles (AuNps) and their electrocatalytic activity for borohydride oxidation reaction (BOR). Ultraviolet spectroscopy (UV- vis) and transmission electron microscopy (TEM) confirmed the formation of poly(vinyl pyrrolidone)protected colloidal AuNps through direct reduction of Au3+ by glycerol in alkaline medium at room temperature. For the BOR tests the AuNps were directly produced onto carbon to yield the Au/C catalyst. Levich plots revealed that the process occured via 7.2 electrons, therefore near the theoretical value of 8 electrons. When compared to bulk Au, the gold nanoparticles presented enhanced catalytic properties since the onset potential for BOR was shifted 200 mV towards negative potentials. (C) 2012 Elsevier B.V. All rights reserved.

An optimization study of PtSn/C catalysts applied to direct ethanol fuel cell: Effect of the preparation method on the electrocatalytic activity of the catalysts

The aim of this work was to perform a systematic study of the parameters that can influence the composition, morphology, and catalytic activity of PtSn/C nanoparticles and compare two different methods of nanocatalyst preparation, namely microwave-assisted heating (MW) and thermal decomposition of polymeric precursors (DPP). An investigation of the effects of the reducing and stabilizing agents on the catalytic activity and morphology of Pt75Sn25/C catalysts prepared by microwave-assisted heating was undertaken for optimization purposes. The effect of short-chain alcohols such as ethanol, ethylene glycol, and propylene glycol as reducing agents was evaluated, and the use of sodium acetate and citric acid as stabilizing agents for the MW procedure was examined. Catalysts obtained from propylene glycol displayed higher catalytic activity compared with catalysts prepared in ethylene glycol. Introduction of sodium acetate enhanced the catalytic activity, but this beneficial effect was observed until a critical acetate concentration was reached. Optimization of the MW synthesis allowed for the preparation of highly dispersed catalysts with average sizes lying between 2.0 and 5.0 nm. Comparison of the best catalyst prepared by MW with a catalyst of similar composition prepared by the polymeric precursors method showed that the catalytic activity of the material can be improved when a proper condition for catalyst preparation is achieved. (C) 2012 Elsevier B.V. All rights reserved.

Xylitol concentrations in artificial saliva after application of different xylitol dental varnishes

Objective: The present study analyzed xylitol concentrations in artificial saliva over time after application of varnishes containing 10% and 20% xylitol. Material and Methods: Fifteen bovine enamel specimens (8x4 mm) were randomly allocated to 3 groups (n=5/group), according to the type of varnish used: 10% xylitol, 20% xylitol and no xylitol (control). After varnish application (4 mg), specimens were immersed in vials containing 500 mu L of artificial saliva. Saliva samples were collected in different times (1, 8, 12, 16, 24, 48 and 72 h) and xylitol concentrations were analyzed. Data were assessed by two-way repeated-measures ANOVA (p<0.05). Results: Colorimetric analysis was not able to detect xylitol in saliva samples of the control group. Salivary xylitol concentrations were significantly higher up to 8 h after application of the 20% xylitol varnish. Thereafter, the 10% xylitol varnish released larger amounts of that polyol in artificial saliva. Conclusions: Despite the results in short-term, sustained xylitol releases could be obtained when the 10% xylitol varnish was used. These varnishes seem to be viable alternatives to increase salivary xylitol levels, and therefore, should be clinically tested to confirm their effectiveness.

Sviluppo di metodi innovativi per la sintesi di nanoparticelle di interesse industriale

Among various nanoparticles, noble metal nanoparticles have attracted considerable attention due to their optical, catalytic and conducting properties. This work has been focused on the development of an innovative method of synthesis for the preparation of metal nanosuspensions of Au, Ag, Cu, in order to achieve stable sols, showing suitable features to allow an industrial scale up of the processes. The research was developed in collaboration with a company interested in the large scale production of the studied nanosuspensions. In order to develop a commercial process, high solid concentration, long time colloidal stability and particle size control, are required. Two synthesis routes, differing by the used solvents, have been implemented: polyol based and water based synthesis. In order to achieve a process intensification the microwave heating has been applied. As a result, colloidal nanosuspensions with suitable dimensions, good optical properties, very high solid content and good stability, have been synthesized by simple and environmental friendly methods. Particularly, due to some interesting results an optimized synthesis process has been patented. Both water and polyol based synthesis, developed in the presence of a reducing agent and of a chelating polymer, allowed to obtain particle size-control and colloidal stability by tuning the different parameters. Furthermore, it has been verified that microwave device, due to its rapid and homogeneous heating, provides some advantages over conventional method. In order to optimize the final suspensions properties, for each synthesis it has been studied the effect of different parameters (temperature, time, precursors concentrations, etc) and throughout a specific optimization action a right control on nucleation and growth processes has been achieved. The achieved nanoparticles were confirmed by XRD analysis to be the desired metal phases, even at the lowest synthesis temperatures. The particles showed a diameter, measured by STEM and dynamic light scattering technique (DLS), ranging from 10 to 60 nm. Surface plasmon resonance (SPR) was monitored by UV-VIS spectroscopy confirming its dependence by nanoparticles size and shape. Moreover the reaction yield has been assessed by ICP analysis performed on the unreacted metal cations. Finally, thermal conductivity and antibacterial activity characterizations of copper and silver sols respectively are now ongoing in order to check their application as nanofluid in heat transfer processes and as antibacterial agent.

Hyperbranched polyether polyols as building blocks for complex macromolecular architectures

The present thesis deals with the development of new branched polymer architectures containing hyperbranched polyglycerol. Materials investigated include hyperbranched oligomers, hyperbranched polyglycerols containing functional initiator-cores at the focal point, well-defined linear-hyperbranched block copolymers and also negatively charged hyperbranched polyelectrolytes.rnHyperbranched oligoglycerols (DPn = 7 and 14) have been synthesized for the first time. The materials show narrow polydispersity (Mw/Mn ca. 1.45) and a very low content in cyclic homopolymers. 13C NMR evidences the dendritic structure of the oligomers and the DB could be calculated (44% and 52%). These new oligoglycerols were compared with the industrial products obtained by polycondensation which exhibit narrow polydispersity (Mw/Mn<1.3) butrnmultimodal distribution in SEC. Detailed 13C NMR and Maldi-ToF studies reveal the presence of branched units and cyclic compounds. In comparison, the hyperbranched oligoglycerols comprise a very low proportion of cyclic homopolymer which render them very interesting materials for biomedical applications for example.rnThe site isolation of the core moiety in dendritic structure offers intriguing potential with respect to peculiar electro-optical properties. Various initiator-cores (n-alkyl amines, UVabsorbing amines and benzophenone) for the ROMBP of glycidol have been tested. The bisglycidolized amine initiator-cores show the best control over the molecular weight and the molecular weight distribution. The photochemical analyses of the naphthalene containingrnhyperbranched polyglycerols show a slight red shift, a pronounced hypochromic effect (decrease of the intensity of the band) compared with the parent model compound and the formation of a relative compact structure. The benzophenone containing polymers adopt an open structure in polar solvents. The fluorescence measurements show a clear “dendritic effect” on the fluorescence intensities and the quantum yield of the encapsulated benzophenone.rnA convenient 3-step strategy has been developed for the preparation of well-defined amphiphilic, linear-hyperbranched block copolymers via hypergrafting. The procedure represents a combination of carbanionic polymerization with the alkoxide-based, controlled ring-opening multibranching polymerization of glycidol. Materials consisting of a polystyrene linear block and a hyperbranched polyglycerol block exhibit narrow polydispersity (1.01-1.02rnfor 5.4% to 27% wt. PG and 1.74 for 52% wt. PG) with a high grafting efficiency. The strategy was also extended to materials with a linear polyisoprene block.rnDetailed investigations of the solution properties of the block copolymers with linear polystyrene blocks show that block copolymer micelles are stabilized by the highly branched block. The morphology of the aggregates is depending on the solvent: in chloroform monodisperse spherical shape aggregates and in toluene ellipsoidal aggregates are formed. On graphite these aggregates show interesting features, giving promising potential applications with respect to the presence of a very dense, functional and stable hyperbranched block.rnThe bulk morphology of the linear-hyperbranched block copolymers has been investigated. The materials with a linear polyisoprene block only behave like complex liquids due to the low Tg and the disordered nature of both components. For the materials with polystyrene, only the sample with 27% wt. hyperbranched polyglycerol forms some domains showing lamellae.rnThe preparation of hyperbranched polyelectrolytes was achieved by post-modification of the hydroxyl groups via Michael addition of acrylonitrile, followed by hydrolysis. In aqueous solution materials form large aggregates with size depending on the pH value. After deposition on mica the structures observed by AFM show the coexistence of aggregates andrnunimers. For the low molecular weight sample (PG 520 g·mol-1) extended and highly ordered terrace structures were observed. Materials were also successfully employed for the fabrication of composite organic-inorganic multilayer thin films, using electrostatic layer-bylayer self-assembly coupled with chemical vapor deposition.

Reductase inhibitory activity of some flavones: Topological descriptors in modeling the activity

In healthy people, glucose is metabolized through Embden-Meyerhoff pathway. In cases of diabetes mellitus, with the increased levels of glucose in insulin-insensitive tissues the Aldose Reductase (AR) in polyol pathway facilitates the conversion of glucose to sorbitol. In this cascade of events the accumulated sorbitol is attributed to be responsible for cataract, neuropathy and retinopathy in diabetic cases.1,2 Thus, the inhibition of AR in polyol pathway may prevent and lead to the cure of the complications arising out of the diabetes mellitus. In this background, Matsuda and coworkers3 studied the AR inhibitory activity of large number of flavones and related compounds from traditional antidiabetic remedies. Here, many of these compounds shared 2-Aryl-benzpyran-4-one as scaffold for different chemical groups surrounding this moiety. This offers scope to investigate the AR inhibitory activity of these compounds in relation to the functional group environment surrounding this core

Myo-Inositol-Dependent Sodium Uptake in Ice Plant1

In salt-stressed ice plants (Mesembryanthemum crystallinum), sodium accumulates to high concentrations in vacuoles, and polyols (myo-inositol, d-ononitol, and d-pinitol) accumulate in the cytosol. Polyol synthesis is regulated by NaCl and involves induction and repression of gene expression (D.E. Nelson, B. Shen, and H.J. Bohnert [1998] Plant Cell 10: 753–764). In the study reported here we found increased phloem transport of myo-inositol and reciprocal increased transport of sodium and inositol to leaves under stress. To determine the relationship between increased translocation and sodium uptake, we analyzed the effects of exogenous application of myo-inositol: The NaCl-inducible ice plant myo-inositol 1-phosphate synthase is repressed in roots, and sodium uptake from root to shoot increases without stimulating growth. Sodium uptake and transport through the xylem was coupled to a 10-fold increase of myo-inositol and ononitol in the xylem. Seedlings of the ice plant are not salt-tolerant, and yet the addition of exogenous myo-inositol conferred upon them patterns of gene expression and polyol accumulation observed in mature, salt-tolerant plants. Sodium uptake and transport through the xylem was enhanced in the presence of myo-inositol. The results indicate an interdependence of sodium uptake and alterations in the distribution of myo-inositol. We hypothesize that myo-inositol could serve not only as a substrate for the production of compatible solutes but also as a leaf-to-root signal that promotes sodium uptake.

Polyols in the crustose lichen Rhizocarpon geographicum

A lichen is an intimate association between an alga and a fungus and is regarded as one of the best examples of ‘mutualism’ or ‘symbiosis’ involving microorganisms. In lichens which have Trebouxia as the algal partner, photosynthesis by the algae results in the production of the soluble polyol ribitol which is then transported to the fungus where it is converted to arabitol and mannitol. Within the fungus, arabitol may act as a short-term carbohydrate reserve while mannitol may be involved in stress resistance. The crustose lichen Rhizocarpon geographicum (L.) DC., has an unusual thallus structure consisting of discrete granules (areolae) containing the algal component growing in association with a non-lichenised fungal hypothallus that extends beyond the areolae to form a marginal ring. The concentrations of ribitol, arabitol, and mannitol were measured, using gas chromatography, in the central areolae and marginal hypothallus of the crustose lichen Rhizocarpon geographicum (L.) DC. growing on slate rocks in north Wales, UK. The concentrations of all three polyols were greater in the central areolae than in the marginal hypothallus. In addition, the ratios of polyols in the marginal hypothallus to that in the central areolae varied through the year. The concentration of an individual poyol in the hypothallus was correlated primarily with the concentrations of the other polyols in the hypothallus and not to their concentrations in the areolae. Low concentration of ribitol, arabitol, and mannitol in the marginal hypothallus compared with the central areolae suggests either a lower demand for carbohydrate by the hypothallus or limited transport of polyols from areolae to hypothallus, and may explain the low growth rates of this species. In addition, polyols appear to be partitioned differently through the year with an increase in mannitol compared with arabitol in more stressful periods.

Polyols in the crustose lichen rhizocarpon geographicum

A lichen is an intimate association between an alga and a fungus and is regarded as one of the best examples of ‘mutualism’ or ‘symbiosis’ involving microorganisms. In lichens which have Trebouxia as the algal partner, photosynthesis by the algae results in the production of the soluble polyol ribitol which is then transported to the fungus where it is converted to arabitol and mannitol. Within the fungus, arabitol may act as a short-term carbohydrate reserve while mannitol may be involved in stress resistance. The crustose lichen Rhizocarpon geographicum (L.) DC., has an unusual thallus structure consisting of discrete granules (areolae) containing the algal component growing in association with a non-lichenised fungal hypothallus that extends beyond the areolae to form a marginal ring. The concentrations of ribitol, arabitol, and mannitol were measured, using gas chromatography, in the central areolae and marginal hypothallus of the crustose lichen Rhizocarpon geographicum (L.) DC. growing on slate rocks in north Wales, UK. The concentrations of all three polyols were greater in the central areolae than in the marginal hypothallus. In addition, the ratios of polyols in the marginal hypothallus to that in the central areolae varied through the year. The concentration of an individual poyol in the hypothallus was correlated primarily with the concentrations of the other polyols in the hypothallus and not to their concentrations in the areolae. Low concentration of ribitol, arabitol, and mannitol in the marginal hypothallus compared with the central areolae suggests either a lower demand for carbohydrate by the hypothallus or limited transport of polyols from areolae to hypothallus, and may explain the low growth rates of this species. In addition, polyols appear to be partitioned differently through the year with an increase in mannitol compared with arabitol in more stressful periods.

Conditional osmotic stress in yeast:a system to study transport through aquaglyceroporins and osmostress signaling

The accumulation and transport of solutes are hallmarks of osmoadaptation. In this study we have employed the inability of the Saccharomyces cerevisiae gpd1Δ gpd2Δ mutant both to produce glycerol and to adapt to high osmolarity to study solute transport through aquaglyceroporins and the control of osmostress-induced signaling. High levels of different polyols, including glycerol, inhibited growth of the gpd1Δ gpd2Δ mutant. This growth inhibition was suppressed by expression of the hyperactive allele Fps1-AΔ of the osmogated yeast aquaglyceroporin, Fps1. The degree of suppression correlated with the relative rate of transport of the different polyols tested. Transport studies in secretory vesicles confirmed that Fps1-Δ1 transports polyols at increased rates compared with wild type Fps1. Importantly, wild type Fps1 and Fps1-Δ1 showed similarly low permeability for water. The growth defect on polyols in the gpd1Δ gpd2Δ mutant was also suppressed by expression of a heterologous aquaglyceroporin, rat AQP9. We surmised that this suppression was due to polyol influx, causing the cells to passively adapt to the stress. Indeed, when aquaglyceroporin-expressing gpd1Δ gpd2Δ mutants were treated with glycerol, xylitol, or sorbitol, the osmosensing HOG pathway was activated, and the period of activation correlated with the apparent rate of polyol uptake. This observation supports the notion that deactivation of the HOG pathway is closely coupled to osmotic adaptation. Taken together, our "conditional" osmotic stress system facilitates studies on aquaglyceroporin function and reveals features of the osmosensing and signaling system. © 2005 by The American Society for Biochemistry and Molecular Biology, Inc.

Aditivo polimérico derivado de fonte renovável para aplicação em cimento asfáltico de petróleo

This study evaluated the effects of incorporating an additive from an agro-industrial residue, after some chemical modification reactions, to petroleum asphalt cement (CAP) through the polymerization reaction of a viscous polyol obtained by bagasse biomass oxypropylation reaction sugarcane with anhydrides. The polyol is obtained by biomass oxypropylation reaction with propylene oxide, the reaction was performed in an autoclave sealed with pressure and temperature control using 25 mL of OP for every 5 grams of biomass 200°C, which time reaction was two hours. The reaction is revealed by varying the system pressure, initially at atmospheric pressure to reach a maximum pressure value and its subsequent return to atmospheric pressure. For the choice of the most suitable reaction time for polymerization of the polyol with pyromellitic anhydride, the reaction was also conducted in an autoclave sealed with temperature controller (150 ° C) using 20 g of polyol, 1 g of sodium acetate (catalyst) and 8 g of pyromellitic anhydride with the times 30 and 60 minutes. The polymerized materials with different times were characterized by determining the relative viscosity and percentage content of extractable in cyclohexane / ethanol. Given the results with the polymerized material 30 minutes showed the lowest percentage content of extractives and an increased viscosity relative indicating that this time is highlighted with respect to time 60 minutes, because the material is possibly in the form of a crosslinked polymer. Given the choice of time of 30 minutes other polymerization reactions were performed with various anhydrides and other conditions employed different proportions by mass of polyol anhydrides we were referred to as condition I (20 g anhydride and 8 g of polyol), II (20 g anhydride and 20 g of polyol) and III (8 g anhydride and 20 g of polyol). The FTIR spectra of polymeric materials with different polymerization conditions used to prove the occurrence of chemical modification due to the appearance of a characteristic band ester groups (1750 cm-1) present in the polymerized material. He chose to work with the condition III, as is the condition which employs a larger amount of polyol, and even with the smaller amount of anhydride used FTIR spectra revealed that the polymerization reaction was performed. Among the various anhydrides (phthalic, maleic and pyromellitic) of the different conditions used that stood out before the solubility test with solvents analyzed was polymerized material with pyromellitic anhydride because the polymerized material likely in the form of a crosslinked polymer because it was insoluble or poorly soluble in the solvents tested. Polymerization of the polyol with pyromellitic anhydride using condition III, that is, BCPP30, CSPP30, PCPP30 e BCPPG30, provided an increase in thermal stability relative to material in the form of polyol. Applicability tests concerning the incorporation of 16% m / m BCPP30, CSPP30, PCPP30 e BCPPG30 additive in relation to the mass of 600 g CAP showed through characterization tests used, softening point, elastic recovery and marshall dosage, it is possible to use BCPP30 as an additive the conventional CAP, because even with the incorporation of this new additive modified CAP met the specifications of the appropriate standard.