Eletrodos modificados por hidróxido de níquel: um estudo de revisão sobre suas propriedades estruturais e eletroquímicas visando suas aplicações em eletrocatálise, eletrocromismo e baterias secundárias

The present review paper describes the main features of nickel hydroxide modified electrodes covering its structural and electrochemical behavior and the newest advances promoted by nanostructured architectures. Important aspects such as synthetic procedures and characterization techniques such as X-Ray diffraction, Raman and Infrared spectroscopy, Electronic Microscopy and many others are detailed herein. The most important aspect concerning nickel hydroxide is related to its great versatility covering different fields in electrochemical-based devices such as batteries, electrocatalytic systems and electrochromic electrodes, the fundamental issues of these devices are also commented. Finally, some of the newest advances achieved in each field by the incorporation of nanomaterials will be shown.

Produção de substratos sers eficientes através da deposição de ouro sobre um molde de microesferas de poliestireno

This work reports on the SERS activity of a nanostructured substrate that was obtained by electrodepositing gold over a template consisting of polystyrene microspheres. This substrate displayed superior SERS performance for the detection of 4-merctaptopyridine as compared to a conventional roughened Au electrode. In order to investigate the substrate capability for the detection at low concentration limits, a series of Rhodamine 6G (1 nM) spectra were registered. Our spectral dynamics data is in agreement with single-molecule behavior, showing that the control over the substrate morphology is crucial to enable the production of highly reproducible and sensitive SERS substrates.

Rheology of decane/water and triglyceride/water emulsions stabilized by β-casein and sodium caseinate

β-Casein and sodium caseinate stabilized emulsions were produced and had their rheological properties investigated as a function of the nature of the oil phase, ionic strength and pH. Oil phases of distinct structural characteristics, namely decane and vegetable oil of high triglyceride content, were assayed. The former was much more effectively emulsified than the latter. Effects of pH and ionic strength were minor. Emulsion rheological properties were strikingly distinct in each case, with viscoelastic, solid-like structures being formed with decane (G' >> G"), differently from what is observed for samples containing triglycerides as the oil phase, in which viscoelasticity was not even apparent. The relevance of the spatial features of the oil phase structure in the development of the emulsion viscoelastic character is discussed. Factors responding for the system distinct behaviour possibly reside at the emulsion droplet interface, unapproachable by optical microscopy, rather than on aspects related to particle size or shape.

Rheology of decane/water and triglyceride/water emulsions stabilized by 'beta'-casein and sodium caseinate

Emulsões estabilizadas por 'beta'-caseína e sódio caseinato tiveram suas propriedades reológicas investigadas em função da natureza da fase oleosa, da força iônica e do pH. Fases oleosas de características estruturais distintas, a saber, decano e óleos vegetais de alto teor triglicerídico, foram ensaiadas. A emulsificação dos sistemas contendo decano foi significativamente mais efetiva do que aquela das amostras contendo triglicérides. Efeitos de pH e força iônica mostraram-se relativamente pouco importantes sobre a capacidade emulsificante da proteína. As propriedades reológicas foram marcadamente distintas em cada caso, com estruturas de caráter sólido (G' G") sendo produzidas com decano, diferentemente do que foi observado para amostras contendo triglicérides, nas quais a viscoelasticidade não foi nem mesmo aparente. A relevância de aspectos espaciais da estrutura da fase oleosa no desenvolvimento do caráter viscoelástico é discutida. Propõe-se que os fatores responsáveis pelo comportamento distinto observado residam possivelmente na interface gotícula/meio dispersante, inacessível por microscopia óptica, e guardam pouca relação com tamanho ou forma da gotícula.

Enhanced luminescence of Tb(3+)/Eu(3+) doped tellurium oxide glass containing silver nanostructures

We report on energy transfer studies in terbium (Tb(3+))-europium (Eu(3+)) doped TeO(2)-ZnO-Na(2)O-PbO glass containing silver nanostructures. The samples excitation was made using ultraviolet radiation at 355 nm. Luminescence spectra were recorded from approximate to 480 to approximate to 700 nm. Enhanced Eu(3+) luminescence at approximate to 590 nm (transition (5)D(0)-(7)F(1)) and approximate to 614 nm (transition (5)D(0)-(7)F(2)) are observed. The large luminescence enhancement was obtained due to the simultaneous contribution of the Tb(3+)-Eu(3+) energy transfer and the contribution of the intensified local field on the Eu(3+) ions located near silver nanostructures.

Modification of composition of a nanoemulsion with different cholesteryl ester molecular species: Effects on stability, peroxidation, and cell uptake

Purpose: Use of lipid nanoemulsions as carriers of drugs for therapeutic or diagnostic purposes has been increasingly studied. Here, it was tested whether modifications of core particle constitution could affect the characteristics and biologic properties of lipid nanoemulsions. Methods: Three nanoemulsions were prepared using cholesteryl oleate, cholesteryl stearate, or cholesteryl linoleate as main core constituents. Particle size, stability, pH, peroxidation of the nanoemulsions, and cell survival and uptake by different cell lines were evaluated. Results: It was shown that cholesteryl stearate nanoemulsions had the greatest particle size and all three nanoemulsions were stable during the 237-day observation period. The pH of the three nanoemulsion preparations tended to decrease over time, but the decrease in pH of cholesteryl stearate was smaller than that of cholesteryl oleate and cholesteryl linoleate. Lipoperoxidation was greater in cholesteryl linoleate than in cholesteryl oleate and cholesteryl stearate. After four hours' incubation of human umbilical vein endothelial cells (HUVEC) with nanoemulsions, peroxidation was minimal in the presence of cholesteryl oleate and more pronounced with cholesteryl linoleate and cholesteryl stearate. In contrast, macrophage incubates showed the highest peroxidation rates with cholesteryl oleate. Cholesteryl linoleate induced the highest cell peroxidation rates, except in macrophages. Uptake of cholesteryl oleate nanoemulsion by HUVEC and fibroblasts was greater than that of cholesteryl linoleate and cholesteryl stearate. Uptake of the three nanoemulsions by monocytes was equal. Uptake of cholesteryl oleate and cholesteryl linoleate by macrophages was negligible, but macrophage uptake of cholesteryl stearate was higher. In H292 tumor cells, cholesteryl oleate showed the highest uptakes. HUVEC showed higher survival rates when incubated with cholesteryl stearate and smaller survival with cholesteryl linoleate. H292 survival was greater with cholesteryl stearate. Conclusion: Although all three nanoemulsion types were stable for a long period, considerable differences were observed in size, oxidation status, and cell survival and nanoemulsion uptake in all tested cell lines. Those differences may be helpful in protocol planning and interpretation of data from experiments with lipid nanoemulsions.

Leukotriene B(4)-loaded microspheres: a new therapeutic strategy to modulate cell activation

Background: Leukotriene B(4) (LTB(4)) is a potent inflammatory mediator that also stimulates the immune response. In addition, it promotes polymorphonuclear leukocyte phagocytosis, chemotaxis, chemokinesis and modulates cytokines release. Regarding chemical instability of the leukotriene molecule, in the present study we assessed the immunomodulatory activities conferred by LTB(4) released from microspheres (MS). A previous oil-in-water emulsion solvent extraction-evaporation method was chosen to prepare LTB(4)-loaded MS. Results: In the mice cremasteric microcirculation, intraescrotal injection of 0.1 ml of LTB(4)-loaded MS provoked significant increases in leukocyte rolling flux, adhesion and emigration besides significant decreases in the leukocyte rolling velocity. LTB(4)-loaded MS also increase peroxisome proliferator-activated receptor-alpha (PPAR alpha) expression by murine peritoneal macrophages and stimulate them to generate nitrite levels. Monocyte chemoattractant protein-I (MCP-I) and nitric oxide (NO) productions were also increased when human umbilical vein and artery endothelial cells (HUVECs and HUAECs, respectively) were stimulated with LTB(4)-loaded MS. Conclusion: LTB(4)-loaded MS preserve the biological activity of the encapsulated mediator indicating their use as a new strategy to modulate cell activation, especially in the innate immune response.

Lipid Metabolism in Subclinical Hypothyroidism: Plasma Kinetics of Triglyceride-Rich Lipoproteins and Lipid Transfers to High-Density Lipoprotein Before and After Levothyroxine Treatment

Background: Subclinical hypothyroidism (SCH) has been associated with atherosclerosis, but the abnormalities in plasma lipids that can contribute to atherogenesis are not prominent. The aim of this study was to test the hypothesis that patients with normocholesterolemic, normotriglyceridemic SCH display abnormalities in plasma lipid metabolism not detected in routine laboratory tests including abnormalities in the intravascular metabolism of triglyceride-rich lipoproteins, lipid transfers to high-density lipoprotein (HDL), and paraoxonase 1 activity. The impact of levothyroxine (LT4) treatment and euthyroidism in these parameters was also tested. Methods: The study included 12 SCH women and 10 matched controls. Plasma kinetics of an artificial triglyceride-rich emulsion labeled with radioactive triglycerides and cholesteryl esters as well as in vitro transfer of four lipids from an artificial donor nanoemulsion to HDL were determined at baseline in both groups and after 4 months of euthyroidism in the SCH group. Results: Fractional clearance rates of triglycerides (SCH 0.035 +/- 0.016 min(-1), controls 0.029 +/- 0.013 min(-1), p=0.336) and cholesteryl esters (SCH 0.009 +/- 0.007 min(-1), controls 0.009 +/- 0.009 min(-1), p=0.906) were equal in SCH and controls and were unchanged by LT4 treatment and euthyroidism in patients with SCH, suggesting that lipolysis and remnant removal of triglyceride-rich lipoproteins were normal. Transfer of triglycerides to HDL (SCH 3.6 +/- 0.48%, controls 4.7 +/- 0.63%, p=0.001) and phospholipids (SCH 16.2 +/- 3.58%, controls 21.2 +/- 3.32%, p=0.004) was reduced when compared with controls. After LT4 treatment, transfers increased and achieved normal values. Transfer of free and esterified cholesterol to HDL, HDL particle size, and paraoxonase 1 activity were similar to controls and were unchanged by treatment. Conclusions: Although intravascular metabolism of triglyceride-rich lipoproteins was normal, patients with SCH showed abnormalities in HDL metabolism that were reversed by LT4 treatment and achievement of euthyroidism.

Spin-wave fluctuations in ferrimagnetic Mg(x)Fe(3-x)O(4) nanoparticles

We have performed a systematic study of the magnetic properties of a series of ferrimagnetic nanoparticles of Mg(x)Fe(3-x)O(4) (0.8 <= x <= 1.5) prepared by the combustion reaction method. The magnetization data can be well fitted by Bloch's law with T(3/2). Bloch's constant B determined from the fitting procedure was found to increase with Mg content x from similar to 3.09 X 10(-5) K(-3/2) for x = 0.8 to 6.27 X 10(-5) K(-3/2) for x=1.5. The exchange integral J(AB) and the spin-wave stiffness constant D of Mg(x)Fe(3-x)O(4) nanoparticles were also determined as similar to 0.842 and 0.574 meV and 296 and 202 meV angstrom(2) for specimens with x=0.8 and 1.5, respectively. These results are discussed in terms of cation redistribution among A and B sites on these nanostructured spinel ferrites. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3359709]

Edge effects in bilayer graphene nanoribbons: Ab initio total-energy density functional theory calculations

We show that the ground state of zigzag bilayer graphene nanoribbons is nonmagnetic. It also possesses a finite gap, which has a nonmonotonic dependence with the width as a consequence of the competition between bulk and strongly attractive edge interactions. All results were obtained using ab initio total-energy density functional theory calculations with the inclusion of parametrized van der Waals interactions.

Electronic, structural, and transport properties of Ni-doped graphene nanoribbons

We have investigated the electronic and transport properties of zigzag Ni-adsorbed graphene nanoribbons (Ni/GNRs) using ab initio calculations. We find that the Ni adatoms lying along the edge of zigzag GNRs represent the energetically most stable configuration, with an energy difference of approximately 0.3 eV when compared to the adsorption in the middle of the ribbon. The carbon atoms at the ribbon edges still present nonzero magnetic moments as in the pristine GNR even though there is a quenching by a factor of almost five in the value of the local magnetic moments at the C atoms bonded to the Ni. This quenching decays relatively fast and at approximately 9 A from the Ni adsorption site the magnetic moments have already values close to the pristine ribbon. At the opposite edge and at the central carbon atoms the changes in the magnetic moments are negligible. The energetic preference for the antiparallel alignment between the magnetization at the opposite edges of the ribbon is still maintained upon Ni adsorption. We find many Ni d-related states within an energy window of 1 eV above and below the Fermi energy, which gives rise to a spin-dependent charge transport. These results suggest the possibility of manufacturing spin devices based on GNRs doped with Ni atoms.

Synergistic interaction between gold nanoparticles and nickel phthalocyanine in layer-by-layer (LbL) films: evidence of constitutional dynamic chemistry (CDC)

The concept of constitutional dynamic chemistry (CDC) based on the control of non-covalent interactions in supramolecular structures is promising for having a large impact on nanoscience and nanotechnology if adequate nanoscale manipulation methods are used. In this study, we demonstrate that the layer-by-layer (LbL) technique may be used to produce electroactive electrodes with ITO coated by tetrasulfonated nickel phthalocyanine (NiTsPc) alternated with poly(allylamine hydrochloride) (PAH) incorporating gold nanoparticles (AuNP), in which synergy has been achieved in the interaction between the nanoparticles and NiTsPc. The catalytic activity toward hydrogen peroxide (H(2)O(2)) in multilayer films was investigated using cyclic voltammetry, where oxidation of H(2)O(2) led to increased currents in the PAH-AuNP/NiTsPc films for the electrochemical processes associated with the phthalocyanine ring and nickel at 0.52 and 0.81 V vs. SCE, respectively, while for PAH/NiTsPc films (without AuNP) only the first redox process was affected. In control experiments we found out that the catalytic activity was not solely due to the presence of AuNP, but rather to the nanoparticles inducing NiTsPc supramolecular structures that favored access to their redox sites, thus yielding strong charge transfer. The combined effects of NiTsPc and AuNP, which could only be observed in nanostructured LbL films, point to another avenue to pursue within the CDC paradigm.

Immobilization and stabilization of microbial lipases by multipoint covalent attachment on aldehyde-resin affinity: Application of the biocatalysts in biodiesel synthesis

Microbial lipase preparations from Thermomyces lanuginosus (TLL) and Pseudomonas fluorescens (PFL) were immobilized by multipoint covalent attachment on Toyopearl AF-amino-650M resin and the most active and thermal stable derivatives used to catalyze the transesterificanon reaction of babassu and palm oils with ethanol in solvent-free media For this different activating agents mainly glutaraldehyde glycidol and epichlorohydrin were used and immobilization parameters were estimated based on the hydrolysis of olive oil emulsion and butyl butyrate synthesis ILL immobilized on glyoxyl-resin allowed obtaining derivatives with the highest hydrolytic activity (HA(der)) and thermal stability between 27 and 31 times more stable than the soluble lipase Although PFL derivatives were found to be less active and thermally stables similar formation of butyl butyrate concentrations were found for both ILL and PFL derivatives The highest conversion into biodiesel was found in the transesterification of palm oil catalyzed by both ILL and PFL glyoxyl-derivatives (c) 2010 Elsevier B V All rights reserved

Influence of Granulometry and Organic Treatment of a Brazilian Montmorillonite on the Properties of Poly(styrene-co-n-butyl acrylate)/Layered Silicate Nanocomposites Prepared by Miniemulsion Polymerization

The influence of granulometry and organic treatment of a Brazilian montmorillonite (MMT) clay on the synthesis and properties of poly(styrene-co-n-butyl acrylate)/layered silicate nanocomposites was studied. Hybrid latexes of poly(styrene-co-butyl acrylate)/MMT were synthesized via miniemulsion polymerization using either sodium or organically modified MMT. Five clay granulometries ranging from clay particles smaller than 75 mu m to colloidal size were selected. The size of the clay particles was evaluated by Specific surface area measurements (BET). Cetyl trimethyl ammonium chloride was used as an organic modifier to enhance the clay compatibility with the monomer phase before polymerization and to improve the clav distribution and dispersion within the polymeric matrix after polymerization. The sodium and organically modified natural clays as well as the composites were characterized by X-ray diffraction analysis. The latexes were characterized by dynamic light scattering. The mechanical, thermal, and rheological properties of the composites obtained were characterized by dynamical-mechanical analysis, thermogravimetry, and small amplitude oscillatory, shear tests, respectively. The results showed that smaller the size of the organically modified MMT, the higher the degree of exfoliation of nanoplatelets. Hybrid latexes in presence of Na-MMT resulted in materials with intercalated structures. (C) 2009 Wiley, Periodicals, Inc. J Appl Polym Sci 112: 1949-1958, 2009

Sensor arrays to detect humic substances and Cu(II) in waters

The interaction between poly(o-ethoxyaniline) (POEA) adsorbed onto solid substrates and humic substances (HS) and Cu(2+) ions has been investigated using UV-vis spectroscopy and atomic force microscopy (AFM). Both HS and Cu(2+) are able to dope POEA and change film morphology. This interaction was exploited in a sensor array made with nanostructured films of POEA, sulfonated lignin and HS, which could detect small concentrations of HS and Cu(2+) in water. (C) 2009 Elsevier B.V. All rights reserved.