Resumo em Inglês:

Many reports associate electrostatic charge in dielectrics with water, either bulk, finely dispersed in aerosol or as atmospheric vapor. Two widespread but currently controversial assumptions relevant to this topic are the prevalence of electroneutrality and the passive role of water in electrical phenomena, dissipating charge due to its significant electrical conductivity. Early reports from Faraday, Kelvin and their contemporaries also point towards an active role of water as an electrifying agent. Unfortunately, these have been largely ignored or treated as scattered pieces of scientific curiosity, for over a century. New trends in this area have been developing since the late 1990s, due to a number of findings leading to radically new ideas. These derive from the experimental demonstration of widespread occurrence of non-electroneutral water and from charge partition associated with a number of interfacial phenomena, even in electrically shielded environments within grounded enclosures. This is an account on the formation and persistence of electrified water in various natural or anthropic environments, followed by experimental results obtained under well-defined conditions that are revealing different mechanisms for the role of water in charge acquisition and dissipation in dielectrics.

Resumo em Inglês:

Self-assembly of molecular gelators in a variety of liquids provides an attractive route for the construction of nanostructured materials with desired functionalities. This review focuses on correlations between structural features of gelators, specifically derivatives of long-chain, naturally-occurring fatty acids in which functional groups have been modified systematically and their gelation efficiencies in a wide range of liquids. It is shown that molecular packing at different distance scales within the gel assemblies and the microscopic and macroscopic physical properties of the gels are sensitive to even small changes in gelator sturcture and properties of the liquid component. Structural insights are provided to understand better the basis for the rational design of molecular gelators.

Resumo em Inglês:

This short review focuses on an extended study of synthetic oligomericphenyleneethynylene (OPE) electrolytes that have been investigated for both their antimicrobial activity and their fluorescence sensing properties. In both cases, interfaces between these synthetic electrolytes and naturally occurring materials such as proteins, lipids, nucleic acids and cells are critical to their function or activity. The review contains a general overview with a focus at the end on three recent examples including biological and chemical sensing, induction of spore germination and fluorescent detection of amyloid protein aggregates.

Resumo em Inglês:

Ionic detergent micelles have the capacity to solubilize organic substrates, interact selectively with counterions, repel coions, exhibit partial "dissociation" of the counterions, grow in size with added salt, affect the position of chemical equilibria, accelerate or inhibit the rates of chemical reactions, modulate photochemical reactivity and determine the dynamics of diffusion or near-diffusion controlled processes. Many of these phenomena can be understood and analyzed quantitatively in terms of relatively simple models for binding, selectivity and electrostatics that often require no knowledge of micellar structure or dynamics (the pseudophase limit), without compromising chemical intuition. An overview is provided of our current understanding of the interplay between micellar structure and electrostatics, selectivity, solubilization, and reactivity and their role in the development of quantitative formalisms for analyzing micellar effects on reactivity and equilibria.

Resumo em Inglês:

This paper reports the effect of the SWy-1 montmorillonite content on the kinetic thermal degradation of poly(2-hydroxyethyl methacrylate) (PHEMA)/SWy-1 nanocomposites prepared by in situ photopolymerization, using thermogravimetry analysis (TGA). 2-Hydroxyethyl methacrylate was photopolymerized in the presence of SWy-1 clay mineral using 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanium chloride (QTX) and triethanolamine as the photoinitiating system. X-Ray diffraction analysis indicates that the PHEMA/SWy-1 nanocomposites present an intercalated structure. The isoconversional Flynn-Wall-Ozawa method was used to estimate activation energies and pre-exponential factors for the thermal decomposition. All nanocomposites exhibited improvement in their thermal stability, mainly due to the large interaction between the PHEMA intercalated in the SWy-1 structure. The activation energies for PHEMA/SWy-1 nanocomposites increased when increasing the clay content. The SWy-1 clay mineral acts as a better insulator, mass transport barrier and as a "crosslinking agent", increasing the activation energies for the decomposition of the polymer present in the nanocomposites.

Resumo em Inglês:

Results confirm the catalytic potential of imidazole groups anchored on the polymeric backbone of polyvinylimidazole (PVI) in dephosphorylation reactions with di- and tri-phosphoesters, promoting impressive enhancements up to 107-fold. We propose the imidazole groups on PVI react by nucleophilic catalysis (neutral specie) with a phosphate triester and bifunctionally by general acid-nucleophilic catalysis (bipolar species) with a diester. Additionally, PVI can incorporate the reactants on its domains by hydrophobic and electrostatic attraction, confirming the polymer multifunctionality. Moreover, a pronounced micellar catalysis was observed for the reactions which, surprisingly, occurs with both cationic and anionic micelles, due to favorable approximation effects. The micellar effects observed confirms the reactivity of the bipolar species. Based on the pseudophase model, the reagents can be incorporated in the micellar phase, mainly by hydrophobic forces. Overall, we confirm that PVI has great potential as an artificial enzyme, since it undergoes enzymatic-like mechanisms with an elegant bifunctional catalysis.

Resumo em Inglês:

Combining two or more different compounds with advantageous properties has been a useful and straightforward strategy in achieving a new class of materials with improved physical properties. This has been especially true for electronic polymers, whose optoelectronic properties can be completely tuned, and even improved, when mixed with other polymeric materials, dye molecules and guest coordination compounds. Here, a light-emitting diode prepared with the conjugated polymer poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(9,9-di-{5'-pentanyl}-fluorenyl-2,7-diyl)] (PFOFPen) as the host material and aquo[N,N'-bis(salicylidene)-o-phenylenediamine]zinc(II) ([Zn(salophen)(OH2)]) as the guest molecule was studied in terms of its photo and electroluminescence properties. The role of the ZnII coordination compound as a guest in the electroluminescence is discussed as a strategy for the improvement of the electroluminescence performance of coordination compounds using conjugated polymers as matrices. An additional advantage of these composites is that they are solution processable, a low-cost and time efficient alternative to vacuum vapor deposition. Additionally, the photophysical processes involved in both electroluminescence and photoluminescence emissions are discussed because they are markedly different.

Resumo em Inglês:

This article reports the characterization of mesoporous Nb2O5 synthesized by the sol-gel method for application in photocatalysis. The emerging contaminant methylviologen was employed for photocatalytic tests. Parameters inherent to the synthesis process, such as stirring rate, aging temperature, and calcination temperature, were employed for a range of values to improve the synthetic route. The powders obtained were characterized by thermogravimetric analysis, X-ray diffraction, scanning and transmission electron microscopy, specific surface area, infrared spectroscopy, energy-dispersive spectroscopy, and diffuse reflectance spectroscopy. In samples calcined at 450 °C, a mixture of amorphous and hexagonal phases was observed, with a predominance of the former, while in samples calcined at 650 °C the orthorhombic phase predominated. Samples calcined at 450 °C exhibited larger specific surface areas. Mesoporous structures were confirmed for samples T8035M450 and T8045mi450, which displayed higher photoactivity, with roughly 90% removal of methylviologen.

Resumo em Inglês:

The dynamics of sucessive impacts of water droplets against flat glass surfaces covered by Langmuir-Blodgett films of zinc stearate with 1, 3, 5 and 7 layers was investigated. The structure and resistance of monolayers to the impact was evaluated by using fast images of the drop deformation, Brewster angle microscopy (BAM) and contact angle measurements. Eventual disruption (erosion) of the layers was investigated by using sum-frequency vibrational spectroscopy (SFG).

Resumo em Inglês:

A biphasic catalytic system based in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate was employed for tandem hydroformylation-amine condensation reactions of soybean FAME using HRhCO(PPh3)3 as the catalyst precursor and n-butylamine. Using a tenfold excess of the ligand PPh3, the presence of the ionic liquid increased the selectivity for imine if compared to the reaction carried out under similar conditions, but in homogeneous media.The yield for imine reached 75% after 24 h. On the other hand, in the absence of a PPh3 excess, the effect of using the ionic liquid was opposite and the selectivity for imine decreased. This supposedly occurred due to the generation ofN-heterocyclics carbenes, which would coordinate to Rh to form species active for parallel and/or consecutive reactions. When an excess PPh3 is used, it suppress the carbenes coordination, maintaining the Rh complex in a form active for hydroformylation.The obtained imine products presented remarkable antimicrobial activity towards a set of fungi and bacteria commonly present in fuel storage tanks.

Resumo em Inglês:

Ethyl- and n- propylbenzene peroxidation has been studied in the presence of supported gold nanoparticles on TiO2(AuNP@TiO2). The decomposition products obtained from Fenton-induced cumene hydroperoxide decomposition, as well as the oxidation products of ethyl- and n- propylbenzene, implicate the participation of reactive oxygen species adsorbed on the AuNP surface. This surface intermediate is believed to be a fundamental participant in hydrogen abstraction reactions required to facilitate the formation of the observed carbonyl derived product.

Resumo em Inglês:

Photo-Fenton degradation of pollutants involves the reaction of FeIIsalts with hydrogen peroxide under ultraviolet A irradiation, which significantly enhances the process. The reaction with FeIIIsalts is slower and therefore less studied. In this work, we compared the efficiencies of FeIIIand FeII salts in the photo-Fenton degradation of malachite green (MG), a known carcinogen. We optimized the concentration of reagents and the pH to achieve the highest MG degradation with the lowest amounts of reagents. Complete MG degradation was achieved under 2 h for the FeIIIsystem and 1 h for FeII, reaching a high degree of mineralization, even in the presence of chloride and sulfate anions. The results show that although slower, the reaction with FeIIIsalts allows significant photodegradation of MG under mild reaction conditions.

Resumo em Inglês:

In this contribution we present an overview on the relation between the complex structure of ionic liquids (ILs) and its impact in the field of surface science. The results herein described result mainly from modeling and simulation work carried out at Centro de Química Estrutural, Universidade de Lisboa, complemented in some cases by experimental results obtained at Instituto de Tecnologia Química e Biológica, Universidade Nova de Lisboa or elsewhere. The overview starts with the description of nano-segregation and self-aggregation phenomena experienced by pure ionic liquids in bulk phases (bi-continuous structures in the isotropic liquid or the formation of liquid-crystal phases). This is followed by the analysis of IL self-aggregation in molecular solvent solutions (micelle or gel formation). The second part of the overview is devoted to the study of the structuration of ILs at the IL/vacuum, IL/liquid or IL/solid interfaces. The final part deals with thin IL films stabilized between air/solid, air/liquid or solid/solid boundaries.

Resumo em Inglês:

In this work, composites based on carbon (1, 10 and 20 wt.%) interfaced with Fe3O4 (magnetite) have been studied as catalysts for the oxidation of aqueous sulfide. The composites were prepared by assembling cellulose nanocrystals surrounding Fe3O4 followed by a controlled thermal decomposition at 400, 600 and 800 ºC. Mössbauer, X-ray diffractometry (XRD), Raman, thermogravimetry (TG), elemental analysis CHN, scanning electron microscopy (SEM/EDS), Fourier transform infrared spectroscopy (FTIR) and potentiometric titration indicated that at 400 and 600 ºC the cellulose nanocrystals decompose to different carbon forms, i.e., films, filaments and particles attached to the Fe3O4 crystals. At higher temperature, i.e., 800 ºC, this carbon on the magnetite surface further reacted to produce Fe0. UV-Vis, Raman and electrospray ionization mass spectrometry (ESI-MS) measurements showed that these composites catalyze the oxidation of aqueous sulfide to convert S2-aq to polysulfides Sn2- (where n = 2-9) and also oxygen containing polysulfides HOSn-. Simple kinetic experiments showed very low sulfide oxidation activities for pure Fe3O4 and pure carbon. On the other hand, the composites, especially with 10% C obtained at 600 ºC, were remarkably active. These results are discussed in terms of a possible participation of oxygen based redox groups present on the carbon surface and an electron transfer from the carbon to the Fe3O4 phase.

Resumo em Inglês:

Palladium nanoparticles (NPs) stabilized by ImS3-14, a zwitterionic surfactant structurally related to ionic liquids, are revealed here to be good catalysts for the reduction of a large number of substituted aromatic nitro compounds. Our mass spectrometry results are consistent with the formation of amino products in a direct route, where the aromatic nitro compounds are initially reduced to nitroso compounds, which are then reduced to the hydroxylamine derivatives and finally to the anilines. Activation parameters showed that for most Pd catalysts reported in the literature, the mechanism seems to be similar, with lower enthalpy of activation (ΔH‡) being compensated by more negative entropy of activation (ΔS‡). As a result, the reaction is thermally compensated and the rate constants for most reactions rather similar. Furthermore, Pd NPs stabilized by ImS3-14 showed efficient catalytic activities for the reduction of aromatic nitro compounds, with high conversion and good selectivity even using very low loadings of metal.

Resumo em Inglês:

This paper aimed to study the mode of inclusion for 7-hydroxyflavone (7HF) in β-cyclodextrin (β-CD) complex in basic (pH 12) and acid (pH 4.5) media. The thermodynamic parameters of the complexation of 7HF with β-CD were evaluated by means of steady-state fluorescence and solubility measurements at several temperatures. The 7HF-β-CD inclusion complex was spontaneously formed at 1:1 stoichiometry in both basic and acid media. The high number of hydrogen bonds formed between the host and the guest molecules favored complexation in the basic medium, with a ground-state equilibrium constant (K) of 990 ± 130 mol-1 L, at 25 ºC. The quantum-mechanics calculations showed that complexation of 7HF (neutral or anionic form) with β-CD occurred mainly via the phenyl group of the flavonoid. This result agreed with the induced circular dichroism signal of 7HF complexed with β-CD.

Resumo em Inglês:

Phase behavior of didodecyl and dioctadecydimethylammonium bromide (DDAB and DODAB) in water was studied using X-ray techniques, differential scanning calorimetry and deuterium nuclear magnetic resonance measurements. Both surfactants self-assemble into lamellar liquid crystalline, either Lα (fluid) and Lβ (gel), phases. The gel-to-fluid phase transition temperature (Tm) in DDAB lamellae was found to be higher than that observed for its vesicles, due to the formation of a stabilized gel phase. In addition, the lamellar phases formed by both amphiphiles differ in their swelling degree and bilayer thickness. DODAB in water formed rather thin bilayers, if compared with the length of the tails, suggesting effective chain interdigitation. These bilayers also presented higher swelling degree than those formed by the shorter-chain homologue DDAB. We propose that these structural properties are strongly influenced by the electrostatic repulsive forces acting on the system.

Resumo em Inglês:

Glycolipids are biomolecules composed of a lipid chain (lipophilic) and a monosaccharide or oligosaccharide as hydrophilic group. Their chemical structure and biological role make them undoubtedly good candidates for a large and continuously growing number of biotechnological applications. Mannose is a carbohydrate present on membrane glycolipids of a wide number of pathogenic microorganisms (bacteria, fungi, protozoa, and viruses) and specifically recognized by several lectins. We synthesized a mannose derivative linked through a short methylene chain to a pyrene moiety which behaves as a surfactant, able to aggregate, and retains the photophysical properties of pyrene: showing comparable absorption and emission spectra, having lower fluorescence quantum yield and the ability to form excimer, and finally the ability to produce O2(1Δg) with high quantum yields. Thus, this novel molecule would open future applications for detection (fluorescence) or inactivation (singlet oxygen) of bacterial pathogens, viruses, tumor cells, or particular cells.

Resumo em Inglês:

Deleterious effect mediated by glucose degradation, as a parallel pathway to Maillard reaction, was analyzed in terms of the feasibility of inducing photo-crosslinking in isolated bovine crystalline proteins when exposed to ultraviolet A (UVA)-visible light. These experiments showed evidence supporting the generation of a glucose-derived chromophore (GDC). The ability of this chromophore to induce oxidative damage in lens protein and bovine lens epithelial cells (BLEC) was further assessed. The analysis of dityrosine and carbonyl levels in lens proteins irradiated at 5 and 20% O2 indicates the occurrence of mixed type I/type II photosensitizing mechanisms. When BLEC were exposed to photosensitized reactions induced by GDC a decrease in cellular viability and intracellular reduced (GSH) and oxidized (GSSG) glutathione ratio was observed, as well as an increase in the amount of intracellular reactive oxygen species. Our data suggest a major effect of type I photosensitizing mechanism in both lens proteins photo-oxidation and oxidative stress induced in BLEC.

Resumo em Inglês:

This work describes ultrafast spectroscopy studies of Au triangular pyramid particle arrays deposited over glass (termed Au/glass), and 190 nm indium tin oxide (ITO) film (termed Au/ITO/glass) prepared by nanosphere lithography. The linear absorption spectra of Au/glass and Au/ITO/glass exhibit surface plasmon resonances at 800 and 870 nm, respectively, in good agreement with discrete dipole approximation simulations. Ultrafast pump-probe measurements at wavelengths below resonance, at resonance, and above the surface plasmon resonance for each of these two systems are presented. The pump-probe measurements on both systems can be well fit with a model accounting for electron-electron scattering, electron-phonon coupling, and acoustic oscillations on top of cooling of the gold lattice. Numerical simulations employing a two-temperature model are consistent with the single-color pump-probe exponential decays. The wavelength-dependent pump-probe results are interpreted in terms of the complex wavelength-dependent refractive index of gold. We show that this interpretation is consistent with diffractive-optic four-wave mixing spectroscopy measurements of absorptive and dispersive parts of the third-order nonlinear polarization at 800 nm.