Estudos da eletrodeposição de metais em regime de subtensão

This work reviews recent studies of underpotential deposition (UPD) of several metals on Pt and Au substrates performed in the Grupo de Materiais Eletroquímicos e Métodos Eletroanalíticos (IQSC -- USP, São Carlos). The UPD Cu, Cd and Pb on Pt were analysed in terms of their influence in the oxygen evolution reaction. Partial blockage of surface active sites, promoted by Pb ad-atoms, resulted in a change from water to hydrogen peroxide as the final product. The Ag UPD on Pt and Au substrates was also discussed in this work. A detailed model of charge calculation for Ag monolayer was developed and confirmed by the rotating ring-disk data. The partial charge transfer in UPD studies was analysed in the Cd/Pt and Cd/Au systems and a value of 0.5 was found for the adsorption electrovalence of Cd ad-ions. The Sn/Pt UPD systems were studied from the point of view of the valences of metallic ions in solution. The deposition from Sn(IV) generates a full monolayer with a maximum occupation of approximately 40% of the surface active sites (340 µC cm-2) plus 105 µC cm-2 of Hads (half monolayer). Changing the metallic ion for Sn(II), it was possible to deposit a full monolayer (210 µC cm-2) without any detectable Hads. Finally, the effect of anions was discussed in the Zn/Pt and Zn/Au systems. Here, the hydrogen evolution reaction (her) and the hydrogen adsorption/desorption were used in order to investigate the maximum coverage of the surface with Zn ad-atoms. The full monolayer, characterised by the complete absence of Hads, was achieved only in 0.5 M HF solutions.

The summer North Atlantic Oscillation in CMIP3 models and related uncertainties in projected summer drying in Europe

This paper discusses uncertainties in model projections of summer drying in the Euro-Mediterranean region related to errors and uncertainties in the simulation of the summer NAO (SNAO). The SNAO is the leading mode of summer SLP variability in the North Atlantic/European sector and modulates precipitation not only in the vicinity of the SLP dipole (northwest Europe) but also in the Mediterranean region. An analysis of CMIP3 models is conducted to determine the extent to which models reproduce the signature of the SNAO and its impact on precipitation and to assess the role of the SNAO in the projected precipitation reductions. Most models correctly simulate the spatial pattern of the SNAO and the dry anomalies in northwest Europe that accompany the positive phase. The models also capture the concurrent wet conditions in the Mediterranean, but the amplitude of this signal is too weak, especially in the east. This error is related to the poor simulation of the upper-level circulation response to a positive SNAO, namely the observed trough over the Balkans that creates potential instability and favors precipitation. The SNAO is generally projected to trend upwards in CMIP3 models, leading to a consistent signal of precipitation reduction in NW Europe, but the intensity of the trend varies greatly across models, resulting in large uncertainties in the magnitude of the projected drying. In the Mediterranean, because the simulated influence of the SNAO is too weak, no precipitation increase occurs even in the presence of a strong SNAO trend, reducing confidence in these projections.

Understanding Flood Regime Changes in Europe: a state-of-the-art assessment

There is growing concern that flooding is becoming more frequent and severe in Europe. A better understanding of flood regime changes and their drivers is therefore needed. The paper reviews the current knowledge on flood regime changes in European rivers that has traditionally been obtained through two alternative research approaches. The first approach is the data-based detection of changes in observed flood events. Current methods are reviewed together with their challenges and opportunities. For example, observation biases, the merging of different data sources and accounting for nonlinear drivers and responses. The second approach consists of modelled scenarios of future floods. Challenges and opportunities associated with flood change scenarios are discussed such as fully accounting for uncertainties in the modelling cascade and feedbacks. To make progress in flood change research, we suggest that a synthesis of these two approaches is needed. This can be achieved by focusing on long duration records and flood-rich and flood-poor periods rather than on short duration flood trends only, by formally attributing causes of observed flood changes, by validating scenarios against observed flood regime dynamics, and by developing low-dimensional models of flood changes and feedbacks. The paper finishes with a call for a joint European flood change research network.

Fiscal Regime Shifts in Portugal

We estimate changes in fiscal policy regimes in Portugal with a Markov Switching regression of fiscal policy rules for the period 1978-2007, using a new dataset of fiscal quarterly series. We find evidence of a deficit bias, while repeated reversals of taxes making the budget procyclical. Economic booms have typically been used to relax tax pressure, especially during elections. One-off measures have been preferred over structural ones to contain the deficit during economic crises. The EU fiscal rules prompted temporary consolidation, but did not permanently change the budgeting process.

Experimentos didáticos envolvendo radiação microondas

Theoretical and practical aspects of the use of microwave-assisted strategies in chemistry are introduced for students using simple and safe experiments employing a domestic oven. Three procedures are proposed for evaluating the distribution of microwave radiation inside the microwave oven cavity: (1) variation of the volume of marshmallows; (2) drying of filter paper wetted with Co(II) solution, and (3) variation of water temperature, after microwave-assisted heating. These experiments establish the position with the highest incidence of microwave radiation in the oven cavity, which was chosen for the synthesis of salicylic acid acetate. This synthesis was performed in 5 min of heating and the yield was around 85%. All experiments can be carried out in a 4 h lab-session using low-cost instrumentation.

The effect of microfibrillated cellulose addition on drying shrinkage and dimensional stability of wood-free paper

Microfibrillated cellulose (MFC) is known to enhance strength properties of paper. Improved strength usually means increased bonding which is strongly connected to dimensional instability of paper. Dimensional instability is due to changes in moisture content of paper; when paper is moistened it expands and when dried, it shrinks. Hygroexpansion is linked to end-use problems and excessive drying shrinkage consumes strength potential. Effective use of materials requires controlling of these phenomena. There isn’t yet data concerning dimensional stability of papers containing MFC which restricts wider use of MFC. Main objective of the work was to evaluate dimensional stability of wood-free paper containing different amounts of MFC. Sheets were dried with different methods to see how drying strains effected on drying shrinkage and hygroexpansion. Also tensile strength was measured to find out the effect of MFC. Results were compared to sheets containing kraft fines and in some test points cationic starch was used alongside with MFC. MFC increased the dimensional instability of freely dried sheets. As the amounts of MFC increased the effects on dimensional stability became more severe. However the fineness of MFC didn’t play any important role. Both hygroexpansion and drying shrinkage were decreased with cationic starch addition. Prevention of drying shrinkage over powered the effects of additives on hygroexpansion. Tensile strength improved up till 7 % addition amount which could be set as the upper limit of MFC addition when paper preparation and tensile strength are concerned.

Microencapsulação do agente quelante sulfoxina em microesferas de quitosana preparadas por spray drying como novo adsorvente para íons metálicos

In this work, a new adsorbent was prepared by microencapsulation of sulfoxine into chitosan microspheres by the spray drying technique. The new adsorbent was characterized by Raman spectroscopy, scanning electron microscopy and microanalysis of energy dispersive X-rays. The Cu(II) adsorption was studied as a function of pH, time and concentration. The optimum pH was found to be 6.0. The kinetic and equilibrium data showed that the adsorption process followed the pseudo second-order kinetic model and the Langmuir isotherm model over the entire concentration range. An increase of 8.0% in the maximum adsorption capacity of the adsorbent (53.8 mg g-1) was observed as compared to chitosan glutaraldehyde cross-linked microspheres.

Imobilização da lacase em micropartículas de quitosana obtidas por spray drying e usadas na construção de biossensores

Biosensors based on laccase immobilized on microparticles of chitosan crosslinked with tripolyphosphate (biosensor I) and glyoxal (biosensor II) obtained by spray drying for the determinations of rutin in pharmaceutical formulations were developed. Under optimized operational conditions (pH 4.0, frequency of 30 Hz, pulse amplitude of 40 mV and scan increment of 2.0 mV) two analytical curves were obtained for both biosensors showing a detection limit of 6.2x10-8 mol L-1 for biosensor (I) and 2.0x10-8 mol L-1 for biosensor (II). The recovery of rutin from pharmaceutical sample ranged from 90.7 to 105.0% and the lifetime of these biosensors were 4 months (at least 400 determinations).

An expeditious and consistent procedure for tetrahydrofuran (THF) drying and deoxygenation by the still apparatus

Despite the availability of alternative methods for drying tetrahydrofuran (THF), the use of the still apparatus, wherein a THF solution containing Na-bezophenone ketyl is heated to reflux, remains widespread. We herein propose a set of procedures to solve the problems usually faced in applying this drying technique. Moreover, a discussion is made on the chemical knowledge underlying such procedures. Safety and economy issues concerned with the operation of the THF still apparatus are also discussed.

Evaluation of chitosan microparticles containing curcumin and crosslinked with sodium tripolyphosphate produced by spray drying

The aim of this study was to encapsulate curcumin into chitosan, using sodium tripolyphosphate (TPP) as an ionic crosslinker by the spray drying method. The influence of TPP on the properties of the final product, such as solubility, morphology, loading efficiency, thermal behavior, swelling degree and release profiles, was evaluated. The microparticles had a spherical morphology (0.5-20 µm) with no apparent porosity or cracks. Results indicated the formation of a polymeric network, which ensures effective protection for curcumin. Controlled-release studies were carried out at pH 1.2 and 6.8, to observe the influence of pH on curcumin release while the mechanism was analyzed using the Korsmeyer-Peppas equation.

ENCAPSULAÇÃO DO ÁCIDO L-ASCÓRBICO NO BIOPOLÍMERO NATURAL GALACTOMANANA POR SPRAY‑DRYING: PREPARAÇÃO, CARACTERIZAÇÃO E ATIVIDADE ANTIOXIDANTE

AbstractIn this study, the spray drying technique was used to prepare L-ascorbic acid (AA) microparticles encapsulated with galactomannan-an extract from the seeds of the Delonix regia species. The physico-chemical characteristics, antioxidant activity, and encapsulation efficiency of the AA microparticles were evaluated and characterized using thermogravimetric analysis, differential scanning calorimetry, infrared spectroscopy, X-ray diffraction, and scanning electron microscopy. The free-radical scavenging activity of the AA microparticles was determined at different environmental conditions using DPPH (1,1-diphenyl-2-picryl-hydrazyl). X-ray diffraction measurements demonstrated a loss of crystallinity in AA after the encapsulation process, and a DSC scan also showed the loss of the compound's melting peak. Thermogravimetric analysis showed small differences in the thermal stability of galactomannan before and after the incorporation of AA. The mean diameters of the obtained spherical microspheres were in the range of 1.39 ± 0.77 µm. The encapsulation efficiency of AA microparticles in different environmental conditions varied from 95.40 to 97.92, and the antioxidant activity showed values ranging from 0.487 to 0.550 mg mL-1.

Regime Switching Models for Electricity Time Series that Capture Fat Tailed Distributions

In the power market, electricity prices play an important role at the economic level. The behavior of a price trend usually known as a structural break may change over time in terms of its mean value, its volatility, or it may change for a period of time before reverting back to its original behavior or switching to another style of behavior, and the latter is typically termed a regime shift or regime switch. Our task in this thesis is to develop an electricity price time series model that captures fat tailed distributions which can explain this behavior and analyze it for better understanding. For NordPool data used, the obtained Markov Regime-Switching model operates on two regimes: regular and non-regular. Three criteria have been considered price difference criterion, capacity/flow difference criterion and spikes in Finland criterion. The suitability of GARCH modeling to simulate multi-regime modeling is also studied.

Efeito do meio de cultura e do regime de luz na esporulação de Cercospora zeae-maydis

Algumas espécies fúngicas não esporulam satisfatoriamente em meio de cultura, a exemplo de Cercospora zeae-maydis, agente causal da cercosporiose do milho. A esporulação deste patógeno foi avaliada em sete meios de cultura agarizados (V8, suco de tomate temperado, água de coco, aveia, BDA, extrato de folha de milho e extrato de folha de milho + CaCO3) sob dois regimes luminosos (fotoperíodo de 12 horas e seqüencial - 6 dias claro/3 dias escuro). O ensaio foi conduzido em esquema fatorial 7 x 2, com os tratamentos dispostos em delineamento inteiramente casualizado com cinco repetições. A parcela experimental compreendeu uma placa de petri contendo 20 mL de meio de cultura sobre o qual foram colocados 200 mL de uma suspensão de 8 x 10(4) esporos/mL. As culturas foram posteriormente incubadas a 27ºC durante nove dias. Os meios V8 e suco de tomate temperado (STT) sob regime de fotoperíodo 12h/12h, foram aqueles que apresentaram melhor indução de esporulação, resultando na produção de 22,4 x 10(4) conídios/ mL e 28,62 x 10(4) conídios/mL, respectivamente.