Simultaneous determination of chromium and manganese in alumina by slurry sampling graphite furnace atomic absorption spectrometry using NbC and NaF as modifiers

This paper reports a method for the direct and simultaneous determination of Cr and Mn in alumina by slurry sampling graphite furnace atomic absorption spectrometry (SiS-SIMAAS) using niobium carbide (NbC) as a graphite platform modifier and sodium fluoride (NaF) as a matrix modifier. 350 mu g of Nb were thermally deposited on the platform surface allowing the formation of NbC (mp 3500 degrees C) to minimize the reaction between aluminium and carbon of the pyrolytic platform, improving the graphite tube lifetime up to 150 heating cycles. A solution of 0.2 mol L(-1) NaF was used as matrix modifier for alumina dissolution as cryolite-based melt, allowing volatilization during pyrolysis step. Masses (c.a. 50 mg) of sample were suspended in 30 ml of 2.0% (v/v) of HNO(3). Slurry was manually homogenized before sampling. Aliquots of 20 mu l of analytical solutions and slurry samples were co-injected into the graphite tube with 20 mu l of the matrix modifier. In the best conditions of the heating program, pyrolysis and atomization temperatures were 1300 degrees C and 2400 degrees C, respectively. A step of 1000 degrees C was optimized allowing the alumina dissolution to form cryolite. The accuracy of the proposed method has been evaluated by the analysis of standard reference materials. The found concentrations presented no statistical differences compared to the certified values at 95% of the confidence level. Limits of detection were 66 ng g(-1) for Cr and 102 ng g(-1) for Mn and the characteristic masses were 10 and 13 pg for Cr and Mn, respectively.

Structural and vibrational characterization of polyaniline nanofibers prepared from interfacial polymerization

This work deals with the structural and vibrational characterization of PANI nanofibers prepared through interfacial polymerization using different concentrations of HCl aqueous solution. The results were compared to those obtained by PANI prepared through the conventional route. X-ray diffraction and small-angle X-ray scattering techniques showed that high concentrations of HCl solutions used in the preparation of the PANI nanofibers reduce their crystallinity. The increase of regions with granular morphology was also observed in the scanning electron microscopy images. The changes in the resonance Raman spectra from 200 to 500 cm(-1), FTIR spectra, and the EPR data of the PANI nanofibers reveal an increase in the torsion angles of C-ring-N-C-ring segments owing the formation of bipolarons in the PANI backbone higher than the PANI samples prepared by conventional route.

Surface active ionic liquids: Study of the micellar properties of 1-(1-alkyl)-3-methylimidazolium chlorides and comparison with structurally related surfactants

The impetus for the increasing interest in studying surface active ionic liquids (SAILs; ionic liquids with long-chain ""tails"") is the enormous potential for their applications, e.g., in nanotechnology and biomedicine. The progress in these fields rests on understanding the relationship between surfactant structure and solution properties, hence applications. This need has prompted us to extend our previous study on 1-(1-hexadecyl)-3-methylimidazolium chloride to 1-(1-alkyl)-3-methylimidazolium chlorides, with alkyl chains containing 10, 12, and 14 carbons. In addition to investigating relevant micellar properties, we have compared the solution properties of the imidazolium-based surfactants with: 1-(1-alkyl)pyridinium chlorides, and benzyl (2-acylaminoethyl)dimethylammonium chlorides. The former series carries a heterocyclic ring head-group, but does not possess a hydrogen that is as acidic as H2 of the imidazolium ring. The latter series carries an aromatic ring, a quaternary nitrogen and (a hydrogen-bond forming) amide group. The properties of the imidazolium and pyridinium surfactants were determined in the temperature range from 15 to 75 degrees C. The techniques employed were conductivity, isothermal titration calorimetry, and static light scattering. The results showed the important effects of the interactions in the interfacial region on the micellar properties over the temperature range studied. (C) 2011 Elsevier Inc. All rights reserved.

Elemental analysis of nuts and seeds by axially viewed ICP OES

A method for the multi-elemental determination of metals (Al, Ba, Ca, Cu, Fe, K, Mg, Mn, Sr and Zn), metalloids (B and Si), and non-metals (Cl, P and 5) in the babassu nut and mesocarp, sapucaia nut, coconut pulp, cupuassu pulp and seed, and cashew nut by axially viewed inductively coupled plasma optical emission spectrometry is presented. A diluted oxidant mixture (2 ml HNO(3) + 1 ml H(2)O(2) + 3 ml H(2)O) was used to achieve the complete decomposition of the organic matrix in a closed-vessel microwave oven. The accuracy of the entire proposed method was confirmed by standard reference material analysis (peach leaves-NIST SRM1547). The certified values showed a good agreement at a 95% confidence limit (Student`s t-test). The average RSD for repeatability of calibration solutions measurements were in the range of 1.1-6.7%. Limits of quantification (LOQ = 10 x LOD) were in the level of 0.00072-0.0532 mg/l. The macro and micronutrient ranges in the different nuts and seeds did not exceed the dietary reference intake (DRI), except for Mn in the babassu nut. (C) 2010 Published by Elsevier Ltd.

Raman spectra of acetonitrile in imidazolium ionic liquids

Raman spectra of dilute solutions of acetonitrile in ionic liquids reveal the characteristic features of ionic liquids` polarity. This is accomplished by investigating the Raman bandshape of the nu (CN) band, corresponding to the CN stretching mode of CH(3)CN, which is a very sensitive probe of the local environment. The amphiphilic nature of the CH(3)CN molecule allows us to observe the effect of electron pair acceptor and electron pair donor characteristics on ionic liquids. It has been found that the overall polarity of nine different ionic liquids based on 1-alkyl-3-methylimidazolium cations is more dependent on the anion than cation. The observed wavenumber shift of the nu (CN) band of CH(3)CN in ionic liquids containing alkylsulfate anions agrees with the significant different values previously measured for the dielectric constant of these ionic liquids. The conclusions obtained from the analysis of the nu (CN) band were corroborated by the analysis of the symmetric nu(1) (CD(3)) stretching mode of deuterated acetonitrile in different ionic liquids. Copyright (C) 2010 John Wiley & Sons, Ltd.

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.

The Evolution of a Responsibility to Protect in Africa : The African Unions Emerging Peace and Security Regime

The thesis focuses on, and tries to evaluate, the role that the African Union (AU) plays in protecting the peace and security on the African continent. The thesis takes an interdisciplinary approach to the topic by both utilizing international relations and international law theories. The two disciplines are combined in an attempt to understand the evolution of the AU’s commitment to the pragmatist doctrine: responsibility to protect (R2P). The AU charter is considered to be the first international law document to cover R2P as it allows the AU to interfere in the internal affairs of its member states. The R2P doctrine was evolved around the notion of a need to arrive at a consensus in regard to the right to intervene in the face of humanitarian emergencies. A part of the post-Cold War shift in UN behaviour has been to support local solutions to local problems. Hereby the UN acts in collaboration with regional organizations, such as the AU, to achieve the shared aspirations to maintain international peace and security without getting directly involved on the ground. The R2P takes a more holistic and long-term approach to interventions by including an awareness of the need to address the root causes of the crisis in order to prevent future resurrections of conflicts. The doctrine also acknowledges the responsibility of the international community and the intervening parties to actively participate in the rebuilding of the post-conflict state. This requires sustained and well planned support to ensure the development of a stable society.While the AU is committed to implementing R2P, many of the AU’s members are struggling, both ideologically and practically, to uphold the foundations on which legitimate intervention rests, such as the protection of human rights and good governance. The fact that many members are also among the poorest countries in the world adds to the challenges facing the AU. A lack of human and material resources leads to a situation where few countries are willing, or able, to support a long-term commitment to humanitarian interventions. Bad planning and unclear mandates also limit the effectiveness of the interventions. This leaves the AU strongly dependent on regional powerbrokers such as Nigeria and South Africa, which in itself creates new problems in regard to the motivations behind interventions. The current AU charter does not provide sufficient checks and balances to ensure that national interests are not furthered through humanitarian interventions. The lack of resources within the AU also generates worries over what pressure foreign nations and other international actors apply through donor funding. It is impossible for the principle of “local solutions for local problems? to gain ground while this donor conditionality exists.The future of the AU peace and security regime is not established since it still is a work in progress. The direction that these developments will take depends on a wide verity of factors, many of which are beyond the immediate control of the AU.

Optimization heuristic solutions, how good can they be? : With empirical applications in location problems

Combinatorial optimization problems, are one of the most important types of problems in operational research. Heuristic and metaheuristics algorithms are widely applied to find a good solution. However, a common problem is that these algorithms do not guarantee that the solution will coincide with the optimum and, hence, many solutions to real world OR-problems are afflicted with an uncertainty about the quality of the solution. The main aim of this thesis is to investigate the usability of statistical bounds to evaluate the quality of heuristic solutions applied to large combinatorial problems. The contributions of this thesis are both methodological and empirical. From a methodological point of view, the usefulness of statistical bounds on p-median problems is thoroughly investigated. The statistical bounds have good performance in providing informative quality assessment under appropriate parameter settings. Also, they outperform the commonly used Lagrangian bounds. It is demonstrated that the statistical bounds are shown to be comparable with the deterministic bounds in quadratic assignment problems. As to empirical research, environment pollution has become a worldwide problem, and transportation can cause a great amount of pollution. A new method for calculating and comparing the CO2-emissions of online and brick-and-mortar retailing is proposed. It leads to the conclusion that online retailing has significantly lesser CO2-emissions. Another problem is that the Swedish regional division is under revision and the border effect to public service accessibility is concerned of both residents and politicians. After analysis, it is shown that borders hinder the optimal location of public services and consequently the highest achievable economic and social utility may not be attained.

Global governance, currency and trade: implications of one on the other, common problems and how to address cooperation through law at the international level

How to deal with the impacts of the exchange rate on the trade balance of Brazil? There is not a single answer to such question. In order to find out some legal approaches for this matter, this paper aims to describe and analyze the role of the IMF, WTO and the governments of Brazil and the United States on the currency misalignments, especially the extraterritorial effects of such misalignment on the Brazil’s bilateral trade with the United States. The article concludes that the Currency Swap Agreements and other bilateral solutions may minimize the distortions that the Brazilian balance of payment against the USA is carrying, due to the lack of legal solutions for the problem of the exchange rate misalignments that Brazil is facing.

Computer simulation of the stochastic transport equation

Trabalho apresentado no 37th Conference on Stochastic Processes and their Applications - July 28 - August 01, 2014 -Universidad de Buenos Aires

Organizations redesign and building of information systems

Develop software is still a risky business. After 60 years of experience, this community is still not able to consistently build Information Systems (IS) for organizations with predictable quality, within previously agreed budget and time constraints. Although software is changeable we are still unable to cope with the amount and complexity of change that organizations demand for their IS. To improve results, developers followed two alternatives: Frameworks that increase productivity but constrain the flexibility of possible solutions; Agile ways of developing software that keep flexibility with less upfront commitments. With strict frameworks, specific hacks have to be put in place to get around the framework construction options. In time this leads to inconsistent architectures that are harder to maintain due to incomplete documentation and human resources turnover. The main goals of this work is to create a new way to develop flexible IS for organizations, using web technologies, in a faster, better and cheaper way that is more suited to handle organizational change. To do so we propose an adaptive object model that uses a new ontology for data and action with strict normalizing rules. These rules should bound the effects of changes that can be better tested and therefore corrected. Interfaces are built with templates of resources that can be reused and extended in a flexible way. The “state of the world” for each IS is determined by all production and coordination acts that agents performed over time, even those performed by external systems. When bugs are found during maintenance, their past cascading effects can be checked through simulation, re-running the log of transaction acts over time and checking results with previous records. This work implements a prototype with part of the proposed system in order to have a preliminary assessment its feasibility and limitations.

HPLC-DAD methodology for the quantification of organic acids, furans and polyphenols by direct injection of wine samples

This article proposes a simple and sensitive HPLC method with photo-diode array detection for the analysis of organic acids, monomeric polyphenols and furanic compounds in wine samples by direct injection. The chromatographic separation of 8 organic acids, 2 furans and 22 phenolic compounds was carried out with a buffered solution (pH 2.70) and acetonitrile as mobile phases and a difunctionally bonded C18 stationary phase, Atlantis dC18 (250 4.6 mm, 5mm) column. The elution was performed in 12 min for the organic acids and in 60 min for the phenolic compounds, including phenolic acids, stilbenes and flavonoids. Target compounds were detected at 210 nm (organic acids, flavan-3-ols and benzoic acids), 254 nm (ellagic acid), 280 nm (furans and cinnamic acid), 315 nm (hydroxycinnamic acids and trans-resveratrol) and 360 nm (flavonoids). The RSD for the repeatability test (n55) of peak area and retention times were below 3.1 and 0.3%, respectively, for phenolics and below 1.0 and 0.2% for organic acids. The RSDs expressing the reproducibility of the method were higher than for the repeatability results but all below 9.0%. Method accuracy was evaluated by the recovery results, with averaged values between 80 and 104% for polyphenols and 97–105% for organic acids. The calibration curves, obtained by triplicate injection of standard solutions, showed good linearity with regression coefficients higher than 0.9982 for polyphenols and 0.9997 for organic acids. The LOD was in the range of 0.07–0.49 mg/L for polyphenols (cinnamic and gallic acids, respectively) and 0.001–0.046 g/L for organic acids (oxalic and lactic acids, respectively). The method was successfully used to measure and assess the polyphenolic fingerprint and organic acids profile of red, white, rose ´ and fortified wines.

Nutrient contents and production of rocket as affected by nitrogen concentrations in the nutritive solution

O empirismo no uso das soluções nutritivas é freqüente. Muitas vezes a mesma solução nutritiva é usada para diferentes espécies baseando-se apenas em semelhanças morfológicas. No entanto esta situação pode proporcionar desequilíbrio nutricional prejudicando tanto a produção quanto a qualidade do produto face o acúmulo de nitrato. Foi conduzido um trabalho em sistema hidropônico - NFT, com o objetivo de avaliar o efeito da concentração de nitrogênio na solução nutritiva na produção, nos teores de nutrientes e de nitrato em folhas de rúcula (Eruca sativa). O trabalho foi conduzido na primavera de 2003. Foram avaliadas quatro concentrações de nitrogênio na solução nutritiva (60,8; 121,6; 182,5; 243,5 mg L-1) e três cultivares de rúcula (Cultivada, Folha Larga e Selvática), sob delineamento de blocos ao acaso, fatorial 4 x 3, com quatro repetições. A cv. Cultivada apresentou maior estatura e fitomassa fresca de folhas, não diferindo da 'Folha Larga' quanto a número de folhas, teor de nitrato nas folhas e fitomassa seca e fresca da raiz. Houve incremento de NO3-, N, Ca e P e diminuição de Mg, K e S com o aumento da concentração de N na solução nutritiva. O cultivo da cv. Cultivada na concentração de 93 mg L-1 é a mais recomendada em função da maior produtividade e baixo teor de nitrato.

Interaction mechanism of poly (o-ethoxyaniline) and collagen blends

Blend films of poly (o-ethoxyaniline) (POEA) and collagen were fabricated by casting under optimized conditions and characterized by Raman scattering and UV-vis absorption spectroscopies. The UV-vis spectra showed that the addition of collagen in the aqueous solution of POEA promotes a dedoping of the POEA. This effect was also observed for the blend films as supported by Raman scattering and a mechanism for the chemical interaction between POEA-collagen is proposed. The influences of different percentage of collagen as well as the pH of stock solutions during the fabrication process of the blend films were also investigated. It was found that the preparation method plays an important role in the flexibility and freestanding properties of the films. Complementary, the surface morphology was studied by atomic force microscopy and the conductivity by dc measurements. (C) 2003 Elsevier Ltd. All rights reserved.

Synthesis and structural characterization of Eu(III)-doped Zn7Sb2O12

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