O comportamento Fotoquímico dos Complexos Pentaaminas de Rutênio(II) com Ligantes π Insaturados

A general overview on the photochemical behaviour of [Ru(NH3)5L]2+ complexes (where L is a p ligand) is presented. The proposed mechanisms and techniques employed for the study of these reactions are discussed. Emphasis is made on the mechanisms that allow the identification of the reactive excited state of the [Ru(NH3)5py]2+ complex.

Fotoiniciação de polimerização vinílica

The initiation step of the light-induced polymerization kinetics of vinyl monomers using dye-sensitized photoinitiators to generate active radicals is discussed. The photoredox processes of basic dyes with amines and sulfinates are described as photochemical systems capable of starting free-radical polymerization of vinyl monomers in homogeneous and microheterogeneous media. Photophysical techniques like laser flash photolysis and time-correlated single photon counting are used to investigate the excited-state kinetics of the dyes.

Interações entre corantes e argilas em suspensão aquosa

Adsorption of cationic dyes on clays can be used as a model for the interactions between organic compounds and these minerals. Cationic dyes like methylene blue are used to study these interactions because of the spectroscopic changes observed when their molecules are adsorbed on clay surfaces. Depending on the structure and layer charge of the clay particles several processes may occur, like adsorption of dye monomers and aggregates on the external and internal surfaces of the clay tactoids, migration towards internal surfaces, protonation, etc. Under certain conditions the deaggregation-aggregation of the clay particles are accelerated trapping dye species during these processes. A general scheme is proposed for the processes occurring between clays and dyes in aqueous suspensions, which can be used to explain the behaviour of specific systems.

Conservation Laws in Cellular Automata

Conservation laws in physics are numerical invariants of the dynamics of a system. In cellular automata (CA), a similar concept has already been defined and studied. To each local pattern of cell states a real value is associated, interpreted as the “energy” (or “mass”, or . . . ) of that pattern.The overall “energy” of a configuration is simply the sum of the energy of the local patterns appearing on different positions in the configuration. We have a conservation law for that energy, if the total energy of each configuration remains constant during the evolution of the CA. For a given conservation law, it is desirable to find microscopic explanations for the dynamics of the conserved energy in terms of flows of energy from one region toward another. Often, it happens that the energy values are from non-negative integers, and are interpreted as the number of “particles” distributed on a configuration. In such cases, it is conjectured that one can always provide a microscopic explanation for the conservation laws by prescribing rules for the local movement of the particles. The onedimensional case has already been solved by Fuk´s and Pivato. We extend this to two-dimensional cellular automata with radius-0,5 neighborhood on the square lattice. We then consider conservation laws in which the energy values are chosen from a commutative group or semigroup. In this case, the class of all conservation laws for a CA form a partially ordered hierarchy. We study the structure of this hierarchy and prove some basic facts about it. Although the local properties of this hierarchy (at least in the group-valued case) are tractable, its global properties turn out to be algorithmically inaccessible. In particular, we prove that it is undecidable whether this hierarchy is trivial (i.e., if the CA has any non-trivial conservation law at all) or unbounded. We point out some interconnections between the structure of this hierarchy and the dynamical properties of the CA. We show that positively expansive CA do not have non-trivial conservation laws. We also investigate a curious relationship between conservation laws and invariant Gibbs measures in reversible and surjective CA. Gibbs measures are known to coincide with the equilibrium states of a lattice system defined in terms of a Hamiltonian. For reversible cellular automata, each conserved quantity may play the role of a Hamiltonian, and provides a Gibbs measure (or a set of Gibbs measures, in case of phase multiplicity) that is invariant. Conversely, every invariant Gibbs measure provides a conservation law for the CA. For surjective CA, the former statement also follows (in a slightly different form) from the variational characterization of the Gibbs measures. For one-dimensional surjective CA, we show that each invariant Gibbs measure provides a conservation law. We also prove that surjective CA almost surely preserve the average information content per cell with respect to any probability measure.

$E_{1}$-Formality of complex algebraic varieties

Let $X$ be a smooth complex algebraic variety. Morgan showed that the rational homotopy type of $X$ is a formal consequence of the differential graded algebra defined by the first term $E_{1}(X,W)$ of its weight spectral sequence. In the present work, we generalize this result to arbitrary nilpotent complex algebraic varieties (possibly singular and/or non-compact) and to algebraic morphisms between them. In particular, our results generalize the formality theorem of Deligne, Griffiths, Morgan and Sullivan for morphisms of compact Kähler varieties, filling a gap in Morgan"s theory concerning functoriality over the rationals. As an application, we study the Hopf invariant of certain algebraic morphisms using intersection theory.

Weight filtration on the cohomology of complex analytic spaces

We extend Deligne's weight filtration to the integer cohomology of complex analytic spaces (endowed with an equivalence class of compactifications). In general, the weight filtration that we obtain is not part of a mixed Hodge structure. Our purely geometric proof is based on cubical descent for resolution of singularities and Poincaré-Verdier duality. Using similar techniques, we introduce the singularity filtration on the cohomology of compactificable analytic spaces. This is a new and natural analytic invariant which does not depend on the equivalence class of compactifications and is related to the weight filtration.

A fotoquímica no Brasil

An historical overview is provided of the origins, growth and development of the field of photochemistry in Brazil, with special emphasis on the last three decades.

Scale-up model obtained from the rheological analysis of highly concentrated emulsions prepared at three scales

We examine the scale invariants in the preparation of highly concentrated w/o emulsions at different scales and in varying conditions. The emulsions are characterized using rheological parameters, owing to their highly elastic behavior. We first construct and validate empirical models to describe the rheological properties. These models yield a reasonable prediction of experimental data. We then build an empirical scale-up model, to predict the preparation and composition conditions that have to be kept constant at each scale to prepare the same emulsion. For this purpose, three preparation scales with geometric similarity are used. The parameter N¿D^α, as a function of the stirring rate N, the scale (D, impeller diameter) and the exponent α (calculated empirically from the regression of all the experiments in the three scales), is defined as the scale invariant that needs to be optimized, once the dispersed phase of the emulsion, the surfactant concentration, and the dispersed phase addition time are set. As far as we know, no other study has obtained a scale invariant factor N¿Dα for the preparation of highly concentrated emulsions prepared at three different scales, which covers all three scales, different addition times and surfactant concentrations. The power law exponent obtained seems to indicate that the scale-up criterion for this system is the power input per unit volume (P/V).

Tuotannonohjauksen kehittäminen piensarjatuotannossa

Tämä diplomityö käsittelee teollisen yrityksen tuotannonohjauksen kehittämistä piensarjatuotannossa. Työn kohteena on ABB Oy:n Tuulivoimageneraattorit-tulosyksikkö, joka valmistaa vakiotuotteita asiakasohjautuvasti. Työssä esitellään aluksi tuotannon ja tuotannonohjauksen teoriaa. Lävitse käydään perusasioiden kuten määritelmien, tavoitteiden ja tehtävien lisäksi tuotannonohjausprosessia sekä tuotannonohjauksen tietotekniikkaa. Teorian jälkeisessä empiriaosuudessa esitellään työssä kehitettyjä keinoja tuotannonohjauksen parantamiseksi. Tutkimus on toteutettu teoreettisen ja empiirisen tutkimustyön avulla. Teoreettiseen tutkimustyöhön sisältyi suomalaisiin ja ulkomaalaisiin kirjallisuuslähteisiin perehtyminen. Empiirinen tutkimustyö suoritettiin itsenäisen ongelman ratkaisutyön avulla. Tämä sisälsi kehittämiskohteiden analysoinnin, tarkempien kehittämistarpeiden määrityksen sekä kokeilujen kautta tapahtuneen kehittämistyön. Tutkimuksen päätavoitteena oli selvittää, miten tuotannonohjauksen kehittämisellä voidaan parantaa kohteena olevan tulosyksikön tuottavuutta ja kannattavuutta. Päätavoitteen pohjalta muodostettiin kuusi osatavoitetta: toimitusvarmuuden parantaminen, kapasiteetin kuormitusasteen nostaminen, kapasiteetin suunnittelun kehittäminen, läpäisyaikojen lyhentäminen, uuden ERP-järjestelmän vaatimusmäärittely sekä tuotannonohjausprosessin määrittäminen. Työssä rakennettiin neljään ensiksi mainittuun osatavoitteeseen tietotekniset sovellukset, jotka mahdollistavat osatavoitteiden suunnittelun ja ohjaamisen. Sovelluksia varten kullekin tuotteelle määriteltiin esimerkiksi työnvaiheketjut läpäisyaikoineen, kuormitusryhmät, kuormitusryhmien kapasiteetit, tuotteiden kuormittavuudet sekä kriittiset työvälineet. Työ osoitti, että tietotekniikka auttaa suuresti tuotannonohjauksessa. Lisääntynyt läpinäkyvyys, parantunut tiedonkulku, simulointimahdollisuudet sekä graafinen esitystapa helpottavat erilaisten suunnitelmien teossa ja parantavat siten päätöksenteon laatua. Tietotekniikan hyväksikäytön pohjana toimii tuotannon perus- ja tapahtumatietojen kurinalainen päivitys. Tämän vuoksi tietojärjestelmistä kannattaa rakentaa mahdollisimman yksinkertaisia.

The impact of FTAs on MENA trade in agricultural and industrial products

This paper analyses the impact of Free Trade Agreements (FTAs) on Middle East and North African Countries (MENA) trade for the period 1994-2010. The analysis distinguishes between industrial and agricultural trade to take into account the different liberalisation schedules. An augmented gravity model is estimated using up-to-date panel data techniques to control for all time-invariant bilateral factors that influence bilateral trade as well as for the so-called multilateral resistance factors. We also control for the endogeneity of the agreements and test for self-selection bias due to the presence of zero trade in our sample. The main findings indicate that North-South-FTAs and South-South- FTAs have a differential impact in terms of increasing trade in MENA countries, with the former being more beneficial in terms of exports for MENA countries, but both showing greater global market integration. We also find that FTAs that include agricultural products, in which MENA countries have a clear comparative advantage, have more favourable effects for these countries than those only including industrial products. JEL code: F10, F15

Calor e trabalho: são estes conceitos invariantes sob a permuta sistema-vizinhança?

It is argued that the invariants associated to the First Law of Thermodynamics and to the concept of identical processes lead to a clear definition of heat and work. The conditions for heat and work to be invariant under a system-surroundings interchange are also investigated. Finally, examples are presented to illustrate the above conditions.

O efeito da desativação térmica nas propriedades oxirredutoras e na atividade catalítica de catalisadores CZ e Pd-CZ

Automotive catalyst, using in Brazil since 1992, is a essential technology for vehicular emissions control. Noble metals are the active phase of these catalysts, and cerium zirconium mixed oxides (CZ), responsibles for the oxygen storage capacity (OSC), one of the most important aspect for the operational performance of the catalyst. In this context, the oxireduction properties analysis of CZ and Pd/CZ (palladium supported in CZ) system are the objective of this study, as well as, the impact of the thermal aging in the OSC. Aging consisted of treatments at 900 or 1200 °C, for 12 or 36 h, in oxidizing condition.

Thermal behaviour of TEGMMA copolymers obtained by photopolymerization using iron complexes

Copolymers of methyl methacrylate (MMA) and triethyleneglycol dimethacrylate (TEGDMA) obtained by photoinitiated polymerization using Fe(III) complexes were submitted to thermogravimetry (TGA) under dynamic air atmosphere and N2, and differential scanning calorimetric analysis (DSC). Thermal events were observed only between 90 - 110 ºC. Glass transitions were observed at ca. 100 ºC, followed by an exothermic peak at 170 ºC. The exothermic peak was assigned to a thermal curing process due to the presence of unreacted vinyl groups of the monomers. DSC revealed to be a useful tool to evaluate the curing completeness in this kind of material, using small amounts of sample in relatively short time.

Teaching mathematics and programming : new approaches with empirical evaluation

Programming and mathematics are core areas of computer science (CS) and consequently also important parts of CS education. Introductory instruction in these two topics is, however, not without problems. Studies show that CS students find programming difficult to learn and that teaching mathematical topics to CS novices is challenging. One reason for the latter is the disconnection between mathematics and programming found in many CS curricula, which results in students not seeing the relevance of the subject for their studies. In addition, reports indicate that students' mathematical capability and maturity levels are dropping. The challenges faced when teaching mathematics and programming at CS departments can also be traced back to gaps in students' prior education. In Finland the high school curriculum does not include CS as a subject; instead, focus is on learning to use the computer and its applications as tools. Similarly, many of the mathematics courses emphasize application of formulas, while logic, formalisms and proofs, which are important in CS, are avoided. Consequently, high school graduates are not well prepared for studies in CS. Motivated by these challenges, the goal of the present work is to describe new approaches to teaching mathematics and programming aimed at addressing these issues: Structured derivations is a logic-based approach to teaching mathematics, where formalisms and justifications are made explicit. The aim is to help students become better at communicating their reasoning using mathematical language and logical notation at the same time as they become more confident with formalisms. The Python programming language was originally designed with education in mind, and has a simple syntax compared to many other popular languages. The aim of using it in instruction is to address algorithms and their implementation in a way that allows focus to be put on learning algorithmic thinking and programming instead of on learning a complex syntax. Invariant based programming is a diagrammatic approach to developing programs that are correct by construction. The approach is based on elementary propositional and predicate logic, and makes explicit the underlying mathematical foundations of programming. The aim is also to show how mathematics in general, and logic in particular, can be used to create better programs.

Ensino de atenção primária à saúde na graduação: fatores que influenciam a satisfação do aluno

Formar profissionais capazes de trabalhar no Sistema Único de Saúde (SUS), na Atenção Primária à Saúde (APS), tem motivado mudanças curriculares e projetos tais como o Programa de Educação pelo Trabalho para a Saúde (PET-Saúde). Sob essa perspectiva, na Universidade Federal do Rio Grande do Sul (UFRGS), a disciplina Métodos de Abordagem em Saúde Comunitária (Masc), que discute o SUS e oferece ao estudante a oportunidade de participar do trabalho da Estratégia Saúde da Família (ESF), foi deslocada da 3ª para a 1ª etapa semestral em 2008 e passou a contar com o PET-Saúde em 2009. Com o objetivo de verificar se estas mudanças tiveram repercussões na satisfação dos alunos com a disciplina, foram estudados os seus instrumentos de avaliação nesse período de transição de semestre e implantação do PET-Saúde. As respostas dos 339 estudantes avaliados mostraram que as intervenções foram exitosas, pois melhoraram a opinião dos alunos em relação o ensino de APS, principalmente no que diz respeito à inserção precoce na ESF. A boa impressão inicial pode ser útil para uma avaliação mais positiva do SUS por esses futuros profissionais.