An insight into the beginning stage of the aqueous ring opening metathesis polymerization of exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid with Ru(III) compounds: the consumption of Ru(III) species in the presence of carboxylic acids monitored by ESR spectroscopy

The presence of paramagnetic species in the aqueous ring opening metathesis polymerizations of the exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid monomer with RuCl(3) and K(2)[RuCl(5)H(2)O] compounds was studied using ESR techniques. It was observed that the intensities of the Ru(III) signals in the ESR spectra decrease on the time scale of the induction period so that the ROMP can take place. The intensity of the Ru(III) signal almost disappeared 50 min after reacting with K(2)[RuCl(5)H(2)O] and after 100 mm in the case of RuCl(3). Reactions of the cis-[Ru(NH(3))(4)(H(2)O)(2)](tfms)(3) and [Ru(NH(3))(5)H(2)O](tfms)(3) complexes with the monomer and different organic compounds representing the organic functions in the monomer (furan, norbornene, but-2-ene-1,4-diol and formic, acetic, oxalic and maleic acids) were also monitored by ESR and UV/vis spectra. It was deduced that the organic acids provide the disappearance of the Ru(III) signal. The proton NMR relaxation times of the residual water in D(2)O for reactions with oxalic acid suggested that the presence of paramagnetic ions in the solution decreases along with

Electronic synergism in [RuCl(2)(PPh(3))(2)(amine)] complexes differing the reactivity for ROMP of norbornene and norbornadiene

The reactivity of the new complex [RuCl(2)(PPh(3))(2)(3,5-Me(2)piperidine)], complex 1, was investigated for ring opening metathesis polymerization (ROMP) of norbornene (NBE) and norbornadiene (NBD) in the presence of ethyl diazoacetate (EDA) in CHCl(3). The aim is to observe the combination of PPh(3) and an amine as ancillary ligands concerning the steric hindrance and the electronic perturbation in the properties of the N-bound site when replacing the amines. Thus, the results with 1 were compared to the results obtained when the amine is piperidine (complex 2). Reaction with 1 provides 70% yield of isolated polyNBE (M(n) =8.3 x 10(4) g/mol; PDI = 2.03), whereas 2 provides quantitative reaction (M(n) = 1.2 x 10(5) g/mol; PDI = 1.90) with [NBE]/[Ru] = 5000, [EDA]/[Ru] = 48 and 1.1 mu mol of Ru for 5 min at 25 degrees C. The resulting polymers showed c.a. 62% of trans-polyNBE, determined by (1)H NMR, and T(g) = 32 degrees C, determined by DSC and DMTA. For ROMP of NBD, 1 showed quantitative yield with PDI =2.62 when [NBD]/[Ru] = 5000 for 20 min at 25 degrees C, whereas the reaction with 2 reached 55% with PDI = 2.16 in the same conditions. It is concluded that the presence of the two methyl groups in the piperidine ring provides an increase in the induction period to produce the Ru-carbene species justifying better polyNBE results with 2, and a greater amine(sigma)-> Ru(pi)-> monomer synergism which contributed to the best activation of less tensioned olefin as NBD. (C) 2010 Elsevier B.V. All rights reserved.

The influence of perhydroazepine and piperidine as further ancillary ligands on Ru-PPh(3)-based catalysts for ROMP of norbornene and norbornadiene

Polynorbornadiene and polynorbornene were synthesized via ring opening metathesis polymerization (ROMP) with [RuCl(2)(PPh(3))(2)(amine)] as catalyst precursors, amine = piperidine (1) or perhydroazepine (2) in the presence of 5 mu L of ethyl diazoacetate (EDA) ([monomer]/[Ru] = 5000; 40 degrees C with 1; 25 degrees C with 2). The effects of the solvent volume (2-8 mL of CHCl(3)) reaction time (5-120 min) and atmosphere type (argon and air) on the yields were investigated to observe the behavior of the two different precursors. Quantitative yields were obtained for 60 or 120 min regardless of the starting volumes, either in argon or air, with both Ru species. However, low yields were obtained for short times (5-30 min) when the reactions are performed with large volumes (6-8 mL). In argon, the yields were larger with 2, associated to a faster propagation reaction controlled by the Ru active species. In air, the yields were larger with 1, associated to a higher resistance to O(2) of the starting and propagating Ru species. The different activities between 1 and 2 are discussed considering the steric hindrance and electronic characteristics of the amines such as ancillary ligands and their arrangements with PPh(3) and Cl(-) ions in the metal centers. (c) 2009 Elsevier B.V. All rights reserved.

Methanol and ethanol electro-oxidation on Pt-SnO(2) and Pt-Ta(2)O(5) sol-gel-modified boron-doped diamond surfaces

The search for more efficient anode catalyst than platinum to be used in direct alcohol fuel cell systems is an important challenge. In this study, boron-doped diamond film surfaces were modified with Pt, Pt-SnO(2) and Pt-Ta(2)O(5) nano-crystalline deposits by the sol-gel method to study the methanol and ethanol electro-oxidation reactions in acidic medium. Electrochemical experiments carried out in steady-state conditions demonstrate that the addition of SnO(2) to Pt produces a very reactive electrocatalyst that possibly adsorbs and/or dissociate ethanol more efficiently than pure Pt changing the onset potential of the reaction by 190 mV toward less positive potentials. Furthermore, the addition of Ta(2)O(5) to Pt enhances the catalytic activity toward the methanol oxidation resulting in a negative shift of the onset potential of 170 mV. These synergic effects indicate that the addition of these co-catalysts inhibits the poisoning effect caused by strongly adsorbed intermediary species. Since the SnO(2) catalyst was more efficient for ethanol oxidation, it could probably facilitate the cleavage of the C-C bond of the adsorbed intermediate fragments of the reaction. (C) 2009 Elsevier B.V. All rights reserved.

Ability of Ru complexes for ROMP tuned through a combination of phosphines and amines

Polynorbonerne with high molecular weight was obtained via ring opening metathesis polymerization using catalysts derived from [RuCl(2)(PPh(2)Bz)(2) L] (1 for L = PPh(2) Bz; 2 for L = piperidine) type of complexes when in the presence of ethyl diazoacetate in CHCl(3). The polymer precipitated within a few minutes at 50 degrees C when using 1 with ca. 50% yield ([NBE]/[Ru] = 5000). Regarding 2, for either 30 min at 25 C or 5 min at 50 degrees C, more than 90% of yields are obtained; and at 50 C for 30 min a quantitative yield is obtained. The yield and PDI values are sensitive to the [NBE]/[Ru] ratio. The reaction of 1 with either isonicotinamide or nicotinamide produces six-coordinated complexes of [RuCl(2)(PPh(2)Bz)(2)(L)(2)] type, which are almost inactive and produce only small amounts of polymers at 50 C for 30 min. Thus, we Concluded that the novel complexes show very distinct reactivities for ROMP of NBE. This has been rationalized on account of a combination of synergistic effects of the phosphine-amine ancillary ligands. (C) 2009 Elsevier B.V. All rights reserved.

Ink-Jet Printing of Color Optical Filters for LCD Applications

At the age of multi-media, portable electronic devices such as mobile phones, personal digital assistant and handheld gaming systems have increased the demand for high performance displays with low cost production. Inkjet printing color optical filters (COF) for LCD applications seem to be an interesting alternative to decrease the production costs. The advantage of inkjet printing technology is to be fast, accurate, easy to run and cheaper than other technologies. In this master thesis work, we used various disciplines such as optical microscopy, rheology, inkjet printing, profilometering and colorimetry. The specific aim of the thesis was to investigate the feasibility of using company-A pigment formulation in inkjet production of COF for active matrix LCD applications. Ideal viscosity parameters were determined from 10 to 20mPa·s for easy inkjet printing at room temperature. The red pigments used are fully dispersed into the solvent and present an excellent homogenous repartition after printing. Thickness investigations revealed that the printed COF were equal or slightly thicker than typically manufactured ones. The colorimetry investigations demonstrated color coordinates very close to the NTSC red standard. LED backlighting seems to be a valuable solution to combine with the printed COF regarding to the spectrum and color analysis. The results on this thesis will increase the understanding of inkjet printing company-A pigments to produce COF for LCD applications.

Materialundersökning

This report emphasizes the importance of seeing a university as a company that offers a service. It isimportant to see the different quality dimensions that distinguish a service. The customer-focused planninghas also set the structure of this degree project.The marketing investigation is based on recruit questionnaires and interviews with secondary schoolstudents. The questionnaires show that the catalogue still reaches out with most information despiteconstant increase of information search at the Internet. The students seem to prefer University ofKristianstad´s catalogue front.The competition analysis is based on telephone interviews and information material sent from theother universities. Structure, usage of the graphic profile amongst more is reviewed for every university.The answers have varied a lot but there are few that have a good structure. University of Dalarna´sinformation material has neither structure nor a homogenous look.The employees at University of Dalarna are not using the universities graphic profile. They are alsodissatisfied regarding the absence of pre-produced, general overhead film series. The internal analysisalso shows that the employees don’t know which material is accessible or where to find it.

Gravitational self-localization for spherical masses

In this work, I consider the center-of-mass wave function for a homogenous sphere under the influence of the self-interaction due to Newtonian gravity. I solve for the ground state numerically and calculate the average radius as a measure of its size. For small masses, M≲10−17 kg, the radial size is independent of density, and the ground state extends beyond the extent of the sphere. For masses larger than this, the ground state is contained within the sphere and to a good approximation given by the solution for an effective radial harmonic-oscillator potential. This work thus determines the limits of applicability of the point-mass Newton Schrödinger equations for spherical masses. In addition, I calculate the fringe visibility for matter-wave interferometry and find that in the low-mass case, interferometry can in principle be performed, whereas for the latter case, it becomes impossible. Based on this, I discuss this transition as a possible boundary for the quantum-classical crossover, independent of the usually evoked environmental decoherence. The two regimes meet at sphere sizes R≈10−7 m, and the density of the material causes only minor variations in this value.

Methodological issues in applying Location Models to Rural areas

Location Models are usedfor planning the location of multiple service centers in order to serve a geographicallydistributed population. A cornerstone of such models is the measure of distancebetween the service center and a set of demand points, viz, the location of thepopulation (customers, pupils, patients and so on). Theoretical as well asempirical evidence support the current practice of using the Euclidian distancein metropolitan areas. In this paper, we argue and provide empirical evidencethat such a measure is misleading once the Location Models are applied to ruralareas with heterogeneous transport networks. This paper stems from the problemof finding an optimal allocation of a pre-specified number of hospitals in alarge Swedish region with a low population density. We conclude that the Euclidianand the network distances based on a homogenous network (equal travel costs inthe whole network) give approximately the same optimums. However networkdistances calculated from a heterogeneous network (different travel costs indifferent parts of the network) give widely different optimums when the numberof hospitals increases.  In terms ofaccessibility we find that the recent closure of hospitals and the in-optimallocation of the remaining ones has increased the average travel distance by 75%for the population. Finally, aggregation the population misplaces the hospitalsby on average 10 km.

Síntese e análise estrutural de novos ciclopaladatos e síntese de N-heterociclos a partir de ciclopaladatos e alenos

Os compostos de paládio vêm apresentado uma vasta linha de aplicação, tanto como catalisadores como precursores em reações de síntese orgânica. Dentre esses compostos, os ciclopaladatos, que são compostos cíclicos com uma ligação Pd-heteroátomo, permite a formação de novas estruturas cíclicas contendo algum heteroátomo, como nitrogênio, oxigênio ou enxofre. Neste trabalho foram sintetizadas aminas propargílicas capazes de se coordenar a sais de paládio, formando novos ciclopaladatos através da reação de cloropaladação. Esses compostos se encontram na forma de dímeros e podem apresentar-se como diferentes isômeros. Estudos espectroscópicos, tais como RMN de 1H, 13C e raios-X de monocristais foram realizados para a elucidação estrutural desses novos compostos. Além dos isômeros geométricos clássicos (cisóide e transóide) foram observados pela primeira vez a formação de atropoisômeros. Esses ciclopaladatos, contendo nitrogênio ligado ao paládio, foram testados frente a alenos diferentemente substituídos, mostrando que ocorre a inserção do aleno na ligação Pd-C e, seguido da depaladação, ocorre a formação de novos compostos heterocíclicos a seis membros. Alguns ciclopaladatos, quando em solução, podem apresentar certa instabilidade, ocorrendo a decomposição do ciclopaladato com a regeneração do alcino precursor do respectivo ciclopaladato. Assim, estudou-se a reação de decomposição de diferentes ciclopaladatos, chamada de retrocloropaladação, utilizando a técnica de RMN de 1H em diferentes intervalos de tempo.

Uma proposta de arquitetura de linha de produto para sistemas de gerenciamento de workflow

A tecnologia de workflow vem apresentando um grande crescimento nos últimos anos. Os Workflow Management Systems (WfMS) ou Sistemas de Gerenciamento de Workflow oferecem uma abordagem sistemática para uniformizar, automatizar e gerenciar os processos de negócios. Esta tecnologia requer técnicas de engenharia de software que facilitem a construção desse tipo de sistema. Há muito vem se formando uma consciência em engenharia de software de que para a obtenção de produtos com alta qualidade e que sejam economicamente viáveis torna-se necessário um conjunto sistemático de processos, técnicas e ferramentas. A reutilização está entre as técnicas mais relevantes desse conjunto. Parte-se do princípio que, reutilizando partes bem especificadas, desenvolvidas e testadas, pode-se construir software em menor tempo e com maior confiabilidade. Muitas técnicas que favorecem a reutilização têm sido propostas ao longo dos últimos anos. Entre estas técnicas estão: engenharia de domínio, frameworks, padrões, arquitetura de software e desenvolvimento baseado em componentes. Porém, o que falta nesse contexto é uma maneira sistemática e previsível de realizar a reutilização. Assim, o enfoque de linha de produto de software surge como uma proposta sistemática de desenvolvimento de software, baseada em uma família de produtos que compartilham um conjunto gerenciado de características entre seus principais artefatos. Estes artefatos incluem uma arquitetura base e um conjunto de componentes comuns para preencher esta arquitetura. O projeto de uma arquitetura para uma família de produtos deve considerar as semelhanças e variabilidades entre os produtos desta família. Esta dissertação apresenta uma proposta de arquitetura de linha de produto para sistemas de gerenciamento de workflow. Esta arquitetura pode ser usada para facilitar o processo de produção de diferentes sistemas de gerenciamento de workflow que possuem características comuns, mas que também possuam aspectos diferentes de acordo com as necessidades da indústria. O desenvolvimento da arquitetura proposta tomou como base a arquitetura genérica e o modelo de referência da Workflow Management Coalition (WfMC) e o padrão de arquitetura Process Manager desenvolvido no contexto do projeto ExPSEE1. O processo de desenvolvimento da arquitetura seguiu o processo sugerido pelo Catalysis com algumas modificações para representar variabilidade. A arquitetura proposta foi descrita e simulada através da ADL (Architecture Description Language) Rapide. A principal contribuição deste trabalho é uma arquitetura de linha de produto para sistemas de gerenciamento de workflow. Pode-se destacar também contribuições para uma proposta de sistematização de um processo de desenvolvimento de arquitetura de linha de produto e também um melhor entendimento dos conceitos e abordagens relacionados à prática de linha de produto, uma vez que esta tecnologia é recente e vem sendo largamente aplicada nas empresas.

Income inequality in a job-search model with heterogeneous time preferences

This paper explores the use of an intertemporal job-search model in the investigation of within-cohort and between-cohort income inequality, the latter being generated by the heterogeneity of time preferences among cohorts of homogenous workers and the former by the cross-sectional turnover in the job market. It also offers an alternative explanation for the empirically-documented negative correlation between time preference and labor income. Under some speciÖc distributions regarding wage offers and time preferences, we show how the within-cohort and between-cohort Gini coe¢ cients of income distribution can be calculated, and how they vary as a function of the parameters of the model.

Using consumer search cost and loyalty to explain dispersion in banking fees

Pode-se observar uma considerável dispersão entre os preços que diferentes bancos comerciais no Brasil cobram por um mesmo pacote homogêneo de serviços— dispersão esta que é sustentada ao longo do tempo. Em uma tentativa de replicar esta observação empírica, foi desenvolvido um simples modelo que lança mão do arcabouço da literatura de custos de procura (search costs) e que baseia-se também na lealdade por parte dos consumidores. Em seguida, dados de preços referentes ao setor bancário brasileiro são aplicados ao modelo desenvolvido e alguns exercícios empíricos são então realizados. Esses exercícios permitem que: (i) os custos de procura incorridos pelos consumidores sejam estimados, ao fixar-se os valores dos demais parâmetros e (ii) as correspondentes perdas de peso-morto que surgem como consequência dos custos de procura incorridos pelos consumidores sejam também estimadas. Quando apenas 80% da população é livre para buscar por bancos que cobrem menores tarifas, à taxa de juros mensal de 0,5%, o valor estimado do custo de procura médio incorrido pelos consumidores chega a 1805,80 BRL, sendo a correspondente perda de peso-morto média na ordem de 233,71 BRL por consumidor.

The impact of property rights and its limits

The empirical evaluation of the effect of land property rights typically suffers from selection problems. The allocation of property rights across households is usually not random but based on wealth, family characteristics, political clientelism, or other mechanisms built on differences between the groups that acquire property rights and the groups that do not. In this paper, we address this selection concern exploiting a natural experiment in the allocation of property rights. Twenty years ago, a homogenous group of squatters occupied a piece of privately owned land in a suburban area of Buenos Aires, Argentina. When the Congress passed an expropriation law transferring the land from the former owners to the squatters, some of the former owners surrendered the land (and received a compensation), while others decide to sue in the slow Argentine courts. These different decisions by the former owners generated an allocation of property rights that is exogenous to the characteristics of the squatters. We take advantage of this natural experiment to evaluate the effect of the allocation of urban land property rights. Our preliminary results show significant effects on housing investment, household size, and school attrition. Contradicting De Soto's hypotheses, we found nonsignificant effects on labor income and access to credit markets.

Configurando a cidade contemporânea em Natal : os processos espaciais em Ponta Negra

This dissertation is about the spatial configuration in Natal and processes in the Ponta Negra neighborhood today. Ponta Negra has undergone a number of critical social and spatial changes due to tourism development after the 1990s. It is of special interest to consider the intensification of real estate investment after 2000, when the new airport terminal, located in the neighboring municipality of Parnamirim, was in use. Ponta Negra is the place where most tourists go to, so attracting considerable public investments. New agents of transformation have produced change in the neighborhood as well. The present study aims at analysing the spatial processes in this part of the city. Here, the spatial configuration that resulted from extended real estate investments, both public and private, in recent years, is analysed in detail. The study identifies the multually differentiated, however internally homogenous areas. The concepts of production of space, contemporanean urban development and spatial dynamics are discussed. The research is based on document analysis and field work. Results were plotted to maps and tables. A detailed analysis of the spatial processes in the Ponta Negra neighborhood is undertaken as a conclusion, considering the contemporanean global scenario