The low-lying electronic states of BeP: a reliable and accurate quantum mechanical prediction

A very high level of theoretical treatment (complete active space self-consistent field CASSCF/MRCI/aug-cc-pV5Z) was used to characterize the spectroscopic properties of a manifold of quartet and doublet states of the species BeP, as yet experimentally unknown. Potential energy curves for 11 electronic states were obtained, as well as the associated vibrational energy levels, and a whole set of spectroscopic constants. Dipole moment functions and vibrationally averaged dipole moments were also evaluated. Similarities and differences between BeN and BeP were analysed along with the isovalent SiB species. The molecule BeP has a X (4)Sigma(-) ground state, with an equilibrium bond distance of 2.073 angstrom, and a harmonic frequency of 516.2 cm(-1); it is followed closely by the states (2)Pi (R(e) = 2.081 angstrom, omega(e) = 639.6 cm(-1)) and (2)Sigma(-) (R(e) = 2.074 angstrom, omega(e) = 536.5 cm(-1)), at 502 and 1976 cm(-1), respectively. The other quartets investigated, A (4)Pi (R(e) = 1.991 angstrom, omega(e) = 555.3 cm(-1)) and B (4)Sigma(-) (R(e) = 2.758 angstrom, omega(e) = 292.2 cm(-1)) lie at 13 291 and 24 394 cm(-1), respectively. The remaining doublets ((2)Delta, (2)Sigma(+)(2) and (2)Pi(3)) all fall below 28 000 cm(-1). Avoided crossings between the (2)Sigma(+) states and between the (2)Pi states add an extra complexity to this manifold of states.

Azo-hydrazone tautomerism in protonated aminoazobenzenes: Resonance Raman spectroscopy and quantum-chemical calculations

The protonation effect on the vibrational and electronic spectra of 4-aminoazobenzene and 4-(dimethylamino)azobenzene was investigated by resonance Raman spectroscopy, and the results were discussed on the basis of quantum-chemical calculations. Although this class of molecular systems has been investigated in the past concerning the azo-hydrazone tautomerism, the present work is the first to use CASSCF/CASPT2 calculations to unveil the structure of both tautomers as well the nature of the molecular orbitals involved in chromophoric moieties responsible for the resonance Raman enhancement patterns. More specifically both the resonance Raman and theoretical results show clearly that in the neutral species, the charge transfer transition involves mainly the azo moiety, whereas in the protonated forms there is a great difference, depending on the tautomer. In fact, for the azo tautomer the transition is similar to that observed in the corresponding neutral species, whereas in the hydrazone tautomer such a transition is much more delocalized due to the contribution of the quinoid structure. The characterization of protonated species and the understanding of the tautomerization mechanism are crucial for controlling molecular properties depending on the polarity and pH of the medium.

Mechanical and tribological properties of PVD-coated cemented carbide as evaluated by a new multi-pass scratch testing method

A new test method based on multipass scratch testing has been developed for evaluating the mechanical and tribological properties of thin, hard coatings. The proposed test method uses a pin-on-disc tribometer and during testing a Rockwell C diamond stylus is used as the “pin” and loaded against the rotating coated sample. The influence of normal load on the number of cycles to coating damage is investigated and the resulting coating damage mechanisms are evaluated by posttest scanning electron microscopy. The present study presents the test method by evaluating the performance of Ti0.86Si0.14N, Ti0.34Al0.66N, and (Al0.7Cr0.3)2O3 coatings deposited by cathodic arc evaporation on cemented carbide inserts. The results show that the test method is quick, simple, and reproducible and can preferably be used to obtain relevant data concerning the fatigue, wear, chipping, and spalling characteristics of different coating-substrate composites. The test method can be used as a virtually nondestructive test and, for example, be used to evaluate the fatigue and wear resistance as well as the cohesive and adhesive interfacial strength of coated cemented carbide inserts prior to cutting tests.

A Broad-spectrum mer Operon in a Multi-drug Resistant Strain of the Fish Pathogen, Aeromonas salmonicida.

Aeromonas salmonicida AS03, a potential fish pathogen, was isolated from Atlantic salmon, Salmo salar, in 2003. This strain was found to be resistant to ≥1000 mM HgCl2 and ≥32 mM phenylmercuric acetate as well as multiple antimicrobials. Mercury (Hg) and antibiotic resistance genes are often located on the same mobile genetic elements, so the genetic determinants of both resistances and the possibility of horizontal gene transfer were examined. Specific PCR primers were used to amplify and sequence distinctive regions of the mer operon. A. salmonicida AS03 was found to have a pDU1358-like broad-spectrum mer operon, containing merB as well as merA, merD, merP, merR and merT, most similar to Klebsiella pneumonaie plasmid pRMH760. To our knowledge, the mer operon has never before been documented in Aeromonas spp. PCR and gene sequencing were used to identify class 1 integron associated antibiotic resistance determinants and the Tet A tetracycline resistance gene. The transposase and resolvase genes of Tn1696 were identified through PCR and sequencing with Tn21 specific PCR primers. We provide phenotypic and genotypic evidence that the mer operon, the aforementioned antibiotic resistances, and the Tn1696 transposition module are located on a single plasmid or conjugative transposon that can be transferred to E. coli DH5α through conjugation in the presence of low level Hg and absence of any antibiotic selective pressure. Additionally, the presence of low-level Hg or chloramphenicol in the mating media was found to stimulate conjugation, significantly increasing the transfer frequency of conjugation above the transfer frequency measured with mating media lacking both antibiotics and Hg. This research demonstrates that mercury indirectly selects for the dissemination of the antibiotic resistance genes of A. salmonicida AS03.

A broad-spectrum mer operon in a multi-drug resistant strain of the fish pathogen, Aeromonas salmonicida

Aeromonas salmonicida AS03, a potential fish pathogen, was isolated from Atlantic salmon, Salmo salar, in 2003. This strain was found to be resistant to ≥1000 mM HgCl2 and ≥32 mM phenylmercuric acetate as well as multiple antimicrobials. Mercury (Hg) and antibiotic resistance genes are often located on the same mobile genetic elements, so the genetic determinants of both resistances and the possibility of horizontal gene transfer were examined. Specific PCR primers were used to amplify and sequence distinctive regions of the mer operon. A. salmonicida AS03 was found to have a pDU1358-like broad-spectrum mer operon, containing merB as well as merA, merD, merP, merR and merT, most similar to Klebsiella pneumonaie plasmid pRMH760. To our knowledge, the mer operon has never before been documented in Aeromonas spp. PCR and gene sequencing were used to identify class 1 integron associated antibiotic resistance determinants and the Tet A tetracycline resistance gene. The transposase and resolvase genes of Tn1696 were identified through PCR and sequencing with Tn21 specific PCR primers. We provide phenotypic and genotypic evidence that the mer operon, the aforementioned antibiotic resistances, and the Tn1696 transposition module are located on a single plasmid or conjugative transposon that can be transferred to E. coli DH5α through conjugation in the presence of low level Hg and absence of any antibiotic selective pressure. Additionally, the presence of low-level Hg or chloramphenicol in the mating media was found to stimulate conjugation, significantly increasing the transfer frequency of conjugation above the transfer frequency measured with mating media lacking both antibiotics and Hg. This research demonstrates that mercury indirectly selects for the dissemination of the antibiotic resistance genes of A. salmonicida AS03.

O Conceito de postponement como estratégia de distribuição: um estudo de multi-casos no mercado brasileiro

Este trabalho discute a implementação da estratégia de postponement, um conceito que vem crescendo de importância nos últimos anos. Postponement é um conceito operacional que consiste em retardar a configuração final de produtos até que os pedidos dos consumidores sejam recebidos. Apesar da atratividade teórica e relevância do tema, pouco ainda se sabe sobre seu processo de implementação, especialmente no ambiente de negócio brasileiro. Este trabalho investigou em profundidade a implementação do postponement em cinco conceituadas empresas no Brasil procurando identificar os motivos que levaram seus respectivos executivos a adotarem tal estratégia, quais foram os agentes facilitadores e os obstáculos à implementação e, finalmente, até que ponto o postponement contribuiu para um aumento da competitividade.

Responsabilidade social empresarial do varejo no Brasil: um estudo, multi casos em empresas de grande porte

O estudo busca investigar a atuação das grandes empresas varejista brasileiras com relação à Responsabilidade Social Empresarial (RSE), procurando levantar o estágio em que estas se encontram, e se são aproveitadas as características do varejo de capilaridade geográfica, contato direto com a comunidade, forte vinculo com os clientes, interação entre funcionários e clientes e proximidade física de Organizações Não Governamentais e instituições públicas. Para tanto, foram utilizados conceitos relacionados à gestão, como comprometimento da cúpula, incorporação de valores de RSE na administração e no planejamento estratégico, autonomia e gestão de RSE nas lojas. A gestão foi avaliada pela ótica do contínuo de colaboração de Austin, e as práticas de RSE por meio da teoria dos stakeholders (públicos interessados), utilizando como base as dimensões dos Indicadores Ethos de Responsabilidade Social. A teoria de Kotler e Lee, para a classificação das iniciativas conforme os conceitos do marketing, também foi empregada. Conduziu-se uma pesquisa exploratória com cinco grandes empresas do setor varejista. Os resultados encontrados apontam que na maioria das empresas a incorporação dessas práticas é recente. Constata-se que as empresas diferem quanto ao estágio de RSE e que as características próprias do varejo não são aproveitadas em sua totalidade. Hipóteses são levantadas para que estas aproveitem a estrutura das lojas para atender às necessidades da comunidade local.

Cooperação e multi-level governance: o caso do Grande Recife Consórcio de Transporte Metropolitano

As primeiras regiões metropolitanas brasileiras foram instituídas de maneira vertical e autoritária como parte da estratégia de desenvolvimento nacional promovida pelo governo militar. Percebidas como instituições não-democráticas e rejeitadas como possível quarto ente federativo, as regiões metropolitanas, desde a Constituição de 1988, foram gradualmente esvaziadas dos seus propósitos originais. Em sua orfandade, os problemas socioeconômicos proliferaram e foram acentuados, e passaram a predominar relações intergovernamentais competitivas em vez de cooperativas. Um dos principais desafios enfrentados pelo modelo federalista brasileiro, em especial quando se trata destas regiões, está relacionado à necessidade de estabelecer maior cooperação e coordenação, tidas como imprescindíveis para garantir um relacionamento mais equilibrado entre os entes federativos, assim como para a efetiva implementação de políticas de enfrentamento das desigualdades e exclusão social nas aglomerações urbanas. Este trabalho analisa o Grande Recife Consórcio Metropolitano de Transportes (CMT), empresa pública multifederativa estabelecida em 2008 entre os governos municipais e estadual da Região Metropolitana de Recife (RMR). Responsável pelo planejamento, gestão e implementação compartilhada da política de transporte público coletivo na RMR, o Grande Recife se tornou realidade com a aprovação e regulamentação da Lei Federal nº 11.107 de 2005, conhecida como a Lei de Consórcios Públicos. O Grande Recife é uma experiência pioneira e inovadora, demonstrando que é possível encontrar uma maneira de superar conflitos e desafios comuns e, ao mesmo tempo, garantir a preservação da autonomia de cada ente, bem como os direitos cidadãos. Neste trabalho consideramos essa experiência de cooperação intergovernamental como um exemplo de multi-level governance (MLG), uma vez que é ilustrativa de um novo arranjo institucional democrático entre distintas esferas governamentais para a gestão compartilhada de um serviço público.

A governança corporativa nos clubes de futebol : um estudo multi-caso baseado nas práticas de governança corporativa dos clubes cariocas

Esta dissertação objetiva mapear as estruturas e as práticas de governança adotadas pelos clubes de futebol profissional no Brasil, aprofundando em estudo de caso o Flamengo, o Vasco da Gama, o Fluminense e o Botafogo. A partir de levantamento da situação econômico-financeira dos clubes brasileiros e da literatura dedicada à governança de associações e de clubes de futebol, foi realizado levantamento de aspectos da governança dispostos no Estatuto dos clubes, e dirigentes anteriores dos clubes foram entrevistados sobre esses aspectos. Para a análise desse material, buscou-se identificar o tratamento vinculado a aspectos fundamentais da boa governança tratados em códigos nacionais e internacionais. Os resultados evidenciaram uma grande diferença entre as estruturas e as práticas de governança dos clubes e aquelas recomendadas pelos códigos, apontando a necessidade de melhorias, mas também de melhores identificação e definição de boas práticas de governança específica para os clubes.

A Informatização da saúde no Brasil: uma análise multi-paper inspirada na teoria ator-rede

As tecnologias da informação e comunicação (TIC) estão presentes nas mais diversas áreas e atividades cotidianas, mas, em que pesem as ações de governos e instituições privadas, a informatização da saúde ainda é um desafio em aberto no Brasil. A situação atual leva a um questionamento sobre as dificuldades associadas à informatização das práticas em saúde, assim como, quais efeitos tais dificuldades têm causado à sociedade Brasileira. Com objetivo de discutir as questões acima citadas, esta tese apresenta quatro artigos sobre processo de informação da saúde no Brasil. O primeiro artigo revisa a literatura sobre TIC em saúde e baseado em duas perspectivas teóricas – estudos Europeus acerca dos Sistemas de Informação em Saúde (SIS) nos Países em Desenvolvimento e estudos sobre Informação e Informática em Saúde, no âmbito do Movimento da Reforma Sanitária –, formula um modelo integrado que combina dimensões de análise e fatores contextuais para a compreensão dos SIS no Brasil. Já o segundo artigo apresenta os conceitos e teóricos e metodológicos da Teoria Ator-Rede (ANT), uma abordagem para o estudo de controvérsias associadas às descobertas científicas e inovações tecnológicas, por meio das redes de atores envolvidos em tais ações. Tal abordagem tem embasado estudos de SI desde 1990 e inspirou as análises dois artigos empíricos desta tese. Os dois últimos artigos foram redigidos a partir da análise da implantação de um SIS em um hospital público no Brasil ocorrida entre os anos de 2010 e 2012. Para a análise do caso, seguiram-se os atores envolvidos nas controvérsias que surgiram durante a implantação do SIS. O terceiro artigo se debruçou sobre as atividades dos analistas de sistema e usuários envolvidos na implantação do SIS. As mudanças observadas durante a implantação do sistema revelam que o sucesso do SIS não foi alcançado pela estrita e técnica execução das atividades incialmente planejadas. Pelo contrário, o sucesso foi construído coletivamente, por meio da negociação entre os atores e de dispositivos de interessamento introduzidos durante o projeto. O quarto artigo, baseado no conceito das Infraestruturas de Informação, discutiu como o sistema CATMAT foi incorporado ao E-Hosp. A análise revelou como a base instalada do CATMAT foi uma condição relevante para a sua escolha durante a implantação do E-Hosp. Além disso, descrevem-se negociações e operações heterogêneas que aconteceram durante a incorporação do CATMAT no sistema E-Hosp. Assim, esta tese argumenta que a implantação de um SIS é um empreendimento de construção coletiva, envolvendo analistas de sistema, profissionais de saúde, políticos e artefatos técnicos. Ademais, evidenciou-se como os SIS inscrevem definições e acordos, influenciando as preferências dos atores na área de saúde.

Touch ‘n’ sketch: pen and fingers on a multi-touch sketch application for tablet PC’s

In many creative and technical areas, professionals make use of paper sketches for developing and expressing concepts and models. Paper offers an almost constraint free environment where they have as much freedom to express themselves as they need. However, paper does have some disadvantages, such as size and not being able to manipulate the content (other than remove it or scratch it), which can be overcome by creating systems that can offer the same freedom people have from paper but none of the disadvantages and limitations. Only in recent years has the technology become massively available that allows doing precisely that, with the development in touch‐sensitive screens that also have the ability to interact with a stylus. In this project a prototype was created with the objective of finding a set of the most useful and usable interactions, which are composed of combinations of multi‐touch and pen. The project selected Computer Aided Software Engineering (CASE) tools as its application domain, because it addresses a solid and well‐defined discipline with still sufficient room for new developments. This was the result from the area research conducted to find an application domain, which involved analyzing sketching tools from several possible areas and domains. User studies were conducted using Model Driven Inquiry (MDI) to have a better understanding of the human sketch creation activities and concepts devised. Then the prototype was implemented, through which it was possible to execute user evaluations of the interaction concepts created. Results validated most interactions, in the face of limited testing only being possible at the time. Users had more problems using the pen, however handwriting and ink recognition were very effective, and users quickly learned the manipulations and gestures from the Natural User Interface (NUI).

Remote presence: supporting deictic gestures through a handheld multi-touch device

This thesis argues on the possibility of supporting deictic gestures through handheld multi-touch devices in remote presentation scenarios. In [1], Clark distinguishes indicative techniques of placing-for and directing-to, where placing-for refers to placing a referent into the addressee’s attention, and directing-to refers to directing the addressee’s attention towards a referent. Keynote, PowerPoint, FuzeMeeting and others support placing-for efficiently with slide transitions, and animations, but support limited to none directing-to. The traditional “pointing feature” present in some presentation tools comes as a virtual laser pointer or mouse cursor. [12, 13] have shown that the mouse cursor and laser pointer offer very little informational expressiveness and do not do justice to human communicative gestures. In this project, a prototype application was implemented for the iPad in order to explore, develop, and test the concept of pointing in remote presentations. The prototype offers visualizing and navigating the slides as well as “pointing” and zooming. To further investigate the problem and possible solutions, a theoretical framework was designed representing the relationships between the presenter’s intention and gesture and the resulting visual effect (cursor) that enables the audience members to interpret the meaning of the effect and the presenter’s intention. Two studies were performed to investigate people’s appreciation of different ways of presenting remotely. An initial qualitative study was performed at The Hague, followed by an online quantitative user experiment. The results indicate that subjects found pointing to be helpful in understanding and concentrating, while the detached video feed of the presenter was considered to be distracting. The positive qualities of having the video feed were the emotion and social presence that it adds to the presentations. For a number of subjects, pointing displayed some of the same social and personal qualities [2] that video affords, while less intensified. The combination of pointing and video proved to be successful with 10-out-of-19 subjects scoring it the highest while pointing example came at a close 8-out-of-19. Video was the least preferred with only one subject preferring it. We suggest that the research performed here could provide a basis for future research and possibly be applied in a variety of distributed collaborative settings.

An Intelligent System for Petroleum Well Drilling Cutting Analysis

Cutting analysis is a important and crucial task task to detect and prevent problems during the petroleum well drilling process. Several studies have been developed for drilling inspection, but none of them takes care about analysing the generated cutting at the vibrating shale shakers. Here we proposed a system to analyse the cutting's concentration at the vibrating shale shakers, which can indicate problems during the petroleum well drilling process, such that the collapse of the well borehole walls. Cutting's images are acquired and sent to the data analysis module, which has as the main goal to extract features and to classify frames according to one of three previously classes of cutting's volume. A collection of supervised classifiers were applied in order to allow comparisons about their accuracy and efficiency. We used the Optimum-Path Forest (OPF), Artificial Neural Network using Multi layer Perceptrons (ANN-MLP), Support Vector Machines (SVM) and a Bayesian Classifier (BC) for this task. The first one outperformed all the remaining classifiers. Recall that we are also the first to introduce the OPF classifier in this field of knowledge. Very good results show the robustness of the proposed system, which can be also integrated with other commonly system (Mud-Logging) in order to improve the last one's efficiency.

Photoinduced hole-transfer in semiconducting polymer/low-bandgap cyanine dye blends: evidence for unit charge separation quantum yield

Power-conversion efficiencies of organic heterojunction solar cells can be increased by using semiconducting donor-acceptor materials with complementary absorption spectra extending to the near-infrared region. Here, we used continuous wave fluorescence and absorption, as well as nanosecond transient absorption spectroscopy to study the initial charge transfer step for blends of a donor poly(p-phenylenevinylene) derivative and low-band gap cyanine dyes serving as electron acceptors. Electron transfer is the dominant relaxation process after photoexcitation of the donor. Hole transfer after cyanine photoexcitation occurs with an efficiency close to unity up to dye concentrations of similar to 30 wt%. Cyanines present an efficient self-quenching mechanism of their fluorescence, and for higher dye loadings in the blend, or pure cyanine films, this process effectively reduces the hole transfer. Comparison between dye emission in an inert polystyrene matrix and the donor matrix allowed us to separate the influence of self-quenching and charge transfer mechanisms. Favorable photovoltaic bilayer performance, including high open-circuit voltages of similar to 1 V confirmed the results from optical experiments. The characteristics of solar cells using different dyes also highlighted the need for balanced adjustment of the energy levels and their offsets at the heterojunction when using low-bandgap materials, and accentuated important effects of interface interactions and solid-state packing on charge generation and transport.

Multi-objective evolutionary particle swarm optimization in the assessment of the impact of distributed generation

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