Rates of electronic energy transfer in conformationally flexible bichromophoric macrocyclic complexes: a combined experimental and molecular modeling study

Electronic energy transfer (EET) rate constants between a naphthalene donor and anthracene acceptor in [ZnL4a](ClO4)(2) and [ZnL4b](ClO4)(2) were determined by time-resolved fluorescence where L-4a and L-4b are the trans and cis isomers of 6-((anthracen-9-yl-methyl)amino)-6,13-dimethyl-13-((naphthalen-1-yl-methyl)amino)-1,4,8,11-tetraazacyclotetradecane, respectively. These isomers differ in the relative disposition of the appended chromophores with respect to the macrocyclic plane. The trans isomer has an energy transfer rate constant (k(EET)) of 8.7 x 10(8) s(-1), whereas that of the cis isomer is significantly faster (2.3 x 10(9) s(-1)). Molecular modeling was used to determine the likely distribution of conformations in CH3CN solution for these complexes in an attempt to identify any distance or orientation dependency that may account for the differing rate constants observed. The calculated conformational distributions together with analysis by H-1 NMR for the [ZnL4a](2+) trans complex in the common trans-III N-based isomer gave a calculated Forster rate constant close to that observed experimentally. For the [ZnL4b](2+) cis complex, the experimentally determined rate constant may be attributed to a combination of trans-Ill and trans-I N-based isomeric forms of the complex in solution.

Consumidor de mídias móveis : a influência do perfil do adotante na relação entre valor percebido e intenção de compra

O presente estudo tem por objetivo avaliar se o perfil do adotante de inovações altera a relação entre o Valor Percebido e a Intenção de Compra de mídias móveis (smartphones, tablets, ultrabooks e leitores de e-books). Trata-se de uma pesquisa quantitativa que busca explorar a relação estrutural entre as variáveis por meio de Modelagem de Equações Estruturais (SEM – Strutural Equation Modeling). O modelo de pesquisa proposto foi desenvolvido tendo como base a Teoria da Difusão da Inovação (TDI), a Teoria Unificada de Aceitação e Uso de Tecnologia (UTAUT), o Modelo de Aceitação de Tecnologia (TAM), o Modelo Baseado em Valor (VAM), o Modelo de Aceitação de Tecnologia pelo Consumidor (CAT) e o Modelo de Influência Social (IS). Para coletar os dados foi utilizada a técnica snowball sampling ou amostragem em bola de neve, forma de amostragem não probabilística utilizada em pesquisas sociais. Foi feito um levantamento (survey), distribuindo-se questionário disponibilizado pela rede social Facebook, a partir dos contatos do autorsolicitando-se que os respondentes replicassem em suas páginas pessoais o link da pesquisa, ampliando a amostra. A coleta dos dados foi realizada nos meses de setembro e outubro de 2013, obtendo-se um total de 362 questionários respondidos. O estudo apresentou um efeito significativo da variável Valor Percebido na Intenção de Compra (estatística t = 4,506; nível de significância de 1%), além de sustentar a influência moderadora do Perfil do Adotante sobre essa relação (estatística t = 4,066; nível de significância de 1%), apresentando alto impacto sobre a Intenção de Compra (f 2 = 0,582) e relevância preditiva moderada (q2 = 0,290). Entre as variáveis antecedentes relacionadas à adoção de tecnologia, não apresentaram efeito significativo sobre o Valor Percebido: a Facilidade de Uso Percebida, a Complexidade Percebida e o Risco Percebido. O modelo contribuiu significativamente para explicar a influência dos fatores que impactam o Valor Percebido (R2 = 51,7%) o efeito do Valor Percebido na Intenção de Compra (R2 = 49,1%) de equipamentos eletrônicos portáteis. O suporte da presumidade influência moderadora do Perfil do Adotante sobre a relação Valor Percebido e Intenção de Compra indica que as organizações devem conhecer melhor os consumidores desse tipo de equipamento móveis, segmentando e desenvolvendo ações alinhadas com cada perfil de adotante.

Estudo do transporte atmosférico de Mp10 e SO2 com os Modelos WRF/CMAQ em regiões costeiras urbanas

O objetivo principal deste trabalho foi o estudo do transporte atmosférico de PM10 e SO2 em regiões costeiras urbanas usando modelos WRF/CMAQ. Duas regiões foram contempladas neste estudo. Uma é a Região da Grande Vitória (RGV), no estado do Espírito Santo, Brasil; a outra é a Região da Grande Dunkerque (RGD), no Departamento Nord Pas-de-Calais, França. A RGV é cercada por uma cadeia de montanhas paralela à costa, resultando num topografia complexa e acidentada. Já a RGD possui uma topografia muito mais suave. As entradas de dados para os modelos WRF/CMAQ englobaram o inventário de emissões de poluentes atmosféricos do IEMA-ES para a RGV, e o inventário de emissões no nível do solo de Nord Pas-de-Calais denominado ―Cadastre_totaux_3km_A2008 _M2010_V2_SNAPN2‖ para a RGD. Ambos os inventários apresentaram restrições, todavia. O inventário da RGV apresentou valores de ressuspensão em vias de tráfego elevados, em comparação com diversos estudos, e teve esses dados modificados. Os dados no nível do solo e a grande área de das células da grade (9 km2) do inventário da RGD não permitiram resultados satisfatórios de modelagem. A validação dos modelos foi realizada por comparação com resultados obtidos em duas campanhas experimentais: uma na cidade de Dunkerque, no norte da França, em setembro de 2009; a outra na cidade de Vitória, no sudeste do Brasil, em julho de 2012. Esses dados foram obtidos pelo uso de sistemas de Light Detection and Ranging (LIDAR) e Sonic Detection and Ranging (SODAR), bem como de Estações Meteorológicas de Superfície (EMS) e de monitoramento atmosférico. Os resultados deste trabalho mostraram que: a) existe uma necessidade de melhorias contínuas nos inventários regionais de emissões, adaptando-os para condições locais específicas e focando na obtenção de parâmetros necessários para modelagem fotoquímica; b) os valores de módulo e direção das velocidades obtidas na modelagem meteorológica influenciam fortemente os resultados da modelagem de concentração de poluentes; c) a qualidade do ar tanto na RGV quanto na RGD merece atenção, sobretudo no que diz respeito às concentrações de MP10. De acordo com os dados das estações de monitoramento, a situação parece mais crítica na RGD; d) a modelagem da RGV apresentou resultados mais satisfatórios do que a da RGD, de acordo com os resultados das validações; e) a entrada da brisa do mar provocou alterações significativas na concentração dos poluentes, o que pôde ser observado na análise da dinâmica da dispersão de MP10 e SO2. Esse fenômeno foi mais marcante na RGV, onde a entrada da brisa marítima provocou um movimento oscilatório na pluma de poluição, levando-a para os bairros mais densamente povoados do conglomerado urbano. Na RGD, a entrada da brisa não foi cotidiana e, no dia em que ela aconteceu, houve uma alteração de quase 180º na direção do movimento da pluma de poluição. Além do aumento da turbulência vertical, o qual já foi estudado por diversos autores, este estudo focou também na influência brisa do mar na dinâmica da pluma de dispersão de poluentes atmosféricos em regiões costeiras.

Multi-level governance and social cohesion in the European Union: the assessment of local agents, a study case inside Galicia

Implementing multi-level governance has been a key priority in EU cohesion policy. This study assesses the perceived achievements and shortcomings in implementing European Social Fund by analyzing the deficits and weaknesses as well as the poor participation of local agents who are in direct contact with the beneficiaries in order to design and implement this fund, which is the main financial instrument of EU social policy.

Modeling Carbon Nanotube Electrical Properties in CNT/Polymer Composites

In this work it is demonstrated that the capacitance between two cylinders increases with the rotation angle and it has a fundamental influence on the composite dielectric constant. The dielectric constant is lower for nematic materials than for isotropic ones and this can be attributed to the effect of the filler alignment in the capacitance. The effect of aspect ratio in the conductivity is also studied in this work. Finally, based on previous work and by comparing to results from the literature it is found that the electrical conductivity in this type of composites is due to hopping between nearest fillers resulting in a weak disorder regime that is similar to the single junction expression.

Multi-scale modeling of the mechanical behavior of polymer-based materials

Polymers have become the reference material for high reliability and performance applications. In this work, a multi-scale approach is proposed to investigate the mechanical properties of polymeric based material under strain. To achieve a better understanding of phenomena occurring at the smaller scales, a coupling of a Finite Element Method (FEM) and Molecular Dynamics (MD) modeling in an iterative procedure was employed, enabling the prediction of the macroscopic constitutive response. As the mechanical response can be related to the local microstructure, which in turn depends on the nano-scale structure, the previous described multi-scale method computes the stress-strain relationship at every analysis point of the macro-structure by detailed modeling of the underlying micro- and meso-scale deformation phenomena. The proposed multi-scale approach can enable prediction of properties at the macroscale while taking into consideration phenomena that occur at the mesoscale, thus offering an increased potential accuracy compared to traditional methods.

Damage level of the two-spotted spider mite Tetranychus urticae Koch (acari: tetranychidae) in soybeans

Among phytophagous spider mites, the two-spotted spider mite Tetranychus urticae Koch, 1836 is one of the most important agricultural pests, not only because of the damage it causes, but also because it has a wide host range, infesting many commercial crops such as leafy greens, cotton, beans, and soybeans, among others. This study was carried out in a greenhouse of the Faculdade de Ciências Agrárias (FCA) of the Universidade Federal da Grande Dourados (UFGD), located in the city of Dourados, state of Mato Grosso do Sul. The experiment was arranged in a randomized block design with 5 treatments and 4 replicates. The treatments consisted of 5 levels in percentage of chlorotic symptoms (indicating mite damage): 0%, 25%, 50%, 75%, and 100%. All of the characteristics evaluated, except for number of pods per plant, the number of seeds per plant, the total weight (productivity), and the weight of 1000 seeds, were significantly influenced by the different levels of chlorotic symptoms. The economic damage level for the two-spotted spider mite Tetranychus urticae, according to the equation y = 66.63-0.51 x, based on the price of US$ 11.00 per bag of soybeans and a control cost of US$ 16.00, would be 15.80% chlorotic symptoms. At a price of US$ 29.00 per bag with the same control cost, the economic damage level would be 13% of chlorotic symptoms.

Prevalence of periodontal disease in dogs and owners' level of awareness - a prospective clinical trial

Periodontal disease (PD) is widely known among veterinarians for its high prevalence and serious consequences to the dogs. The objective of this study was to assess the occurrence of PD in dogs that live in the micro-region of Viçosa, treated at the Veterinary Hospital of the Federal University of Viçosa (HVT - Hospital Veterinário da Universidade Federal de Viçosa), as well as to assess how aware of this disease dog owners are. In order to do so, all dogs treated at the HVT from March 10th, 2009 to November 30th, 2009, on alternate days, had their oral cavities examined. Medical history data, such as age, type of food, main complaint and owner consent, halitosis, presence of dental calculus, inflammation and gingival recession and tooth loss, were collected. A prevalence of 88.67% was found for PD in dogs referred to the HVT, and 2.67% were referred due to this disease. Of all the owners who participated in the study, 43.83% knew about periodontal disease and of these 17.46% made use of some type of prevention or treatment. Therefore, periodontal disease is highly prevalent and the owners are not aware of the disease. Thus, a dog owner clarification program on periodontal disease is needed in the area where HVT-UFV operates.

Assessment of 3D scanners for modeling Pectus Carinatum corrective bar

Pectus Carinatum (PC) is a chest deformity consisting on the anterior protrusion of the sternum and adjacent costal cartilages. Non-operative corrections, such as the orthotic compression brace, require previous information of the patient chest surface, to improve the overall brace fit. This paper focuses on the validation of the Kinect scanner for the modelling of an orthotic compression brace for the correction of Pectus Carinatum. To this extent, a phantom chest wall surface was acquired using two scanner systems – Kinect and Polhemus FastSCAN – and compared through CT. The results show a RMS error of 3.25mm between the CT data and the surface mesh from the Kinect sensor and 1.5mm from the FastSCAN sensor

Automatic modeling of an orthotic bracing for nonoperative correction of PectusCarinatum

Pectus Carinatum is a deformity of the chest wall, characterized by an anterior protrusion of the sternum, often corrected surgically due to cosmetic motivation. This work presents an alternative approach to the current open surgery option, proposing a novel technique based on a personalized orthosis. Two different processes for the orthosis’ personalization are presented. One based on a 3D laser scan of the patient chest, followed by the reconstruction of the thoracic wall mesh using a radial basis function, and a second one, based on a computer tomography scan followed by a neighbouring cells algorithm. The axial position where the orthosis is to be located is automatically calculated using a Ray-Triangle intersection method, whose outcome is input to a pseudo Kochenek interpolating spline method to define the orthosis curvature. Results show that no significant differences exist between the patient chest physiognomy and the curvature angle and size of the orthosis, allowing a better cosmetic outcome and less initial discomfort

Automatic modeling of pectus excavatum corrective prosthesis using artificial neural networks

Pectus excavatum is the most common deformity of the thorax. Pre-operative diagnosis usually includes Computed Tomography (CT) to successfully employ a thoracic prosthesis for anterior chest wall remodeling. Aiming at the elimination of radiation exposure, this paper presents a novel methodology for the replacement of CT by a 3D laser scanner (radiation-free) for prosthesis modeling. The complete elimination of CT is based on an accurate determination of ribs position and prosthesis placement region through skin surface points. The developed solution resorts to a normalized and combined outcome of an artificial neural network (ANN) set. Each ANN model was trained with data vectors from 165 male patients and using soft tissue thicknesses (STT) comprising information from the skin and rib cage (automatically determined by image processing algorithms). Tests revealed that ribs position for prosthesis placement and modeling can be estimated with an average error of 5.0 ± 3.6 mm. One also showed that the ANN performance can be improved by introducing a manually determined initial STT value in the ANN normalization procedure (average error of 2.82 ± 0.76 mm). Such error range is well below current prosthesis manual modeling (approximately 11 mm), which can provide a valuable and radiation-free procedure for prosthesis personalization.

Automatic modeling of pectus excavatum corrective prosthesis using artificial neural networks

Pectus excavatum is the most common deformity of the thorax. Pre-operative diagnosis usually includes Computed Tomography (CT) to successfully employ a thoracic prosthesis for anterior chest wall remodeling. Aiming at the elimination of radiation exposure, this paper presents a novel methodology for the replacement of CT by a 3D laser scanner (radiation-free) for prosthesis modeling. The complete elimination of CT is based on an accurate determination of ribs position and prosthesis placement region through skin surface points. The developed solution resorts to a normalized and combined outcome of an artificial neural network (ANN) set. Each ANN model was trained with data vectors from 165 male patients and using soft tissue thicknesses (STT) comprising information from the skin and rib cage (automatically determined by image processing algorithms). Tests revealed that ribs position for prosthesis placement and modeling can be estimated with an average error of 5.0 ± 3.6 mm. One also showed that the ANN performance can be improved by introducing a manually determined initial STT value in the ANN normalization procedure (average error of 2.82 ± 0.76 mm). Such error range is well below current prosthesis manual modeling (approximately 11 mm), which can provide a valuable and radiation-free procedure for prosthesis personalization.

Assessment of 3D scanners for modeling pectus carinatum corrective bar

Pectus Carinatum (PC) is a chest deformity consisting on the anterior protrusion of the sternum and adjacent costal cartilages. Non-operative corrections, such as the orthotic compression brace, require previous information of the patient chest surface, to improve the overall brace fit. This paper focuses on the validation of the Kinect scanner for the modelling of an orthotic compression brace for the correction of Pectus Carinatum. To this extent, a phantom chest wall surface was acquired using two scanner systems – Kinect and Polhemus FastSCAN – and compared through CT. The results show a RMS error of 3.25mm between the CT data and the surface mesh from the Kinect sensor and 1.5mm from the FastSCAN sensor.

Automatic modeling of an orthotic bracing for nonoperative correction of pectus carinatum

Pectus Carinatum is a deformity of the chest wall, characterized by an anterior protrusion of the sternum, often corrected surgically due to cosmetic motivation. This work presents an alternative approach to the current open surgery option, proposing a novel technique based on a personalized orthosis. Two different processes for the orthosis’ personalization are presented. One based on a 3D laser scan of the patient chest, followed by the reconstruction of the thoracic wall mesh using a radial basis function, and a second one, based on a computer tomography scan followed by a neighbouring cells algorithm. The axial position where the orthosis is to be located is automatically calculated using a Ray-Triangle intersection method, whose outcome is input to a pseudo Kochenek interpolating spline method to define the orthosis curvature. Results show that no significant differences exist between the patient chest physiognomy and the curvature angle and size of the orthosis, allowing a better cosmetic outcome and less initial discomfort.

An optimal level of technology reliance on foreign partners in a global sourcing partnership: components procurement, technology management and market performance

Existing studies on global sourcing strategy have implicitly adopted a cJosed-systems perspective in which sourcing activities are managed within a multinational company across national boundaries. Produd and process innovations and components procurement that are jointly managed by a consortium of cooperating firms have not been examined. In this paper, we empiricallyexamine the issues concerning sourcing partnerships in an open-systems perspective. Findings suggest that even in a sourcing partnership arrangement with a foreign supplier, the principal firm's ability to procure and control the supply of major components has a positive bearing on its market performance.