Equilibrium self-assembly of colloids with distinct interaction sites: Thermodynamics, percolation, and cluster distribution functions

We calculate the equilibrium thermodynamic properties, percolation threshold, and cluster distribution functions for a model of associating colloids, which consists of hard spherical particles having on their surfaces three short-ranged attractive sites (sticky spots) of two different types, A and B. The thermodynamic properties are calculated using Wertheim's perturbation theory of associating fluids. This also allows us to find the onset of self-assembly, which can be quantified by the maxima of the specific heat at constant volume. The percolation threshold is derived, under the no-loop assumption, for the correlated bond model: In all cases it is two percolated phases that become identical at a critical point, when one exists. Finally, the cluster size distributions are calculated by mapping the model onto an effective model, characterized by a-state-dependent-functionality (f) over bar and unique bonding probability (p) over bar. The mapping is based on the asymptotic limit of the cluster distributions functions of the generic model and the effective parameters are defined through the requirement that the equilibrium cluster distributions of the true and effective models have the same number-averaged and weight-averaged sizes at all densities and temperatures. We also study the model numerically in the case where BB interactions are missing. In this limit, AB bonds either provide branching between A-chains (Y-junctions) if epsilon(AB)/epsilon(AA) is small, or drive the formation of a hyperbranched polymer if epsilon(AB)/epsilon(AA) is large. We find that the theoretical predictions describe quite accurately the numerical data, especially in the region where Y-junctions are present. There is fairly good agreement between theoretical and numerical results both for the thermodynamic (number of bonds and phase coexistence) and the connectivity properties of the model (cluster size distributions and percolation locus).

Percolation of colloids with distinct interaction sites

We generalize the Flory-Stockmayer theory of percolation to a model of associating (patchy) colloids, which consists of hard spherical particles, having on their surfaces f short-ranged-attractive sites of m different types. These sites can form bonds between particles and thus promote self-assembly. It is shown that the percolation threshold is given in terms of the eigenvalues of a m x m matrix, which describes the recursive relations for the number of bonded particles on the ith level of a cluster with no loops; percolation occurs when the largest of these eigenvalues equals unity. Expressions for the probability that a particle is not bonded to the giant cluster, for the average cluster size and the average size of a cluster to which a randomly chosen particle belongs, are also derived. Explicit results for these quantities are computed for the case f = 3 and m = 2. We show how these structural properties are related to the thermodynamics of the associating system by regarding bond formation as a (equilibrium) chemical reaction. This solution of the percolation problem, combined with Wertheim's thermodynamic first-order perturbation theory, allows the investigation of the interplay between phase behavior and cluster formation for general models of patchy colloids.

Caracterização tecnológica da mamografia digital em Portugal: progresso de um projeto em implementação

Introdução – A mamografia é o principal método de diagnóstico por imagem utilizado no rastreio e diagnóstico do cancro da mama, sendo a modalidade de imagem recomendada em vários países da Europa e Estados Unidos para utilização em programas de rastreio. A implementação da tecnologia digital causou alterações na prática da mamografia, nomeadamente a necessidade de adaptar os programas de controlo de qualidade. Objetivos – Caracterizar a tecnologia instalada para mamografia em Portugal e as práticas adotadas na sua utilização pelos profissionais de saúde envolvidos. Concluir sobre o nível de harmonização das práticas em mamografia em Portugal e a conformidade com as recomendações internacionais. Identificar oportunidades para otimização que permitam assegurar a utilização eficaz e segura da tecnologia. Metodologia – Pesquisa e recolha de dados sobre a tecnologia instalada, fornecidos por fontes governamentais, prestadores de serviços de mamografia e indústria. Construção de três questionários, orientados ao perfil do médico radiologista, técnico de radiologia com atividade em mamografia digital e técnico de radiologia coordenador. Os questionários foram aplicados em 65 prestadores de serviços de mamografia selecionados com base em critérios de localização geográfica, tipo de tecnologia instalada e perfil da instituição. Resultados – Foram identificados 441 sistemas para mamografia em Portugal. A tecnologia mais frequente (62%) e vulgarmente conhecida por radiografia computorizada (computed radiography) é constituída por um detector (image plate) de material fotoestimulável inserido numa cassete de suporte e por um sistema de processamento ótico. A maioria destes sistemas (78%) está instalada em prestadores privados. Aproximadamente 12% dos equipamentos instalados são sistemas para radiografia digital direta (Direct Digital Radiography – DDR). Os critérios para seleção dos parâmetros técnicos de exposição variam, observando-se que em 65% das instituições são adotadas as recomendações dos fabricantes do equipamento. As ferramentas de pós-processamento mais usadas pelos médicos radiologistas são o ajuste do contraste e brilho e magnificação total e/ou localizada da imagem. Quinze instituições (em 19) têm implementado um programa de controlo de qualidade. Conclusões – Portugal apresenta um parque de equipamentos heterogéneo que inclui tecnologia obsoleta e tecnologia “topo de gama”. As recomendações/guidelines (europeias ou americanas) não são adotadas formalmente na maioria das instituições como guia para fundamentação das práticas em mamografia, dominando as recomendações dos fabricantes do equipamento. Foram identificadas, pelos técnicos de radiologia e médicos radiologistas, carências de formação especializada, nomeadamente nas temáticas da intervenção mamária, otimização da dose e controlo da qualidade. A maioria dos inquiridos concorda com a necessidade de certificação da prática da mamografia em Portugal e participaria num programa voluntário. ABSTRACT - Introduction – Mammography is the gold standard for screening and imaging diagnosis of breast disease. It is the imaging modality recommended by screening programs in various countries in Europe and the United States. The implementation of the digital technology promoted changes in mammography practice and triggered the need to adjust quality control programs. Aims –Characterize the technology for mammography installed in Portugal. Assess practice in use in mammography and its harmonization and compliance to international guidelines. Identify optimization needs to promote an effective and efficient use of digital mammography to full potential. Methodology – Literature review was performed. Data was collected from official sources (governmental bodies, mammography healthcare providers and medical imaging industry) regarding the number and specifications of mammography equipment installed in Portugal. Three questionnaires targeted at radiologists, breast radiographers and the chief-radiographer were designed for data collection on the technical and clinical practices in mammography. The questionnaires were delivered in a sample of 65 mammography providers selected according to geographical criteria, type of technology and institution profile. Results – Results revealed 441 mammography systems installed in Portugal. The most frequent (62%) technology type are computerized systems (CR) mostly installed in the private sector (78%). 12% are direct radiography systems (DDR). The criteria for selection of the exposure parameters differ between the institutions with the majority (65%) following the recommendations from the manufacturers. The use of available tools for post-processing is limited being the most frequently reported tools used the contrast/ brightness and Zoom or Pan Magnification tools. Fifteen participant institutions (out of 19) have implemented a quality control programme. Conclusions – The technology for mammography in Portugal is heterogeneous and includes both obsolete and state of the art equipment. International guidelines (European or American) are not formally implemented and the manufacturer recommendations are the most frequently used guidance. Education and training needs were identified amongst the healthcare professionals (radiologists and radiographers) with focus in the areas of mammography intervention, patient dose optimization and quality control. The majority of the participants agree with the certification of mammography in Portugal.

As televisões generalistas portuguesas online: estudo sobre a presença de conteúdos Informativos nos sites da RTP, SIC e TVI

Dissertação apresentada à Escola Superior de Comunicação Social como parte dos requisitos para obtenção de grau de mestre em Audiovisual e Multimédia.