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.

Riders in the storm: the professions and healthcare governance

The public sector is facing turbulent times and this also challenges the health professions who are expected to serve both the interests of the citizens and the cost-containment and austerity policies of governments. This article seeks to explore the changing role of the health professions. I introduce an approach on ‘citizen professionals’ as active players in the policy process and mediators between the state/policymakers and the citizens/patients. The aim is to highlight a transformative potential of professionalism and the connectedness with other sets of governance, like management. Empirical material from a German case study and a comparative European study serve to illustrate the arguments, drawing on policy analysis and secondary sources. The results bring the complexity of transformations and new emergent forms of professionalism into view that cannot be understood in traditional categories of conflict, exclusion and jurisdiction. Exploring the potential of the health professions to creatively respond to new challenges may reveal new opportunities for innovating healthcare policy beyond market and management.

A individualização do direito à saúde: contributos a partir de um olhar analítico

Este artigo de natureza ensaística procura contribuir para o desenvolvimento de argumentos já apresentados a respeito de reconfigurações ideológicas nas políticas de saúde. A partir de dimensões analíticas discute-se o espaço e implicações da individualização do direito à saúde no contexto de maior liberalização dos mercados e de maior exposição ao investimento privado lucrativo. A individualização do direito à saúde assume-se como contrária aos princípios éticos e morais consolidados entre os países ocidentais a partir da 2ª metade do séc. XX, em que o acesso aos cuidados passa gradualmente a estar dependente das condições individuais das famílias, não obstante o pagamento de impostos e outros seguros. Não só passa a existir espaço para formas desiguais de acesso ao direito à saúde, como o princípio da utilização racional que baseia esta reconfiguração é uma crença managerialista falaciosa e, em larga medida, irrealista. Esta discussão é ilustrada a partir de dados da OCDE, os quais demonstram tendências díspares a respeito desta dinâmica.

Sistemas de saúde e participação cidadã: algumas reflexões críticas na perspetiva da sociologia da saúde

Nos últimos dez a quinze anos temos assistido a um aumento do número de iniciativas com a participação da sociedade civil, no sentido de exercer pressão para a reformulação dos direitos sociais. Estes já não são tão vistos como direitos para aceder aos serviços estruturados e administrados pelo Estado (de acordo com o conceito de cidadania de Marshall), mas como uma reivindicação dos cidadãos para terem um papel ativo na definição das políticas públicas e dos serviços. Este debate tem sido muito intenso entre os cientistas sociais desde a década de 1980 e está bastante presente no sistema de cuidados de saúde. Vários estudos têm salientado a forte tensão entre o tecnicismo da medicina e a organização burocrática do sistema de saúde, por um lado, e o modelo de comunicação quotidiana, por outro lado. De facto, um dos temas centrais das reformas dos cuidados de saúde nos últimos 20 anos centrou-se na valorização da experiência e da perspetiva dos cidadãos. O artigo começa com um breve esboço das novas abordagens sociológicas em torno da relação entre os sistemas sociais e o mundo real – nas dimensões micro e macro; estrutura e ação. Assim, apresenta-se o estado da arte atual sobre a participação nos sistemas de saúde ocidentais, resultante da revisão da literatura, destacando as novas estratégias de envolvimento dos doentes bem como as questões relativas às críticas e às limitações. Para terminar, procede-se a uma reflexão acerca da complexidade da relação entre o sistema de cuidados de saúde e as associações de doentes e utentes.

Cultural organizations and communication in portuguese decentralization policy

This paper intends to show the Portuguese municipalities’ commitment, since the first decade of this century, in cultural facilities of municipal management and how it provided 12 of the 18 district capitals of mainland Portugal with cultural equipment, but after all we want to know if this effort resulted in a regular, diverse, and innovative schedule. Investing in urban regeneration, local governments have tried to convert cities’ demographic changes (strengthening of the most educated and professionally qualified groups) in effective cultural demands that consolidate the three axes of development competitiveness-innovation-creativity. What the empirical study to the programming and communication proposals of those equipment shows is that it is not enough to provide cities with facilities; to escape to a utilitarian conception of culture, there is a whole work to be done so that such equipment be experienced and felt as new public sphere. Equipment in which proposals go through a fluid bind, constructed through space and discourse with local community, devoted a diversified and innovative bet full filling development axis. This paper presents in a systematic way what contributes to this binding on the analyzed equipment.

Cultural organizations and communication in portuguese decentralization policy

This presentation intends to show to what extent the Portuguese municipalities’ commitment, from the first decade of this century, in cultural facilities of municipal management and which has provided 12 of the 18 district capitals of mainland Portugal with equipment, resulted in a regular, diverse and innovative schedule. Investing in urban regeneration, local government has tried to convert cities’ demographic changes (strengthening of the most educated and professionally qualified groups) in effective cultural demands that consolidate the three axes of development competitiveness-innovation-creativity. What the empirical study to the programming and communication proposals of those equipment shows is that it is not enough to provide cities with facilities; to escape to a utilitarian conception of culture, there is a whole work to be done so that such equipment be experienced and felt as new public sphere. Equipment in which proposals go through a fluid bind, constructed through space and discourse with local community, devotes a diversified and innovative bet full filling development axis. This paper presents in a systematic way what contributes to this binding on the analyzed equipment.

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.