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.

Receptor MIMO em FPGA baseado no esquema de Alamouti

A oferta de serviços baseados em comunicações sem fios tem vindo a crescer exponencialmente na última década. Cada vez mais são exigidas maiores taxas de transmissão assim como uma melhor QoS, sem comprometer a potência de transmissão ou argura de banda disponível. A tecnologia MIMO consegue oferecer um aumento da capacidade destes sistemas sem requerer aumento da largura de banda ou da potência transmitida. O trabalho desenvolvido nesta dissertação consistiu no estudo dos sistemas MIMO, caracterizados pela utilização de múltiplas antenas para transmitir e receber a informação. Com um sistema deste tipo consegue-se obter um ganho de diversidade espacial utilizando códigos espaço-temporais, que exploram simultaneamente o domínio espacial e o domínio do tempo. Nesta dissertação é dado especial ênfase à codificação por blocos no espaço-tempo de Alamouti, a qual será implementada em FPGA, nomeadamente a parte de recepção. Esta implementação é efectuada para uma configuração de antenas 2x1, utilizando vírgula flutuante e para três tipos de modulação: BPSK, QPSK e 16-QAM. Por fim será analisada a relação entre a precisão alcançada na representação numérica dos resultados e os recursos consumidos pela FPGA. Com a arquitectura adoptada conseguem se obter taxas de transferência na ordem dos 29,141 Msimb/s (sem pipelines) a 262,674 Msimb/s (com pipelines), para a modulação BPSK.

Contact angle of a hemispherical bubble: An analytical approach

We have calculated the equilibrium shape of the axially symmetric Plateau border along which a spherical bubble contacts a flat wall, by analytically integrating Laplace's equation in the presence of gravity, in the limit of small Plateau border sizes. This method has the advantage that it provides closed-form expressions for the positions and orientations of the Plateau border surfaces. Results are in very good overall agreement with those obtained from a numerical solution procedure, and are consistent with experimental data. In particular we find that the effect of gravity on Plateau border shape is relatively small for typical bubble sizes, leading to a widening of the Plateau border for sessile bubbles and to a narrowing for pendant bubbles. The contact angle of the bubble is found to depend even more weakly on gravity. (C) 2009 Elsevier Inc. All rights reserved.

Geostatistical Mapping of Outfall Plume Dispersion Data gathered with an autonomous underwater vehicle

The main purpose of this study was to examine the applicability of geostatistical modeling to obtain valuable information for assessing the environmental impact of sewage outfall discharges. The data set used was obtained in a monitoring campaign to S. Jacinto outfall, located off the Portuguese west coast near Aveiro region, using an AUV. The Matheron’s classical estimator was used the compute the experimental semivariogram which was fitted to three theoretical models: spherical, exponential and gaussian. The cross-validation procedure suggested the best semivariogram model and ordinary kriging was used to obtain the predictions of salinity at unknown locations. The generated map shows clearly the plume dispersion in the studied area, indicating that the effluent does not reach the near by beaches. Our study suggests that an optimal design for the AUV sampling trajectory from a geostatistical prediction point of view, can help to compute more precise predictions and hence to quantify more accurately dilution. Moreover, since accurate measurements of plume’s dilution are rare, these studies might be very helpful in the future for validation of dispersion models.

Performance of microstrip antennas in the presence of EBG in an indoor localization system

Indoor localization systems in nowadays is a huge area of interest not only at academic but also at industry and commercial level. The correct location in these systems is strongly influenced by antennas performance which can provide several gains, bandwidths, polarizations and radiation patterns, due to large variety of antennas types and formats. This paper presents the design, manufacture and measurement of a compact microstrip antenna, for a 2.4 GHZ frequency band, enhanced with the use of Electromagnetic Band-Gap (EBG) structures, which improve the electromagnetic behavior of the conventional antennas. The microstrip antenna with an EBG structure integrated allows an improvement of the location system performance in about 25% to 30% relatively to a conventional microstrip antenna.

Patching up dipoles: can dipolar particles be viewed as patchy colloids?

We investigate whether the liquid-vapour phase transition of strongly dipolar fluids can be understood using a model of patchy colloids. These consist of hard spherical particles with three short-ranged attractive sites (patches) on their surfaces. Two of the patches are of type A and one is of type B. Patches A on a particle may bond either to a patch A or to a patch B on another particle. Formation of an AA (AB) bond lowers the energy by epsilon AA (epsilon AB). In the limit [image omitted], this patchy model exhibits condensation driven by AB-bonds (Y-junctions). Y-junctions are also present in low-density, strongly dipolar fluids, and have been conjectured to play a key role in determining their critical behaviour. We map the dipolar Yukawa hard-sphere (DYHS) fluid onto this 2A + 1B patchy model by requiring that the latter reproduce the correct DYHS critical point as a function of the isotropic interaction strength epsilon Y. This is achieved for sensible values of epsilon AB and the bond volumes. Results for the internal energy and the particle coordination number are in qualitative agreement with simulations of DYHSs. Finally, by taking the limit [image omitted], we arrive at a new estimate for the critical point of the dipolar hard-sphere fluid, which agrees with extrapolations from simulation.

Real-time rheology of actively growing bacteria

The population growth of a Staphylococcus aureus culture, an active colloidal system of spherical cells, was followed by rheological measurements, under steady-state and oscillatory shear flows. We observed a rich viscoelastic behavior as a consequence of the bacteria activity, namely, of their multiplication and density-dependent aggregation properties. In the early stages of growth (lag and exponential phases), the viscosity increases by about a factor of 20, presenting several drops and full recoveries. This allows us to evoke the existence of a percolation phenomenon. Remarkably, as the bacteria reach their late phase of development, in which the population stabilizes, the viscosity returns close to its initial value. Most probably, this is caused by a change in the bacteria physiological activity and in particular, by the decrease of their adhesion properties. The viscous and elastic moduli exhibit power-law behaviors compatible with the "soft glassy materials" model, whose exponents are dependent on the bacteria growth stage. DOI: 10.1103/PhysRevE.87.030701.

Study of the one dimensional and transient bioheat transfer equation: Multi-layer solution development and applications

: In this work we derive an analytical solution given by Bessel series to the transient and one-dimensional (1D) bioheat transfer equation in a multi-layer region with spatially dependent heat sources. Each region represents an independent biological tissue characterized by temperature-invariant physiological parameters and a linearly temperature dependent metabolic heat generation. Moreover, 1D Cartesian, cylindrical or spherical coordinates are used to define the geometry and temperature boundary conditions of first, second and third kinds are assumed at the inner and outer surfaces. We present two examples of clinical applications for the developed solution. In the first one, we investigate two different heat source terms to simulate the heating in a tumor and its surrounding tissue, induced during a magnetic fluid hyperthermia technique used for cancer treatment. To obtain an accurate analytical solution, we determine the error associated with the truncated Bessel series that defines the transient solution. In the second application, we explore the potential of this model to study the effect of different environmental conditions in a multi-layered human head model (brain, bone and scalp). The convective heat transfer effect of a large blood vessel located inside the brain is also investigated. The results are further compared with a numerical solution obtained by the Finite Element Method and computed with COMSOL Multi-physics v4.1 (c). (c) 2013 Elsevier Ltd. All rights reserved.

Antena multi-banda para comunicações móveis

O desenvolvimento dos sistemas de comunicações móveis tem vindo a ser cada vez maior, fazendo com que os sistemas funcionem em várias bandas de operação. Neste sentido, surge a necessidade de desenvolver antenas que superem aquelas já existentes, ao nível das suas propriedades electromagnéticas, para que os sistemas apresentem uma maior qualidade e possam corresponder às exigências inerentes ao desenvolvimento das sociedades. O objectivo desta dissertação de Mestrado é dimensionar, construir e medir uma antena multi-banda para comunicações móveis, com base em estruturas EBG (Electromagnetic Band-Gap) que melhorem o comportamento electromagnético daquelas já existentes, para a banda de frequências de 2.4 GHz e de 5.2 GHz. Começa-se por fazer-se um estudo acerca do estado da arte de estruturas EBG, muito utilizadas em várias áreas, nomeadamente a área das antenas, área sobre a qual esta dissertação assenta. Posteriormente é feita uma breve introdução às antenas microstrip, particularizando de seguida para antenas PIFA e as suas características. Posteriormente é feito o estudo de uma antena PIFA, com e sem a influência de estruturas EBG, para as bandas de 2.4 GHz e 5.2 GHz. Posteriormente são apresentados e comparados resultados das várias antenas. Da análise desses resultados, verifica-se que é possível obter uma antena de baixo perfil com a utilização de estruturas EBG como plano de massa. Além disso, verifica-se também que é possível diminuir a radiação traseira e aumentar a largura de banda. Finalmente, são apresentadas algumas conclusões e várias propostas de trabalho futuro.

Colloidal interactions in two-dimensional nematics

The interaction between two disks immersed in a 2D nernatic is investigated i) analytically using the tenser order parameter formalism for the nematic configuration around isolated disks and ii) numerically using finite-element methods with adaptive meshing to minimize the corresponding Landau-de Gennes free energy. For strong homeotropic anchoring, each disk generates a pair of defects with one-half topological charge responsible for the 2D quadrupolar interaction between the disks at large distances. At short distance, the position of the defects may change, leading to unexpected complex interactions with the quadrupolar repulsive interactions becoming attractive. This short-range attraction in all directions is still anisotropic. As the distance between the disks decreases, their preferred relative orientation with respect to the far-field nernatic director changes from oblique to perpendicular.

Particle agglomeration study in rf silane plasmas: In situ study by polarization-sensitive laser light scattering

To determine self-consistently the time evolution of particle size and their number density in situ multi-angle polarization-sensitive laser light scattering was used. Cross-polarization intensities (incident and scattered light intensities with opposite polarization) measured at 135 degrees and ex situ transmission electronic microscopy analysis demonstrate the existence of nonspherical agglomerates during the early phase of agglomeration. Later in the particle time development both techniques reveal spherical particles again. The presence of strong cross-polarization intensities is accompanied by low-frequency instabilities detected on the scattered light intensities and plasma emission. It is found that the particle radius and particle number density during the agglomeration phase can be well described by the Brownian free molecule coagulation model. Application of this neutral particle coagulation model is justified by calculation of the particle charge whereby it is shown that particles of a few tens of nanometer can be considered as neutral under our experimental conditions. The measured particle dispersion can be well described by a Brownian free molecule coagulation model including a log-normal particle size distribution. (C) 1996 American Institute of Physics.

How patchy can one get and still condense? The role of dissimilar patches in the interactions of colloidal particles

We investigate the influence of strong directional, or bonding, interactions on the phase diagram of complex fluids, and in particular on the liquid-vapour critical point. To this end we revisit a simple model and theory for associating fluids which consist of spherical particles having a hard-core repulsion, complemented by three short-ranged attractive sites on the surface (sticky spots). Two of the spots are of type A and one is of type B; the interactions between each pair of spots have strengths [image omitted], [image omitted] and [image omitted]. The theory is applied over the whole range of bonding strengths and results are interpreted in terms of the equilibrium cluster structures of the coexisting phases. In systems where unlike sites do not interact (i.e. where [image omitted]), the critical point exists all the way to [image omitted]. By contrast, when [image omitted], there is no critical point below a certain finite value of [image omitted]. These somewhat surprising results are rationalised in terms of the different network structures of the two systems: two long AA chains are linked by one BB bond (X-junction) in the former case, and by one AB bond (Y-junction) in the latter. The vapour-liquid transition may then be viewed as the condensation of these junctions and we find that X-junctions condense for any attractive [image omitted] (i.e. for any fraction of BB bonds), whereas condensation of the Y-junctions requires that [image omitted] be above a finite threshold (i.e. there must be a finite fraction of AB bonds).

Criticality of colloids with distinct interaction patches: The limits of linear chains, hyperbranched polymers, and dimers

We use a simple model of associating fluids which consists of spherical particles having a hard-core repulsion, complemented by three short-ranged attractive sites on the surface (sticky spots). Two of the spots are of type A and one is of type B; the bonding interactions between each pair of spots have strengths epsilon(AA), epsilon(BB), and epsilon(AB). The theory is applied over the whole range of bonding strengths and the results are interpreted in terms of the equilibrium cluster structures of the phases. In addition to our numerical results, we derive asymptotic expansions for the free energy in the limits for which there is no liquid-vapor critical point: linear chains (epsilon(AA)not equal 0, epsilon(AB)=epsilon(BB)=0), hyperbranched polymers (epsilon(AB)not equal 0, epsilon(AA)=epsilon(BB)=0), and dimers (epsilon(BB)not equal 0, epsilon(AA)=epsilon(AB)=0). These expansions also allow us to calculate the structure of the critical fluid by perturbing around the above limits, yielding three different types of condensation: of linear chains (AA clusters connected by a few AB or BB bonds); of hyperbranched polymers (AB clusters connected by AA bonds); or of dimers (BB clusters connected by AA bonds). Interestingly, there is no critical point when epsilon(AA) vanishes despite the fact that AA bonds alone cannot drive condensation.

Preservation of catechin antioxidant properties loaded in carbohydrate nanoparticles

Epigallocatechin gallate (EGCG), an antioxidant with several pharmacological and biological activities, was encapsulated in carbohydrate particles to preserve its antioxidant properties and improve its bioavailability. Gum arabic–maltodextrin particles loaded with EGCG (EGCG/P) were successfully produced by homogenization and spray-drying, with an EGCG loading efficiency of 96 ± 3%. Spray-dried particles are spherical or corrugated and polydisperse with diameters less than 20 m. The particles in aqueous suspension revealed two main populations, with mean average diameters of 40 nm and 400 nm. Attenuated total reflection-infrared spectroscopy (ATR-IR) confirmed that EGCG was incorporated in the carbohydrate matrix by intermolecular interactions, maintaining its chemical integrity. Atomic force microscopy imaging proved the particle spherical shape and size. The present study demonstrates that the carbohydrate matrix is able to preserve EGCG antioxidant properties, as proof of concept to be used as polymeric drug carrier.