Synthesis, structure, and optical properties of an alternating calix[4]arene-based meta-linked phenylene ethynylene copolymer

Novel alternating copolymers comprising biscalix[4]arene-p-phenylene ethynylene and m-phenylene ethynylene units (CALIX-m-PPE) were synthesized using the Sonogashira-Hagihara cross-coupling polymerization. Good isolated yields (60-80%) were achieved for the polymers that show M-n ranging from 1.4 x 10(4) to 5.1 x 10(4) gmol(-1) (gel permeation chromatography analysis), depending on specific polymerization conditions. The structural analysis of CALIX-m-PPE was performed by H-1, C-13, C-13-H-1 heteronuclear single quantum correlation (HSQC), C-13-H-1 heteronuclear multiple bond correlation (HMBC), correlation spectroscopy (COSY), and nuclear overhauser effect spectroscopy (NOESY) in addition to Fourier transform-Infrared spectroscopy and microanalysis allowing its full characterization. Depending on the reaction setup, variable amounts (16-45%) of diyne units were found in polymers although their photophysical properties are essentially the same. It is demonstrated that CALIX-m-PPE does not form ground-or excited-state interchain interactions owing to the highly crowded environment of the main-chain imparted by both calix[4]arene side units which behave as insulators inhibiting main-chain pi-pi staking. It was also found that the luminescent properties of CALIX-m-PPE are markedly different from those of an all-p-linked phenylene ethynylene copolymer (CALIX-p-PPE) previously reported. The unexpected appearance of a low-energy emission band at 426 nm, in addition to the locally excited-state emission (365 nm), together with a quite low fluorescence quantum yield (Phi = 0.02) and a double-exponential decay dynamics led to the formulation of an intramolecular exciplex as the new emissive species.

Chaos and crises in a model for cooperative hunting: A symbolic dynamics approach

In this work we investigate the population dynamics of cooperative hunting extending the McCann and Yodzis model for a three-species food chain system with a predator, a prey, and a resource species. The new model considers that a given fraction sigma of predators cooperates in prey's hunting, while the rest of the population 1-sigma hunts without cooperation. We use the theory of symbolic dynamics to study the topological entropy and the parameter space ordering of the kneading sequences associated with one-dimensional maps that reproduce significant aspects of the dynamics of the species under several degrees of cooperative hunting. Our model also allows us to investigate the so-called deterministic extinction via chaotic crisis and transient chaos in the framework of cooperative hunting. The symbolic sequences allow us to identify a critical boundary in the parameter spaces (K, C-0) and (K, sigma) which separates two scenarios: (i) all-species coexistence and (ii) predator's extinction via chaotic crisis. We show that the crisis value of the carrying capacity K-c decreases at increasing sigma, indicating that predator's populations with high degree of cooperative hunting are more sensitive to the chaotic crises. We also show that the control method of Dhamala and Lai [Phys. Rev. E 59, 1646 (1999)] can sustain the chaotic behavior after the crisis for systems with cooperative hunting. We finally analyze and quantify the inner structure of the target regions obtained with this control method for wider parameter values beyond the crisis, showing a power law dependence of the extinction transients on such critical parameters.

Some bounds of loss in classical semideterministic immunization

Since Samuelson, Redington and Fisher and Weil, duration and immunization are very important topics in bond portfolio analysis from both a theoretical and a practical point of view. Many results have been established, especially in semi-deterministic framework. As regards, however, the loss may be sustained, we do not think that the subject has been investigated enough, except for the results found in the wake of the theorem of Fong and Vasicek. In this paper we present some results relating to the limitation of the loss in the case of local immunization for multiple liabilities.

Pricing intraday dynamics across EUAS and CERS markets

The relative contribution of European Union Allowances (EUAs) and Certified Emission Reductions (CERs) to the price discovery of their common true value has been empirically studied using daily data with inconclusive results. In this paper, we study the short-run and long-run price dynamics between EUAs and CERs future contracts using intraday data. We report a bidirectional feedback causality relationship both in the short-run and in the long-run, with the EUA's market being the leader.

Autoinhibition of TBCB regulates EB1-mediated microtubule dynamics

Tubulin cofactors (TBCs) participate in the folding, dimerization, and dissociation pathways of the tubulin dimer. Among them, TBCB and TBCE are two CAP-Gly domain-containing proteins that together efficiently interact with and dissociate the tubulin dimer. In the study reported here we showed that TBCB localizes at spindle and midzone microtubules during mitosis. Furthermore, the motif DEI/M-COO− present in TBCB, which is similar to the EEY/F-COO− element characteristic of EB proteins, CLIP-170, and α-tubulin, is required for TBCE–TBCB heterodimer formation and thus for tubulin dimer dissociation. This motif is responsible for TBCB autoinhibition, and our analysis suggests that TBCB is a monomer in solution. Mutants of TBCB lacking this motif are derepressed and induce microtubule depolymerization through an interaction with EB1 associated with microtubule tips. TBCB is also able to bind to the chaperonin complex CCT containing α-tubulin, suggesting that it could escort tubulin to facilitate its folding and dimerization, recycling or degradation.

Symbolic dynamics and renormalization of non-autonomous k periodic dynamical systems

The purpose of this paper was to introduce the symbolic formalism based on kneading theory, which allows us to study the renormalization of non-autonomous periodic dynamical systems.

An Extension of Gompertzian Growth Dynamics Weibull and Frechet Models

In this work a new probabilistic and dynamical approach to an extension of the Gompertz law is proposed. A generalized family of probability density functions, designated by Beta* (p, q), which is proportional to the right hand side of the Tsoularis-Wallace model, is studied. In particular, for p = 2, the investigation is extended to the extreme value models of Weibull and Frechet type. These models, described by differential equations, are proportional to the hyper-Gompertz growth model. It is proved that the Beta* (2, q) densities are a power of betas mixture, and that its dynamics are determined by a non-linear coupling of probabilities. The dynamical analysis is performed using techniques of symbolic dynamics and the system complexity is measured using topological entropy. Generally, the natural history of a malignant tumour is reflected through bifurcation diagrams, in which are identified regions of regression, stability, bifurcation, chaos and terminus.

Topological Complexity and Predictability in the Dynamics of a Tumor Growth Model with Shilnikov's Chaos

Dynamical systems modeling tumor growth have been investigated to determine the dynamics between tumor and healthy cells. Recent theoretical investigations indicate that these interactions may lead to different dynamical outcomes, in particular to homoclinic chaos. In the present study, we analyze both topological and dynamical properties of a recently characterized chaotic attractor governing the dynamics of tumor cells interacting with healthy tissue cells and effector cells of the immune system. By using the theory of symbolic dynamics, we first characterize the topological entropy and the parameter space ordering of kneading sequences from one-dimensional iterated maps identified in the dynamics, focusing on the effects of inactivation interactions between both effector and tumor cells. The previous analyses are complemented with the computation of the spectrum of Lyapunov exponents, the fractal dimension and the predictability of the chaotic attractors. Our results show that the inactivation rate of effector cells by the tumor cells has an important effect on the dynamics of the system. The increase of effector cells inactivation involves an inverse Feigenbaum (i.e. period-halving bifurcation) scenario, which results in the stabilization of the dynamics and in an increase of dynamics predictability. Our analyses also reveal that, at low inactivation rates of effector cells, tumor cells undergo strong, chaotic fluctuations, with the dynamics being highly unpredictable. Our findings are discussed in the context of tumor cells potential viability.

Strong and weak Allee effects and chaotic dynamics in Richards' growths

In this paper we define and investigate generalized Richards' growth models with strong and weak Allee effects and no Allee effect. We prove the transition from strong Allee effect to no Allee effect, passing through the weak Allee effect, depending on the implicit conditions, which involve the several parameters considered in the models. New classes of functions describing the existence or not of Allee effect are introduced, a new dynamical approach to Richards' populational growth equation is established. These families of generalized Richards' functions are proportional to the right hand side of the generalized Richards' growth models proposed. Subclasses of strong and weak Allee functions and functions with no Allee effect are characterized. The study of their bifurcation structure is presented in detail, this analysis is done based on the configurations of bifurcation curves and symbolic dynamics techniques. Generically, the dynamics of these functions are classified in the following types: extinction, semi-stability, stability, period doubling, chaos, chaotic semistability and essential extinction. We obtain conditions on the parameter plane for the existence of a weak Allee effect region related to the appearance of cusp points. To support our results, we present fold and flip bifurcations curves and numerical simulations of several bifurcation diagrams.

Mould and yeast identification in archival settings: preliminary results on the use of traditional methods and molecular biology options in Portuguese archives

This project was developed to fully assess the indoor air quality in archives and libraries from a fungal flora point of view. It uses classical methodologies such as traditional culture media – for the viable fungi – and modern molecular biology protocols, especially relevant to assess the non-viable fraction of the biological contaminants. Denaturing high-performance liquid chromatography (DHPLC) has emerged as an alternative to denaturing gradient gel electrophoresis (DGGE) and has already been applied to the study of a few bacterial communities. We propose the application of DHPLC to the study of fungal colonization on paper-based archive materials. This technology allows for the identification of each component of a mixture of fungi based on their genetic variation. In a highly complex mixture of microbial DNA this method can be used simply to study the population dynamics, and it also allows for sample fraction collection, which can, in many cases, be immediately sequenced, circumventing the need for cloning. Some examples of the methodological application are shown. Also applied is fragment length analysis for the study of mixed Candida samples. Both of these methods can later be applied in various fields, such as clinical and sand sample analysis. So far, the environmental analyses have been extremely useful to determine potentially pathogenic/toxinogenic fungi such as Stachybotrys sp., Aspergillus niger, Aspergillus fumigatus, and Fusarium sp. This work will hopefully lead to more accurate evaluation of environmental conditions for both human health and the preservation of documents.

Como melhorar a preparação física dos alunos do 3º ano vocacional da Academia de Música de Vilar do Paraíso no âmbito da disciplina de Técnica de Dança Clássica

Relatório Final de Estágio apresentado à Escola Superior de Dança, com vista à obtenção do grau de Mestre em Ensino de Dança.

Dynamics and orchestral effects in late Eighteenth-Century portuguese organ music: the works of José Marques e Silva (1782-1837) and the organs of António Xavier Machado e Cerveira (1756-1828)

A maioria dos órgãos históricos portugueses data dos finais do século XVIII ou do princípio do século XIX. Durante este período foi construído um invulgar número de instrumentos em Lisboa e nas áreas circundantes por António Xavier Machado e Cerveira (1756-1828) e outros organeiros menos prolíficos. O estudo desses órgãos, muitos dos quais (restaurados ou não) se encontram próximos das condições originais, permite a identificação de um tipo de instrumento com uma morfologia específica, claramente emancipada do chamado «órgão ibérico». No entanto, até muito recentemente, não era conhecida música que se adaptasse às idiossincrasisas daqueles instrumentos. O recente estudo das obras para órgão de José Marques e Silva (1782-1837) permitiu clarificar esta situação. Bem conhecido durante a sua vida como organista e compositor, José Marques e Silva foi um dos ultimos mestres do Seminário Patriarcal. A importância da sua produção musical reside não só num substancial número de obras com autoria firmemente estabelecida – escritas, na maior parte, para coro misto com acompanhamento de órgão obbligato – mas também na íntima relação entre a sua escrita e a morfologia dos órgãos construídos em Portugal durante a sua vida. Este artigo enfatiza a importância de José Marques e Silva (indubitavelmente, o mais significativo compositor português para órgão do seu tempo) sublinhando a relevância das suas obras para órgão solo, cujo uso extensivo de escrita idiomática e indicações de registação fazem delas um dos mais importantes documentos só início do século XIX sobre a prática organística em Portugal.

Identificação modal e simulação da resposta sísmica de barragens abóbada

Trabalho Final de Mestrado elaborado no Laboratório Nacional de Engenharia Civil (LNEC) para a obtenção do grau de Mestre em Engenharia Civil pelo Instituto Superior de Engenharia de Lisboa no âmbito do protocolo de cooperação ente o ISEL e o LNEC

Simulation model for driving dynamics, energy use and power supply

Dissertação para obtenção do grau de Mestre em Engenharia Electrotécnica Ramo de Energia