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.

Fluorescence Microscopy Imaging Denoising with Log-Euclidean Priors and Photobleaching Compensation

Fluorescent protein microscopy imaging is nowadays one of the most important tools in biomedical research. However, the resulting images present a low signal to noise ratio and a time intensity decay due to the photobleaching effect. This phenomenon is a consequence of the decreasing on the radiation emission efficiency of the tagging protein. This occurs because the fluorophore permanently loses its ability to fluoresce, due to photochemical reactions induced by the incident light. The Poisson multiplicative noise that corrupts these images, in addition with its quality degradation due to photobleaching, make long time biological observation processes very difficult. In this paper a denoising algorithm for Poisson data, where the photobleaching effect is explicitly taken into account, is described. The algorithm is designed in a Bayesian framework where the data fidelity term models the Poisson noise generation process as well as the exponential intensity decay caused by the photobleaching. The prior term is conceived with Gibbs priors and log-Euclidean potential functions, suitable to cope with the positivity constrained nature of the parameters to be estimated. Monte Carlo tests with synthetic data are presented to characterize the performance of the algorithm. One example with real data is included to illustrate its application.

Dynamic equilibrium through reinforcement learning

Reinforcement Learning is an area of Machine Learning that deals with how an agent should take actions in an environment such as to maximize the notion of accumulated reward. This type of learning is inspired by the way humans learn and has led to the creation of various algorithms for reinforcement learning. These algorithms focus on the way in which an agent’s behaviour can be improved, assuming independence as to their surroundings. The current work studies the application of reinforcement learning methods to solve the inverted pendulum problem. The importance of the variability of the environment (factors that are external to the agent) on the execution of reinforcement learning agents is studied by using a model that seeks to obtain equilibrium (stability) through dynamism – a Cart-Pole system or inverted pendulum. We sought to improve the behaviour of the autonomous agents by changing the information passed to them, while maintaining the agent’s internal parameters constant (learning rate, discount factors, decay rate, etc.), instead of the classical approach of tuning the agent’s internal parameters. The influence of changes on the state set and the action set on an agent’s capability to solve the Cart-pole problem was studied. We have studied typical behaviour of reinforcement learning agents applied to the classic BOXES model and a new form of characterizing the environment was proposed using the notion of convergence towards a reference value. We demonstrate the gain in performance of this new method applied to a Q-Learning agent.

Evaluation of the respiratory motion effect in small animal PET images with GATE Monte Carlo simulations

The rapid growth in genetics and molecular biology combined with the development of techniques for genetically engineering small animals has led to increased interest in in vivo small animal imaging. Small animal imaging has been applied frequently to the imaging of small animals (mice and rats), which are ubiquitous in modeling human diseases and testing treatments. The use of PET in small animals allows the use of subjects as their own control, reducing the interanimal variability. This allows performing longitudinal studies on the same animal and improves the accuracy of biological models. However, small animal PET still suffers from several limitations. The amounts of radiotracers needed, limited scanner sensitivity, image resolution and image quantification issues, all could clearly benefit from additional research. Because nuclear medicine imaging deals with radioactive decay, the emission of radiation energy through photons and particles alongside with the detection of these quanta and particles in different materials make Monte Carlo method an important simulation tool in both nuclear medicine research and clinical practice. In order to optimize the quantitative use of PET in clinical practice, data- and image-processing methods are also a field of intense interest and development. The evaluation of such methods often relies on the use of simulated data and images since these offer control of the ground truth. Monte Carlo simulations are widely used for PET simulation since they take into account all the random processes involved in PET imaging, from the emission of the positron to the detection of the photons by the detectors. Simulation techniques have become an importance and indispensable complement to a wide range of problems that could not be addressed by experimental or analytical approaches.

Ferromagnetic order in aged Co-doped TiO2 anatase nanopowders

Oxide based diluted magnetic semiconductor (DMS) materials have been a subject of increasing interest due to reports of room temperature ferromagnetism in several systems and their potential use in the development of spintronic devices. However, concerns on the stability of the magnetic properties of different DMS systems have been raised. Their magnetic moment is often unstable, vanishing with a characteristic decay time of weeks or months, which precludes the development of real applications. This paper reports on the ferromagnetic properties of two-year-aged Ti1-xCoxO2-δ reduced anatase nanopowders with different Co contents (0.03≤x≤0.10). Aged samples retain rather high values of magnetization, remanence and coercivity which provide strong evidence for a quite preserved long-range ferromagnetic order. In what concern Co segregation, some degree of metastability of the diluted Co doped anatase structure could be inferred in the case of the sample with the higher Co content.

Leptonic CP violation

Several topics on CP violation in the lepton sector are reviewed. A few theoretical aspects concerning neutrino masses, leptonic mixing, and CP violation will be covered, with special emphasis on seesaw models. A discussion is provided on observable effects which are manifest in the presence of CP violation, particularly, in neutrino oscillations and neutrinoless double beta decay processes, and their possible implications in collider experiments such as the LHC. The role that leptonic CP violation may have played in the generation of the baryon asymmetry of the Universe through the mechanism of leptogenesis is also discussed.

SU(5) x SU(5) unification revisited

The idea of grand unification in a minimal supersymmetric SU(5) x SU(5) framework is revisited. It is shown that the unification of gauge couplings into a unique coupling constant can be achieved at a high-energy scale compatible with proton decay constraints. This requires the addition of minimal particle content at intermediate energy scales. In particular, the introduction of the SU(2)(L) triplets belonging to the (15, 1)+((15) over bar, 1) representations, as well as of the scalar triplet Sigma(3) and octet Sigma(8) in the (24, 1) representation, turns out to be crucial for unification. The masses of these intermediate particles can vary over a wide range, and even lie in the TeV region. In contrast, the exotic vector-like fermions must be heavy enough and have masses above 10(10) GeV. We also show that, if the SU(5) x SU(5) theory is embedded into a heterotic string scenario, it is not possible to achieve gauge coupling unification with gravity at the perturbative string scale.

Two-Higgs-doublet model in light of the standard model H -> tau(+)tau(-) search at the LHC

We study the implications of the searches based on H -> tau(+)tau-by the ATLAS and CMS collaborations on the parameter space of the two-Higgs-doublet model (2HDM). In the 2HDM, the scalars can decay into a tau pair with a branching ratio larger than the SM one, leading to constraints on the 2HDM parameter space. We show that in model II, values of tan beta > 1.8 are definitively excluded if the pseudoscalar is in the mass range 110 GeV < m(A) < 145 GeV. We have also discussed the implications for the 2HDM of the recent dimuon search by the ATLAS collaboration for a CP-odd scalar in the mass range 4-12 GeV.

Spontaneous leptonic CP violation and nonzero theta(13)

We consider a simple extension of the Standard Model by adding two Higgs triplets and a complex scalar singlet to its particle content. In this framework, the CP symmetry is spontaneously broken at high energies by the complex vacuum expectation value of the scalar singlet. Such a breaking leads to leptonic CP violation at low energies. The model also exhibits an A(4) X Z(4) flavor symmetry which, after being spontaneously broken at a high-energy scale, yields a tribimaximal pattern in the lepton sector. We consider small perturbations around the tribimaximal vacuum alignment condition in order to generate nonzero values of theta(13), as required by the latest neutrino oscillation data. It is shown that the value of theta(13) recently measured by the Daya Bay Reactor Neutrino Experiment can be accommodated in our framework together with large Dirac-type CP violation. We also address the viability of leptogenesis in our model through the out-of-equilibrium decays of the Higgs triplets. In particular, the CP asymmetries in the triplet decays into two leptons are computed and it is shown that the effective leptogenesis and low-energy CP-violating phases are directly linked.

Leptonic mixing, family symmetries, and neutrino phenomenology

Tribimaximal leptonic mixing is a mass-independent mixing scheme consistent with the present solar and atmospheric neutrino data. By conveniently decomposing the effective neutrino mass matrix associated to it, we derive generic predictions in terms of the parameters governing the neutrino masses. We extend this phenomenological analysis to other mass-independent mixing schemes which are related to the tribimaximal form by a unitary transformation. We classify models that produce tribimaximal leptonic mixing through the group structure of their family symmetries in order to point out that there is often a direct connection between the group structure and the phenomenological analysis. The type of seesaw mechanism responsible for neutrino masses plays a role here, as it restricts the choices of family representations and affects the viability of leptogenesis. We also present a recipe to generalize a given tribimaximal model to an associated model with a different mass-independent mixing scheme, which preserves the connection between the group structure and phenomenology as in the original model. This procedure is explicitly illustrated by constructing toy models with the transpose tribimaximal, bimaximal, golden ratio, and hexagonal leptonic mixing patterns.

Biodiesel production from waste frying oils over lime catalysts

Biodiesel production from semi-refined oils (SRO) and waste frying oils (WFO) was studied using commercial CaO as heterogeneous catalyst. The methanolysis tests were carried out in mild reaction conditions (62 A degrees C, atmospheric pressure). With such conditions, SRO (soybean and rapeseed) allowed to produce a biodiesel containing 97-98 % of methyl esters (FAME), whereas WFO only provided 86-87 % of FAME. The lower FAME yield for WFO oil is ascribable to the partial neutralization of the catalyst by free fatty acids. Also, soaps formation from the WFO oil reduced the weight yield of the oil phase (containing FAME) obtained and increased the MONG content of the glycerin phase. The catalysts stability tests showed high stability even when WFO oil was processed. Catalytic tests performed with blends of WFO/semi-refined oils showed blending as a good strategy to process low value raw oils with minor decay of the catalyst performance. Both WFO and semi-refined oils showed S-shape kinetics curves thus discarding significant differences of the reaction mechanisms.

A hybrid MLS technique for room impulse response estimation

The measurement of room impulse response (RIR) when there are high background noise levels frequently means one must deal with very low signal-to-noise ratios (SNR). if such is the case, the measurement might yield unreliable results, even when synchronous averaging techniques are used. Furthermore, if there are non-linearities in the apparatus or system time variances, the final SNR can be severely degraded. The test signals used in RIR measurement are often disturbed by non-stationary ambient noise components. A novel approach based on the energy analysis of ambient noise - both in the time and in frequency - was considered. A modified maximum length sequence (MLS) measurement technique. referred to herein as the hybrid MLS technique, was developed for use in room acoustics. The technique consists of reducing the noise energy of the captured sequences before applying the averaging technique in order to improve the overall SNRs and frequency response accuracy. Experiments were conducted under real conditions with different types of underlying ambient noises. Results are shown and discussed. Advantages and disadvantages of the hybrid MLS technique over standard MLS technique are evaluated and discussed. Our findings show that the new technique leads to a significant increase in the overall SNR. (C) 2008 Elsevier Ltd. All rights reserved.

Proposta de modelo de avaliação do estado de conservação de equipamentos escolares

Dissertação para obtenção de grau de Mestre em Engenharia Civil na Área de Especialização de Edificações

Leptogenesis, CP violation and neutrino data: what can we learn?

A detailed analytic and numerical study of baryogenesis through leptogenesis is performed in the framework of the standard model of electroweak interactions extended by the addition of three right-handed neutrinos, leading to the seesaw mechanism. We analyze the connection between GUT-motivated relations for the quark and lepton mass matrices and the possibility of obtaining a viable leptogenesis scenario. In particular, we analyze whether the constraints imposed by SO(10) GUTs can be compatible with all the available solar, atmospheric and reactor neutrino data and, simultaneously, be capable of producing the required baryon asymmetry via the leptogenesis mechanism. It is found that the Just-So(2) and SMA solar solutions lead to a viable leptogenesis even for the simplest SO(10) GUT, while the LMA, LOW and VO solar solutions would require a different hierarchy for the Dirac neutrino masses in order to generate the observed baryon asymmetry. Some implications on CP violation at low energies and on neutrinoless double beta decay are also considered. (C) 2002 Elsevier Science B.V. All rights reserved.

Removing ambiguities in the neutrino mass matrix

We suggest that the weak-basis independent condition det(M-nu) = 0 for the effective neutrino mass matrix can be used in order to remove the ambiguities in the reconstruction of the neutrino mass matrix from input data available from present and future feasible experiments. In this framework, we study the full reconstruction of M-nu with special emphasis on the correlation between the Majorana CP-violating phase and the various mixing angles. The impact of the recent KamLAND results on the effective neutrino mass parameter is also briefly discussed. (C) 2003 Elsevier Science B.V. All rights reserved.