Azo-hydrazone tautomerism in protonated aminoazobenzenes: Resonance Raman spectroscopy and quantum-chemical calculations

The protonation effect on the vibrational and electronic spectra of 4-aminoazobenzene and 4-(dimethylamino)azobenzene was investigated by resonance Raman spectroscopy, and the results were discussed on the basis of quantum-chemical calculations. Although this class of molecular systems has been investigated in the past concerning the azo-hydrazone tautomerism, the present work is the first to use CASSCF/CASPT2 calculations to unveil the structure of both tautomers as well the nature of the molecular orbitals involved in chromophoric moieties responsible for the resonance Raman enhancement patterns. More specifically both the resonance Raman and theoretical results show clearly that in the neutral species, the charge transfer transition involves mainly the azo moiety, whereas in the protonated forms there is a great difference, depending on the tautomer. In fact, for the azo tautomer the transition is similar to that observed in the corresponding neutral species, whereas in the hydrazone tautomer such a transition is much more delocalized due to the contribution of the quinoid structure. The characterization of protonated species and the understanding of the tautomerization mechanism are crucial for controlling molecular properties depending on the polarity and pH of the medium.

Towards Presidential Rule in Ukraine : Hybrid Regime Dynamics under Semi-Presidentialism

This article sets out to analyse recent regime developments in Ukraine in relation to semi-presidentialism. The article asks: to what extent and in what ways theoretical arguments against semi-presidentialism (premier-presidential and president-parliamentary systems) are relevant for understanding the changing directions of the Ukrainian regime since the 1990s? The article also reviews the by now overwhelming evidence suggesting that President Yanukovych is turning Ukraine into a more authoritarian hybrid regime and raises the question to what extent the president-parliamentary system might serve this end. The article argues that both kinds of semi-presidentialism have, in different ways, exacerbated rather than mitigated institutional conflict and political stalemate. The return to the president-parliamentary system in 2010 – the constitutional arrangement with the most dismal record of democratisation – was a step in the wrong direction. The premier-presidential regime was by no means ideal, but it had at least two advantages. It weakened the presidential dominance and it explicitly anchored the survival of the government in parliament. The return to the 1996 constitution ties in well with the notion that President Viktor Yanukovych has embarked on an outright authoritarian path.

A (semi-)parametric functional coefficient autoregressive conditional duration model

In this paper, we propose a class of ACD-type models that accommodates overdispersion, intermittent dynamics, multiple regimes, and sign and size asymmetries in financial durations. In particular, our functional coefficient autoregressive conditional duration (FC-ACD) model relies on a smooth-transition autoregressive specification. The motivation lies on the fact that the latter yields a universal approximation if one lets the number of regimes grows without bound. After establishing that the sufficient conditions for strict stationarity do not exclude explosive regimes, we address model identifiability as well as the existence, consistency, and asymptotic normality of the quasi-maximum likelihood (QML) estimator for the FC-ACD model with a fixed number of regimes. In addition, we also discuss how to consistently estimate using a sieve approach a semiparametric variant of the FC-ACD model that takes the number of regimes to infinity. An empirical illustration indicates that our functional coefficient model is flexible enough to model IBM price durations.

Efeitos de manipulações ascendentes e descendentes sobre a comunidade fitoplanctônica em um reservatório eutrófico no semi-árido brasileiro

Top-down (grazing) and bottom-up (nutrient, light) controls are important in freshwater ecosystems regulation. Relative importance of these factors could change in space and time, but in tropical lakes bottom-up regulation has to been appointed as more influent. Present study aimed to test the hypothesis that phytoplankton growths rate in Armando Ribeiro reservoir, a huge eutrophic reservoir in semi-arid region of Rio Grande do Norte state, is more limited by nutrient available then zooplankton grazing pressure. Bioassay was conduced monthly from September (2008) to August (2009) manipulating two levels of nutrients (with/without addition) and two level of grazers (with/without removal). Experimental design was factorial 2X2 with four treatments (X5), (i) control with water and zooplankton from natural spot ( C ), (ii) with nutrient addition ( +NP ), (iii) with zooplankton remove ( -Z ) and (iv) with zooplankton remove and nutrient addition ( -Z+NP ). For bioassay confection transparent plastic bottles (500ml) was incubate for 4 or 5 days in two different depths, Secchi`s depth (high luminosity) and 3 times Secchi`s depth (low luminosity). Water samples were collected from each bottle in begins and after incubates period for chlorophyll a concentration analysis and zoopalnktonic organisms density. Phytoplankton growths rates were calculated. Bifactorial ANOVA was performance to test if had a significant effect (p<0,005) of nutrient addition and grazers remove as well a significant interaction between factors on phytoplankton growths rates. Effect magnitude was calculated the relative importance of each process. Results show that phytoplankton growth was in generally stimulated by nutrient addition, as while zooplankton remove rarely stimulated phytoplankton growth. Some significant interactions happening between nutrient additions and grazers remove on phytoplankton growth. In conclusion this study suggests that in studied reservoir phytoplankton growth is more controlled by ascendent factors than descendent

Modelagem molecular na caracterização eletrônica de oligopeptídeos e na descrição quântica da interação fármaco-receptor

In this dissertation, the theoretical principles governing the molecular modeling were applied for electronic characterization of oligopeptide α3 and its variants (5Q, 7Q)-α3, as well as in the quantum description of the interaction of the aminoglycoside hygromycin B and the 30S subunit of bacterial ribosome. In the first study, the linear and neutral dipeptides which make up the mentioned oligopeptides were modeled and then optimized for a structure of lower potential energy and appropriate dihedral angles. In this case, three subsequent geometric optimization processes, based on classical Newtonian theory, the semi-empirical and density functional theory (DFT), explore the energy landscape of each dipeptide during the search of ideal minimum energy structures. Finally, great conformers were described about its electrostatic potential, ionization energy (amino acids), and frontier molecular orbitals and hopping term. From the hopping terms described in this study, it was possible in subsequent studies to characterize the charge transport propertie of these peptides models. It envisioned a new biosensor technology capable of diagnosing amyloid diseases, related to an accumulation of misshapen proteins, based on the conductivity displayed by proteins of the patient. In a second step of this dissertation, a study carried out by quantum molecular modeling of the interaction energy of an antibiotic ribosomal aminoglicosídico on your receiver. It is known that the hygromycin B (hygB) is an aminoglycoside antibiotic that affects ribosomal translocation by direct interaction with the small subunit of the bacterial ribosome (30S), specifically with nucleotides in helix 44 of the 16S ribosomal RNA (16S rRNA). Due to strong electrostatic character of this connection, it was proposed an energetic investigation of the binding mechanism of this complex using different values of dielectric constants (ε = 0, 4, 10, 20 and 40), which have been widely used to study the electrostatic properties of biomolecules. For this, increasing radii centered on the hygB centroid were measured from the 30S-hygB crystal structure (1HNZ.pdb), and only the individual interaction energy of each enclosed nucleotide was determined for quantum calculations using molecular fractionation with conjugate caps (MFCC) strategy. It was noticed that the dielectric constants underestimated the energies of individual interactions, allowing the convergence state is achieved quickly. But only for ε = 40, the total binding energy of drug-receptor interaction is stabilized at r = 18A, which provided an appropriate binding pocket because it encompassed the main residues that interact more strongly with the hygB - C1403, C1404, G1405, A1493, G1494, U1495, U1498 and C1496. Thus, the dielectric constant ≈ 40 is ideal for the treatment of systems with many electrical charges. By comparing the individual binding energies of 16S rRNA nucleotides with the experimental tests that determine the minimum inhibitory concentration (MIC) of hygB, it is believed that those residues with high binding values generated bacterial resistance to the drug when mutated. With the same reasoning, since those with low interaction energy do not influence effectively the affinity of the hygB in its binding site, there is no loss of effectiveness if they were replaced.

Relações de poder, fragmentação e gestão do território no semi-árido nordestinho: um outro olhar sobre o Cariri paraibano

This study aims to analize the Cariri Paraibano territory, as a product of relations of power that were being established along its historic process of territory formation. In this process, the fragmentation and the territory management are fundamental elements to socioterritorial reality comprehension. The theoretical-conceptual basis is based on notions of territory, region, power and territory management, which are articulated to the opinions and empiric confirmations origined from interviews made with several social actions. They also were made photographical records and researches on books, newspapers and magazines, as well on other information sources related to the object of studying. Obtained data confirm the pressuposement on which the relations of dominations and the used methods by the power s owners in the region created a little fruitful political practice and little adequate to the process of active participation of the local population on the territory management, even being on disagreement with the new political-institutional mechanisms, which take to political-administrative more democratic and participative in the country

Políticas públicas para o turismo e desenvolvimento local: reflexões a partir dos "caminhos de fé" no semi-árido potiguar

This study analyzes the event of the Feast of Our Lady of Grace, located in the municipality of Florania / RN as a tourism product, inserted in a process of transformation of a sacred place, in principle determined by religious motives, in a destination "tourist-religious". We seek to understand to what extent state intervention, with policies aimed at boosting the tourism sector as well as the interactions among key actors in the space, are able to modify and streamline the city of Florania, particularly Feast of Our Lady of Grace. The methodology also includes the review of the literature using the deductive method the application of questionnaires to the pilgrims, tourists and pilgrims totaling 150 questionnaires. Along with the economic agents of the municipality, 36 questionnaires were administered according to the model adopted by REDESIST. Complement this research interviews with key Officials of the Municipal Government and the Church. Despite the recognition by the actors of the importance of tourism to the economy of the city of Florania, encouraging the development of the sector is still lagging, some worked and policies / programs listed actually pass by the "Paths of Faith" of Florania. Concerning the Feast of Our Lady of Grace, the bottlenecks reported by researchers and economic agents are very partially affected by the policies / programs and when this occurs, the effort seems to be only reactive, resulting from the pressures experienced by the municipal government (mayor)

Characterization of condensed tannins from native legumes of the Brazilian northeastern semi-arid

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Um sistema de visão para navegação robusta de uma plataforma robótica semi-autônoma

Large efforts have been maden by the scientific community on tasks involving locomotion of mobile robots. To execute this kind of task, we must develop to the robot the ability of navigation through the environment in a safe way, that is, without collisions with the objects. In order to perform this, it is necessary to implement strategies that makes possible to detect obstacles. In this work, we deal with this problem by proposing a system that is able to collect sensory information and to estimate the possibility for obstacles to occur in the mobile robot path. Stereo cameras positioned in parallel to each other in a structure coupled to the robot are employed as the main sensory device, making possible the generation of a disparity map. Code optimizations and a strategy for data reduction and abstraction are applied to the images, resulting in a substantial gain in the execution time. This makes possible to the high level decision processes to execute obstacle deviation in real time. This system can be employed in situations where the robot is remotely operated, as well as in situations where it depends only on itself to generate trajectories (the autonomous case)

Photoinduced hole-transfer in semiconducting polymer/low-bandgap cyanine dye blends: evidence for unit charge separation quantum yield

Power-conversion efficiencies of organic heterojunction solar cells can be increased by using semiconducting donor-acceptor materials with complementary absorption spectra extending to the near-infrared region. Here, we used continuous wave fluorescence and absorption, as well as nanosecond transient absorption spectroscopy to study the initial charge transfer step for blends of a donor poly(p-phenylenevinylene) derivative and low-band gap cyanine dyes serving as electron acceptors. Electron transfer is the dominant relaxation process after photoexcitation of the donor. Hole transfer after cyanine photoexcitation occurs with an efficiency close to unity up to dye concentrations of similar to 30 wt%. Cyanines present an efficient self-quenching mechanism of their fluorescence, and for higher dye loadings in the blend, or pure cyanine films, this process effectively reduces the hole transfer. Comparison between dye emission in an inert polystyrene matrix and the donor matrix allowed us to separate the influence of self-quenching and charge transfer mechanisms. Favorable photovoltaic bilayer performance, including high open-circuit voltages of similar to 1 V confirmed the results from optical experiments. The characteristics of solar cells using different dyes also highlighted the need for balanced adjustment of the energy levels and their offsets at the heterojunction when using low-bandgap materials, and accentuated important effects of interface interactions and solid-state packing on charge generation and transport.

Excitations and finite-size properties of an integrable supersymmetric electronic model

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Analysis of Semi-solid Processing for Metal Matrix Composite Synthesis Using Factorial Design

The main goal in this work is to conduct a quantitative analysis of the mechanical stir casting process for obtaining particulate metal matrix composites. A combined route of stirring at semi-solid state followed by stirring at liquid state is proposed. A fractional factorial design was developed to investigate the influence and interactions of factors as: time, rotation, initial fraction and particle size, on the incorporated fraction. The best incorporations were obtained with all factors at high levels, as well as that very long stirring periods have no strong influence being particle size and rotation the most important factors on the incorporated fraction. Particle wetting occurs during stirring at semisolid state, highlighting the importance of the interactions between particles and the alloy globularized phase. The role of the alloying element Mg as a wettability-promoting agent is discussed. The shear forces resulting from the stirring system is emphasized and understood as the effect of rotation itself added to the propeller blade geometry.

Orientation dependence of stored energy of cold work in semi-processed electrical steels after temper rolling

Microhardness measurements were carried out in a low carbon lamination steel after 6% of temper rolling, in order to evaluate local variations of work hardening as a function of crystallographic orientation. EBSD (electron back scattered diffraction) was used to determine grain orientations with respect to individual rolling planes and rolling directions. Hardness was shown to increase with the local Taylor factor. TEM observations and a well-known dislocation hardening model were used to confirm the equivalence between hardness values and the stored energy of cold work. A definite correlation between stored energy and Taylor factors could therefore be established, being more consistent than previous data reported in the literature. The improvement was thought to be related to the rather small plastic deformation, during which Taylor factors could be considered to remain constant. (c) 2006 Elsevier B.V. All rights reserved.

Cytotoxic effects of permethrin in salivary glands of Rhipicephalus sanguineus (Latreille, 1806) (Acari: Ixodidae) semi-engorged females

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Fipronil-induced cell death in salivary glands of Rhipicephalus sanguineus (Latreille, 1806) (Acari: Ixodidae) semi-engorged females

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)