Langmuir and Langmuir-Blodgett films containing a porphyrin-ruthenium complex

The fabrication of supramolecular structures from the tetraruthenated porphyrin-containing phosphines, {TPyP[RuCl3(dppb)](4)}, RuTPyP, is demonstrated with Langmuir and Langmuir-Blodgett films. The surface pressure-molecular area isotherms (pi-A) point to an edge-on arrangement for the RuTPyP molecules in the condensed state. Weak aggregation in the Langmuir films was indicated by non-zero surface potentials at large areas per molecule and a slight red shift in the ultraviolet-visible absorption spectrum in comparison to the spectrum in solution. Further aggregation occurs in the Z-type Lang muir-Blodgett films, which was confirmed with ultraviolet-visible spectroscopy of the deposited films. Fourier transform infrared and Raman spectroscopic data for powder and Langmuir-Blodgett films indicate that the RuTPyP molecules are chemically stable in Langmuir-Blodgett films regardless of the contact with water during film fabrication. The nanostructured nature of the Langmuir-Blodgett films was manifested in cyclic voltammetry due to the high sensitivity of the metallic centers in RuTPyR Electrodes modified with Langmuir-Blodgett films exhibit an anodic peak at 100 mV and a cathodic peak at 7 mV, which is assigned to RuIII/RuII redox processes. Furthermore, Langmuir-Blodgett films from RuTPyP showed electrocatalytic activity for oxidation of benzyl alcohol, illustrated by a large shift of 100 mV in the anodic peak at 400 mV, while electropolymerized and cast films of the same compound displayed smaller and no activities, respectively.

Thermomechanical characterization of PVDF and P(VDF-TrFE) blends containing corn starch and natural rubber

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

Propriedades críticas do modelo z(4) em sistemas bi e tridimensionais

A real space renormalization group method is used to investigate the criticality (phase diagrams, critical expoentes and universality classes) of Z(4) model in two and three dimensions. The values of the interaction parameters are chosen in such a way as to cover the complete phase diagrams of the model, which presents the following phases: (i) Paramagnetic (P); (ii) Ferromagnetic (F); (iii) Antiferromagnetic (AF); (iv) Intermediate Ferromagnetic (IF) and Intermediate Antiferromagnetic (IAF). In the hierarquical lattices, generated by renormalization the phase diagrams are exact. It is also possible to obtain approximated results for square and simple cubic lattices. In the bidimensional case a self-dual lattice is used and the resulting phase diagram reproduces all the exact results known for the square lattice. The Migdal-Kadanoff transformation is applied to the three dimensional case and the additional phases previously suggested by Ditzian et al, are not found

Efeitos das inomogeneidades da matéria em Cosmologias Aceleradas

The recent observational advances of Astronomy and a more consistent theoretical framework turned Cosmology in one of the most exciting frontiers of contemporary science. In this thesis, homogeneous and inhomogeneous Universe models containing dark matter and different kinds of dark energy are confronted with recent observational data. Initially, we analyze constraints from the existence of old high redshift objects, Supernovas type Ia and the gas mass fraction of galaxy clusters for 2 distinct classes of homogeneous and isotropic models: decaying vacuum and X(z)CDM cosmologies. By considering the quasar APM 08279+5255 at z = 3.91 with age between 2-3 Gyr, we obtain 0,2 < OM < 0,4 while for the j3 parameter which quantifies the contribution of A( t) is restricted to the intervalO, 07 < j3 < 0,32 thereby implying that the minimal age of the Universe amounts to 13.4 Gyr. A lower limit to the quasar formation redshift (zJ > 5,11) was also obtained. Our analyzes including flat, closed and hyperbolic models show that there is no an age crisis for this kind of decaying A( t) scenario. Tests from SN e Ia and gas mass fraction data were realized for flat X(z)CDM models. For an equation of state, úJ(z) = úJo + úJIZ, the best fit is úJo = -1,25, úJl = 1,3 and OM = 0,26, whereas for models with úJ(z) = úJo+úJlz/(l+z), we obtainúJo = -1,4, úJl = 2,57 and OM = 0,26. In another line of development, we have discussed the influence of the observed inhomogeneities by considering the Zeldovich-Kantowski-DyerRoeder (ZKDR) angular diameter distance. By applying the statistical X2 method to a sample of angular diameter for compact radio sources, the best fit to the cosmological parameters for XCDM models are OM = O, 26,úJ = -1,03 and a = 0,9, where úJ and a are the equation of state and the smoothness parameters, respectively. Such results are compatible with a phantom energy component (úJ < -1). The possible bidimensional spaces associated to the plane (a , OM) were restricted by using data from SNe Ia and gas mass fraction of galaxy clusters. For Supernovas the parameters are restricted to the interval 0,32 < OM < 0,5(20") and 0,32 < a < 1,0(20"), while to the gas mass fraction we find 0,18 < OM < 0,32(20") with alI alIowed values of a. For a joint analysis involving Supernovas and gas mass fraction data we obtained 0,18 < OM < 0,38(20"). In general grounds, the present study suggests that the influence of the cosmological inhomogeneities in the matter distribution need to be considered with more detail in the analyses of the observational tests. Further, the analytical treatment based on the ZKDR distance may give non-negligible corrections to the so-calIed background tests of FRW type cosmologies

IFTrace: Video segmentation of deformable objects using the Image Foresting Transform

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

(Z)-Ethyl 2-hydroxyimino-2-(4-nitrobenzyl)ethanoate

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

Prolapse-free relativistic Gaussian basis sets for the superheavy elements up to Uuo (Z=118) and Lr (Z=103)

Prolapse-free basis sets suitable for four-component relativistic quantum chemical calculations are presented for the superheavy elements UP to (118)Uuo ((104)Rf, (105)Db, (106)Sg, (107)Bh, (108)Hs, (109)Mt, (110)Ds, (111)Rg, (112)Uub, (113)Uut, (114)Uuq, (115)Uup, (116)Uuh, (117)Uus, (118)Uuo) and Lr-103. These basis sets were optimized by minimizing the absolute values of the energy difference between the Dirac-Fock-Roothaan total energy and the corresponding numerical value at a milli-Hartree order of magnitude, resulting in a good balance between cost and accuracy. Parameters for generating exponents and new numerical data for some superheavy elements are also presented. (c) 2007 Elsevier B.V. All rights reserved.

Material processing by plasma shock wave generated in an inverse Z-pinch plasma expander

The applicability of plasma shock wave for material processing was investigated using modified inverse Z-pinch device. Shock wave expanding speed and plasma spectral analysis were studied using an internal magnetic,probe and spatially collimated light spectroscopy. The material processing capability of the device was shown by many different surface analysis techniques such as AES, IRS, EPM and SEM. The interactions between a plasma shock wave of similar to4x10(6) cm/s speed with a Si substrate surface shows some ion implantation capability using a nitrogen plasma and thin film formation using a methane plasma.

Secular dynamics and family identification among highly inclined asteroids in the Euphrosyne region

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

Sub-Optimal Orbital Maneuvers for Artificial Satellites

The determination of a specific orbit and the procedure to calculate orbital maneuvers of artificial satellites are problems of extreme importance in the study of orbital mechanics. Therefore, the transferring problem of a spaceship from one orbit to another, and the attention due to this subject has in increased during the last years. Many applications can be found in several space activities, for example, to put a satellite in a geostationary orbit, to change the position of a spaceship, to maintain a specific satellite's orbit, in the design of an interplanetary mission, and others. The Brazilian Satellite SCD-1 (Data Collecting Satellite) will be used as example in this paper. It is the first satellite developed entirely in Brazil, and it remains in operation to this date. SCD-1 was designed, developed, built, and tested by Brazilian scientists, engineers, and technicians working at INPE (National Institute for Space Research, and in Brazilian Industries. During the lifetime, it might be necessary do some complementary maneuvers, being this one either an orbital transferring, or just to make periodical corrections. The purpose of transferring problem is to change the position, velocity and the satellite's mass to a new pre determined state. This transfer can be totally linked (in the case of "Rendezvous") or partially free (free time, free final velocity, etc). In the global case, the direction, the orientation and the magnitude of the thrust to be applied must be chosen, respecting the equipment's limit. In order to make this transferring, either sub-optimal or optimal maneuvers may be used. In the present study, only the sub-optimal will be shown. Hence, this method will simplify the direction of thrust application, to allow a fast calculation that may be used in real time, with a very fast processing. The thrust application direction to be applied will be assumed small and constant, and the purpose of this paper is to find the time interval that the thrust is applied. This paper is basically divided into three parts: during the first one the sub-optimal maneuver is explained and detailed, the second presents the Satellite SCD-1, and finally the last part shows the results using the sub-optimal maneuver applied to the Brazilian Satellite.

Systematic analysis of the Fourier transform spectrum of (CH3OH)-C-13 between 400 and 950 cm(-1)

We have investigated a high-resolution Fourier transform (FT) absorption spectrum of the (CH3OH)-C-13 isotopomer of methanol from 400 to 950 cm(-1) with the Ritz program. We present the assignments of 7160 transitions, 3021 of which belong to Asymmetry, and 4139 to E-symmetry. These transitions occur between states labeled by K quantum numbers up to 14, and by torsional quantum numbers n up to 4. The Ritz program evaluated the energies of the 4684 involved levels with an accuracy of the order of 10(-4) cm(-1). All of the assigned lines correspond to transitions involving torsionally excited levels within the ground small-amplitude vibrational state. (c) 2005 Elsevier B.V. All rights reserved.

The Interval Constructor on classes of ML-algebras

Monoidal logic, ML for short, which formalized the fuzzy logics of continuous t-norms and their residua, has arisen great interest, since it has been applied to fuzzy mathematics, artificial intelligence, and other areas. It is clear that fuzzy logics basically try to represent imperfect or fuzzy information aiming to model the natural human reasoning. On the other hand, in order to deal with imprecision in the computational representation of real numbers, the use of intervals have been proposed, as it can guarantee that the results of numerical computation are in a bounded interval, controlling, in this way, the numerical errors produced by successive roundings. There are several ways to connect both areas; the most usual one is to consider interval membership degrees. The algebraic counterpart of ML is ML-algebra, an interesting structure due to the fact that by adding some properties it is possible to reach different classes of residuated lattices. We propose to apply an interval constructor to ML-algebras and some of their subclasses, to verify some properties within these algebras, in addition to the analysis of the algebraic aspects of them

Lógica BDI fuzzy

Intendding to understand how the human mind operates, some philosophers and psycologists began to study about rationality. Theories were built from those studies and nowadays that interest have been extended to many other areas such as computing engineering and computing science, but with a minimal distinction at its goal: to understand the mind operational proccess and apply it on agents modelling to become possible the implementation (of softwares or hardwares) with the agent-oriented paradigm where agents are able to deliberate their own plans of actions. In computing science, the sub-area of multiagents systems has progressed using several works concerning artificial intelligence, computational logic, distributed systems, games theory and even philosophy and psycology. This present work hopes to show how it can be get a logical formalisation extention of a rational agents architecture model called BDI (based in a philosophic Bratman s Theory) in which agents are capable to deliberate actions from its beliefs, desires and intentions. The formalisation of this model is called BDI logic and it is a modal logic (in general it is a branching time logic) with three access relations: B, D and I. And here, it will show two possible extentions that tranform BDI logic in a modal-fuzzy logic where the formulae and the access relations can be evaluated by values from the interval [0,1]

Litoestratigrafia e deformação cenzóica na região de Icapuí, Ceará, e implicações para a estruturação de campos de petróleo na borda ocidental da bacia Potiguar(NE do Brasil)

This thesis deals with the sedimentological/stratigraphic and structural evolution of the sedimentary rocks that occur in the NW continental border of the Potiguar Basin. These rocks are well exposed along coastal cliffs between the localities of Lagoa do Mato and Icapuí, Ceará State (NE Brazil). The sedimentological/stratigraphic study involved, at the outcrop scale, detailed facies descriptions, profile mapping of the vertical succession of different beds, and columnar sections displaying inferred lateral relationships. The approach was complemented by granulometric and petrographic analyses, including the characterization of heavy mineral assemblages. The data set allowed to recognize two kinds of lithological units, a carbonate one of very restricted occurrence at the base of the cliffs, and three younger, distinct siliciclastic units, that predominate along the cliffs, in vertical and lateral extent. The carbonate rocks were correlated to the late Cretaceous Jandaíra Formation, which is covered by the siliciclastic Barreiras Formation. The Barreiras Formation occurs in two distinct structural settings, the usual one with nondeformed, subhorizontal strata, or as tilted beds, affected by strong deformation. Two lithofacies were recognized, vertically arranged or in fault contacts. The lower facies is characterized by silty-argillaceous sandstones with low-angle cross bedding; the upper facies comprises medium to coarse grained sandstones, with conglomeratic layers. The Tibau Formation (medium to coarse-grained sandstones with argillite intercalations) occurs at the NW side of the studied area, laterally interlayered with the Barreiras Formation. Eolic sediments correlated to the Potengi Formation overly the former units, either displaying an angular unconformity, or simply an erosional contact (stratigraphic unconformity). Outstanding structural features, identified in the Barreiras Formation, led to characterize a neocenozoic stress field, which generated faults and folds and/or reactivated older structures in the subjacent late cretaceous (to paleogene, in the offshore basin) section. The structures recognized in the Barreiras Formation comprise two distinct assemblages, namely a main extensional deformation between the localities of Ponta Grossa and Redonda, and a contractional style (succeeded by oblique extensional structures) at Vila Nova. In the first case, the structural assemblage is dominated by N-S (N±20°Az) steep to gently-dipping extensional faults, displaying a domino-style or listric geometry with associated roll-over structures. This deformation pattern is explained by an E-W/WNW extension, contemporaneous with deposition of the upper facies of the Barreiras Formation, during the time interval Miocene to Pleistocene. Strong rotation of blocks and faults generated low-angle distensional faults and, locally, subvertical bedding, allowing to estimate very high strain states, with extension estimates varying between 40% up to 200%. Numerous detachment zones, parallel to bedding, help to acommodate this intense deformation. The detachment surfaces and a large number of faults display mesoscopic features analoguous to the ones of ductile shear zones, with development of S-C fabrics, shear bands, sigmoidal clasts and others, pointing to a hydroplastic deformation regime in these cases. Local occurrences of the Jandaíra limestone are controled by extensional faults that exhume the pre-Barreiras section, including an earlier event with N-S extension. Finally, WNWtrending extensional shear zones and faults are compatible with the Holocene stress field along the present continental margin. In the Vila Nova region, close to Icapuí, gentle normal folds with fold hinges shallowly pluging to SSW affect the lower facies of the Barreiras Formation, displaying an incipient dissolution cleavage associated with an extension lineation at high rake (a S>L fabric). Deposition of the upper facies siliciclastics is controlled by pull-apart graben structures, bordered by N-NE-trending sinistral-normal shear zones and faults, characterizing an structural inversion. Microstructures are compatible with tectonic deformation of the sedimentary pile, burried at shallow depths. The observed features point to high pore fluid pressures during deformation of the sediments, producing hydroplastic structures through mechanisms of granular flow. Such structures are overprinted by microfractures and microfaults (an essentially brittle regime), tracking the change to microfracturing and frictional shear mechanisms accompanying progressive dewatering and sediment lithification. Correlation of the structures observed at the surface with those present at depth was tested through geophysical data (Ground Penetrating Radar, seismics and a magnetic map). EW and NE-trending lineaments are observed in the magnetic map. The seismic sections display several examples of positive flower structures which affect the base of the cretaceous sediments; at higher stratigraphic levels, normal components/slips are compatible with the negative structural inversion characterized at the surface. Such correlations assisted in proposing a structural model compatible with the regional tectonic framework. The strong neogenepleistocene deformation is necessarily propagated in the subsurface, affecting the late cretaceous section (Açu and Jandaíra formations), wich host the hydrocarbon reservoirs in this portion of the Potiguar Basin. The proposed structural model is related to the dextral transcurrent/transform deformation along the Equatorial Margin, associated with transpressive terminations of E-W fault zones, or at their intersections with NE-trending lineaments, such as the Ponta Grossa-Fazenda Belém one (the LPGFB, itself controlled by a Brasiliano-age strike-slip shear zone). In a first step (and possibly during the late Cretaceous to Paleogene), this lineament was activated under a sinistral transpressional regime (antithetic to the main dextral deformation in the E-W zones), giving way to the folds in the lower facies of the Barreiras Formation, as well as the positive flower structures mapped through the seismic sections, at depth. This stage was succeeded (or was penecontemporaneous) by the extensional structures related to a (also sinistral) transtensional movement stage, associated to volcanism (Macau, Messejana) and thermal doming processes during the Neogene-Pleistocene time interval. This structural model has direct implications to hydrocarbon exploration and exploitation activities at this sector of the Potiguar Basin and its offshore continuation. The structure of the reservoirs at depth (Açu Formation sandstones of the post-rift section) may be controlled (or at least, strongly influenced) by the deformation geometry and kinematics characterized at the surface. In addition, the deformation event recognized in the Barreiras Formation has an age close to the one postulated for the oil maturation and migration in the basin, between the Oligocene to the Miocene. In this way, the described structural cenario represents a valid model to understand the conditions of hydrocarbon transport and acummulation through space openings, trap formation and destruction. This model is potentially applicable to the NW region of the Potiguar Basin and other sectors with a similar structural setting, along the brazilian Equatorial Atlantic Margin

Maximum Phonation Time and s/z Ratio in a Large Child Cohort

Aim. The purpose of this study was to provide normal values for maximum phonation time (MPT) and the s/z ratio by examining 1660 children aged 4-12 years and without vocal signs or symptoms.Methods. The technique was based on the sustained emission of the /a/ vowel and fricatives /s/ and /z/.Results. The average of the MPT in children of the different age groups was as follows: 6.09 seconds for the age group 4-6 years (males, 5.97; female, 6.21 seconds), 7.94 seconds for the age group 7-9 years (males, 8.07; females, 7.79 seconds), and 8.98 for the age group 10-12 years (males, 9.05; females, 8.92 seconds). The overall average for males was 7.78 and females 7.64 seconds. The s/z ratio was near 1.0 in most children but above 1.2 in 133 children and below 0.8 in 133 children.Conclusion. These values of MPT and s/z ratio can be used as normative in further pediatric studies.