Synthesis, spectral and thermal studies on pyrazolate-bridged palladium(II) coordination polymers

Synthesis, spectroscopic characterization and thermal behavior of pyrazolate-bridged palladium complexes [Pd(mu-Pz)(2)](n) (1), [Pd(mu-mPz)(2)](n) (2), [Pd(mu-dmPz)(2)](n) (3), [Pd(mu-IPz)(2)](n) (4) {pyrazolate (Pz(-)), 4-methylpyrazolate (mPz(-)), 3,5-dimethylpyrazolate (dmPz(-)), 4-iodopyrazolate (IPz(-))} have been described in this work. The exobidentate coordination mode of pyrazolato ligands in 1-4 was inferred on basis of IR spectroscopic evidences. TG investigations indicated that the introduction of substituents at the 4 position in the pyrazolyl moiety into coordination polymers do not affect significantly their thermal stability, whereas at the 3 and 5 position reduced the stability of the main chain. Metal palladium was the final product of the thermal decompositions, which was identified by X-ray powder diffraction.

Design of Gaussian basis sets to the theoretical interpretation of IR-spectrum of hexaaquachromium (III) ion, tetraoxochromium (IV) ion, and tetraoxochromium (VI) ion

The Generator Coordinate Hartree-Fock (GCHF) method is employed to design 16s, 16s10p, 24s17p13d, 25s17p13d, and 26s17p Gaussian basis sets for the H ((2)S), O ((3)P), O(2-) ((1)S), Cr(3+) ((4)F), Cr(4+) ((3)F), and Cr(6+) ((1)S) atomic species. These basis sets are then contracted to (4s) for H ((2)S), (6s4p) for O ((3)P), and O(2-) ((1)S), (986p3d) for Cr(3+) ((4)F), (10s8p3d) for Cr(4+) ((3)F), and (13s7p) for Cr(6+) (1S) by a standard procedure. For evaluation of the quality of those basis sets in molecular calculations, we have accomplished studies of total and orbital (HOMO and HOMO-1) energies at the HF-Roothaan level for the molecular species of our interest. The results obtained with the contracted basis sets are compared to the values obtained with our extended basis sets and to the standard 6-311G basis set from literature. Finally, the contracted basis sets are enriched with polarization function and then utilized in the theoretical interpretation of IR-spectrum of hexaaquachromium (III) ion, [Cr(H(2)O)(6)](3+), tetraoxochromium (IV) ion, [CrO(4)](4-), and tetraoxochromium (VI) ion, [CrO(4)](2-). The respective theoretical harmonic frequencies and IR-intensities were computed at the density functional theory (DFT) level. In the DFT calculations we employed the Becke's 1988 functional using the LYP correlation functional. The comparison between the results obtained and the corresponding experimental values indicates a very good description of the IR-spectra of the molecular ions studied, and that the GCHF method is still a legitimate alternative for selection of Gaussian basis sets. (C) 2003 Elsevier B.V. All rights reserved.

Fluctuating dimension in a discrete model for quantum gravity based on the spectral principle

The spectral principle of Connes and Chamseddine is used as a starting point to define a discrete model for Euclidean quantum gravity. Instead of summing over ordinary geometries, we consider the sum over generalized geometries where topology, metric, and dimension can fluctuate. The model describes the geometry of spaces with a countable number n of points, and is related to the Gaussian unitary ensemble of Hermitian matrices. We show that this simple model has two phases. The expectation value , the average number of points in the Universe, is finite in one phase and diverges in the other. We compute the critical point as well as the critical exponent of . Moreover, the space-time dimension delta is a dynamical observable in our model, and plays the role of an order parameter. The computation of is discussed and an upper bound is found, < 2.

Electron impact and chemical ionization mass spectral analyses of methyl esters species of free mycolic acid fraction from Rhodococcus lentifragmentus

The free mycolic acid fraction from Rhodococcus lentifragmentus was derivatized to methyl esters and further fractionated into saturated (F-0), monounsaturated (F-1) and diunsaturated (F-2) species using argentation-TLC. Methyl esters fractions F-0, F-1 and F-2, accounting for approximately 7.4%, 53.1% and 39.5%, respectively, were analyzed by electron impact (EI) and chemical ionization (CI) mass spectrometries. According to EI-MS, peaks observed for M(+)-18, that were prominent compared to those representing M(+)-32 and M(+)-(18 + 32), indicated that the carbon chain size ranged from C-36 to C-48. The pyrolytic cleavage of methyl mycolates (R(2)-CHOH-CH(R(1))-COOCH3), following the McLafferty rearrangement released fragment ions corresponding to, (a) the alpha-subunit, representing the fatty acid methyl ester (R(1)-CH2-COOCH3), methyl hexadecanoate, methyl tetradecanoate and methyl dodecanoate in decreasing order of relative intensity of peaks, and (b) the beta-subunit, representing the meroaldehyde moiety (R(2)-CHO). The saturated meroaldehyde species exhibited peaks representing meroaldehyde minus 18 mass units in which R(2) ranged from C19H39 to C31H63. The monunsaturated species exhibited peaks representing the meroaldehyde in which R(2) ranged from C19H37 to C31H61; peaks corresponding to meroaldehyde minus 18 mass units appeared only in the most abundant components, C29H57CHO, C27H53CHO, C25H49CHO and C31H61CHO, in a decreasing order of relative abundance. The diunsaturated species exhibited peaks essentially corresponding to meroaldehyde in which R(2) corresponded to C31H59 and C29H55; the latter displayed a relative intensity that was about one-half compared to that of the former. Fractions F-0, F-1 and F-2 showed a more intense pyrolytic fragmentation under CI-MS in contrast to results found under EI-MS. Therefore, peaks representing the alpha-subunit and the beta-subunit were more prominent than the ones representing the fragmentation of the hydrocarbon chain. Moreover, the beta-subunit of saturated species exhibited peaks corresponding to meroaldehyde plus hydrogen, and no dehydration of the beta-subunit occurred in this case. In turn, the beta-subunit of monounsaturated and diunsaturated species showed peaks representing both the meroaldehyde plus hydrogen and its dehydration product plus hydrogen. Thus, the presence of unsaturation in the meroaldehyde subunit of methyl mycolate facilitates appearance of dehydration fragment ions under chemical ionization procedure.

Gravitational Lorentz force and the description of the gravitational interaction

In the context of a gauge theory for the translation group, we have obtained, for a spinless particle, a gravitational analogue of the Lorentz force. Then, we have shown that this force equation can be rewritten in terms of magnitudes related to either the teleparallel or the Riemannian structures induced in spacetime by the presence of the gravitational field. In the first case, it gives a force equation, with torsion playing the role of force. In the second, it gives the usual geodesic equation of general relativity. The main conclusion is that scalar matter is able to feel any one of the above spacetime geometries, the teleparallel and the metric ones. Furthermore, both descriptions are found to be completely equivalent in the sense that they give the same physical trajectory for a spinless particle in a gravitational field.

Deformed Gaussian orthogonal ensemble and the statistical fluctuations in the spectra of the quartic oscillator

The nearest-neighbor spacing distributions proposed by four models, namely, the Berry-Robnik, Caurier-Grammaticos-Ramani, Lenz-Haake, and the deformed Gaussian orthogonal ensemble, as well as the ansatz by Brody, are applied to the transition between chaos and order that occurs in the isotropic quartic oscillator. The advantages and disadvantages of these five descriptions are discussed. In addition, the results of a simple extension of the expression for the Dyson-Mehta statistic Δ3 are compared with those of a more popular one, usually associated with the Berry-Robnik formalism. ©1999 The American Physical Society.

Invariant conserved currents in gravity theories with local Lorentz and diffeomorphism symmetry

We discuss conservation laws for gravity theories invariant under general coordinate and local Lorentz transformations. We demonstrate the possibility to formulate these conservation laws in many covariant and noncovariant(ly looking) ways. An interesting mathematical fact underlies such a diversity: there is a certain ambiguity in a definition of the (Lorentz-) covariant generalization of the usual Lie derivative. Using this freedom, we develop a general approach to the construction of invariant conserved currents generated by an arbitrary vector field on the spacetime. This is done in any dimension, for any Lagrangian of the gravitational field and of a (minimally or nonminimally) coupled matter field. A development of the regularization via relocalization scheme is used to obtain finite conserved quantities for asymptotically nonflat solutions. We illustrate how our formalism works by some explicit examples. © 2006 The American Physical Society.

Spectral analysis and low-frequency multipath mitigation for kinematic applications

Low-frequency multipath is still one of the major challenges for high precision GPS relative positioning. In kinematic applications, mainly, due to geometry changes, the low-frequency multipath is difficult to be removed or modeled. Spectral analysis has a powerful technique to analyze this kind of non-stationary signals: the wavelet transform. However, some processes and specific ways of processing are necessary to work together in order to detect and efficiently mitigate low-frequency multipath. In this paper, these processes are discussed. Some experiments were carried out in a kinematic mode with a controlled and known vehicle movement. The data were collected in the presence of a reflector surface placed close to the vehicle to cause, mainly, low-frequency multipath. From theanalyses realized, the results in terms of double difference residuals and statistical tests showed that the proposed methodology is very efficient to detect and mitigate low-frequency multipath effects. © 2008 IEEE.

Search for violation of Lorentz invariance in top quark pair production and decay

Using data collected with the D0 detector at the Fermilab Tevatron Collider, corresponding to 5.3fb -1 of integrated luminosity, we search for violation of Lorentz invariance by examining the tt̄ production cross section in lepton+jets final states. We quantify this violation using the standard-model extension framework, which predicts a dependence of the tt̄ production cross section on sidereal time as the orientation of the detector changes with the rotation of the Earth. Within this framework, we measure components of the matrices (c Q) μν33 and (c U) μν33 containing coefficients used to parametrize violation of Lorentz invariance in the top quark sector. Within uncertainties, these coefficients are found to be consistent with zero. © 2012 American Physical Society.

Influence of the concentration of polyols on the rheological and spectral characteristics of guar gum

Polyols are widely used as sugar substitutes and provide texture to foods. Guar gum has many applications in food industry such as increasing product viscosity and improving texture. Knowledge of rheological properties of gum/polyol systems is important to permit replacing sugar while maintaining product texture. In this work, rheological properties of 0.1, 0.5 and 1 g/100 g guar solutions containing 10 and 40 g/100 g of maltitol, sorbitol, or xylitol were studied. The behavior of these mixtures was evaluated by steady and oscillatory shear measurements, and after a freezing/thawing cycle. Apparent viscosity of guar solutions increased with addition of polyols and with the increase in their concentrations, except for 40 g/100 g sorbitol addition to 1 g/100 g guar gum, in which the apparent viscosity decreased. Addition of polyols also increased the dynamic moduli of the systems. In mixtures of guar with 40 g/100 g polyol, the phase angle (δ) was below unity, but was dependent on frequency, which is characteristic of concentrated solutions with a certain degree of structuring. FTIR spectroscopy was studied to provide information on possible interactions between guar gum and polyols. Analyses carried out after freezing/thawing showed no changes in the viscoelastic behavior of the solutions. © 2013 Elsevier Ltd.

Quantification of Biological Tissue and Construction of Patient Equivalent Phantom (Skull and Chest) for Infants (1-5 years old)

Our main purpose in this study was to quantify biological tissue in computed tomography (CT) examinations with the aim of developing a skull and a chest patient equivalent phantom (PEP), both specific to infants, aged between 1 and 5 years old. This type of phantom is widely used in the development of optimization procedures for radiographic techniques, especially in computed radiography (CR) systems. In order to classify and quantify the biological tissue, we used a computational algorithm developed in Matlab (R). The algorithm performed a histogram of each CT slice followed by a Gaussian fitting of each tissue type. The algorithm determined the mean thickness for the biological tissues (bone, soft, fat, and lung) and also converted them into the corresponding thicknesses of the simulator material (aluminum, PMMA, and air). We retrospectively analyzed 148 CT examinations of infant patients, 56 for skull exams and 92 were for chest. The results provided sufficient data to construct a phantom to simulate the infant chest and skull in the posterior anterior or anterior posterior (PA/AP) view. Both patient equivalent phantoms developed in this study can be used to assess physical variables such as noise power spectrum (NPS) and signal to noise ratio (SNR) or perform dosimetric control specific to pediatric protocols.

Singular Value Decomposition and Ligand Binding Analysis

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Growth in weight and of some tissues in the bullfrog: fitting nonlinear models during the fattening phase

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

A Comparative Analysis of In-Medium Spectral Functions for N(940) and N (au)(1535) in Real-Time Thermal Field Theory

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