The effect of carbonyl group in the asymmetry Of (3,4)J(CH) coupling constants in norbornanones

A rationalization of the known difference between the (3,4)J(C4H1) and (3,4)J(C1H4) couplings transmitted mainly through the 7-bridge in norbornanone is presented in terms of the effects of hyperconjugative interactions involving the carbonyl group. Theoretical and experimental studies Of (3,4)J(CH) couplings were carried out in 3-endo- and 3-exo-X-2-norbornanone derivatives (X = Cl, Br) and in exo- and endo-2-noborneol compounds. Hyperconjugative interactions were studied with the natural bond orbital (NBO) method. Hyperconjugative interactions involving the carbonyl pi*c(2) =o and sigma*c(2) =o antibonding orbitals produce a decrease of three-bond contribution to both (3,4) J(C4H1) and (3,4)J(C1H4) couplings. However, the latter antibonding orbital also undergoes a strong sigma c(3)-c(4) ->sigma*c(2) =o interaction, which defines an additional coupling pathway for (3,4)J(C4H1) but not for (3,4)J(C1H4). This pathway is similar to that known for homoallylic couplings, the only difference being the nature of the intermediate antibonding orbital; i.e. for (3,4)J(C4H1) it is of sigma*-type, while in homoallylic couplings it is of pi*-type. Copyright (c) 2007 John Wiley & Sons, Ltd.

A new member of the ribbon-helix-helix transcription factor superfamily from the plant pathogen Xanthomonas axonopodis pv. citri

XACb0070 is an uncharacterized protein coded by the two large plasmids isolated from Xanthomonas axonopodis pv. cirri, the agent of citrus canker and responsible for important economical losses in citrus world production. XACb0070 presents sequence homology only with other hypothetical proteins belonging to plant pathogens, none of which have their structure determined. The NMR-derived solution structure reveals this protein is a homodimer in which each monomer presents two domains with different structural and dynamic properties: a folded N-terminal domain with beta alpha alpha topology which mediates dimerization and a long disordered C-terminal tail. The folded domain shows high structural similarity to the ribbon-helix-helix transcriptional repressors, a family of DNA-binding proteins of conserved 3D fold but low sequence homology: indeed XACb0070 binds DNA. Primary sequence and fold comparison of XACb0070 with other proteins of the ribbon-helix-helix family together with examination of the genes in the vicinity of xacb0070 suggest the protein might be the component of a toxin-antitoxin system. (C) 2010 Elsevier Inc. All rights reserved.

New metallomolecular wires based on carbon-rich bridging systems: a systematic study

This dissertation presents and discusses the preparation of molecular wires (MW) candidates that would then be probed for electron transfer properties. These wires are bridged by 1,4-diethynylbenzene derivatives with alkoxy side chains with palladium and ruthenium metal complex termini. Characterization of these compounds was performed by usual spectroscopic techniques like 1H, 13C{1H} and 31P{1H} NMR, MS, FTIR and UV-Vis as well as by cyclic voltammetry which allowed classifying the candidates in the Robin–Day system and determination of bridges side chain and length effects on electronic transport. Preparation of the 1,4-diethynylbenzene derivatives was done with synthetic pathways that relied heavily in palladium catalyzed cross-couplings (Sonogashira). A family of single ringed 1,4-diethynylbenzene ligands with different length alkoxy side chains (OCH3, OC2H5, OC7H15) was thus prepared allowing for the influence of these ring decorations to be assessed. The ruthenium binuclear rods showed communication between metal centres only when the shorter ligands were used whereas the longer Ru complexes showed only one redox pair in CV studies which is in agreement to non-communicating metal centres. Cyclic voltammetry studies show irreversible one wave processes for palladium dinuclear complexes, making these rods function as molecular insulators. Fluorescence decay studies performed on the prepared compounds (ligands and complexes) show a pattern of decreasing decay times upon coordination to the metal centres which can due to ligand charge redistribution upon coordination leading to non-radiative relaxation paths. Regarding the X-ray structures, two new ligand related structures were obtained as well as new structure for a palladium rod. The effect of the side chains was observed to be important to the wires’ electronic properties when comparing with the analogues without a side chain. The effect brought by longer chains is nevertheless almost negligible.

Are cutout handles used when available in real occupational settings? Description of grips and upper extremities movements during industrial box handling

In order to achieve better postures and decrease musculoskeletal risks adequate design of hand/box couplings for manual materials handling (MMH) are still needed. No studies evaluating upper limb movement thorough direct measurements during box handling in workplace were identified in the literature. In this study we describe the types of grip and movements adopted by ten workers when handling redesigned boxes with cutout handles between different heights on industrial pallets. The new handles were used by 90% of the workers through different types of grip. Electrogoniometric measurements showed relatively safe forearm and wrist movements, although elbow inadequate range of movement was recorded. Despite the good acceptance of the cutout by workers, the new design requires extra internal space in the boxes reducing applications for this alternative of box.

Aplicações de Dispositivos de Microondas utilizando Substrato EBG/PBG para Comunicações Móveis

The modern society depends on an efficient communications system able to of transmitting and receiving information with a higher speed and reliability every time. The need for ever more efficient devices raises optimization techniques of microstrip devices, such as techniques to increase bandwidth: thicker substrates and substrate structures with EBG (Electromagnetic Band Gap) and PBG (Photonic Band Gap). This work has how aims the study of the application of PBG materials on substrates of planar structures in microstrip, more precisely in directional quadrature couplers and in rat-race and impedance of transformers. A study of the planar structures in microstrip and substrates EBG is presented. The PBG substrates can be used to optimize the radiation through the air, thus reducing the occurrence of surface waves and the resulting diffraction edge responsible for degradation of radiation pattern. Through specific programs in FORTRAN Power Station obtained the frequencies and couplings for each structure. Are used the program PACMO - Computer Aided Design in Microwave. Results are obtained of the frequency and coupling devices, ranging the frequency band used (cellular communication and Wimax systems) and the permittivity of the substrate, comparing the results of conventional material and PBG materials in the s and p polarizations.

Fases e criticalidade no modelo ashkin - teller de três cores

The usual Ashkin-Teller (AT) model is obtained as a superposition of two Ising models coupled through a four-spin interaction term. In two dimension the AT model displays a line of fixed points along which the exponents vary continuously. On this line the model becomes soluble via a mapping onto the Baxter model. Such richness of multicritical behavior led Grest and Widom to introduce the N-color Ashkin-Teller model (N-AT). Those authors made an extensive analysis of the model thus introduced both in the isotropic as well as in the anisotropic cases by several analytical and computational methods. In the present work we define a more general version of the 3-color Ashkin-Teller model by introducing a 6-spin interaction term. We investigate the corresponding symmetry structure presented by our model in conjunction with an analysis of possible phase diagrams obtained by real space renormalization group techniques. The phase diagram are obtained at finite temperature in the region where the ferromagnetic behavior is predominant. Through the use of the transmissivities concepts we obtain the recursion relations in some periodical as well as aperiodic hierarchical lattices. In a first analysis we initially consider the two-color Ashkin-Teller model in order to obtain some results with could be used as a guide to our main purpose. In the anisotropic case the model was previously studied on the Wheatstone bridge by Claudionor Bezerra in his Master Degree dissertation. By using more appropriated computational resources we obtained isomorphic critical surfaces described in Bezerra's work but not properly identified. Besides, we also analyzed the isotropic version in an aperiodic hierarchical lattice, and we showed how the geometric fluctuations are affected by such aperiodicity and its consequences in the corresponding critical behavior. Those analysis were carried out by the use of appropriated definitions of transmissivities. Finally, we considered the modified 3-AT model with a 6-spin couplings. With the inclusion of such term the model becomes more attractive from the symmetry point of view. For some hierarchical lattices we derived general recursion relations in the anisotropic version of the model (3-AAT), from which case we can obtain the corresponding equations for the isotropic version (3-IAT). The 3-IAT was studied extensively in the whole region where the ferromagnetic couplings are dominant. The fixed points and the respective critical exponents were determined. By analyzing the attraction basins of such fixed points we were able to find the three-parameter phase diagram (temperature £ 4-spin coupling £ 6-spin coupling). We could identify fixed points corresponding to the universality class of Ising and 4- and 8-state Potts model. We also obtained a fixed point which seems to be a sort of reminiscence of a 6-state Potts fixed point as well as a possible indication of the existence of a Baxter line. Some unstable fixed points which do not belong to any aforementioned q-state Potts universality class was also found

Efeitos de acoplamentos biquadráticos e campos aleatórios em vidros de spins

In this work we have studied the effects of random biquadratic and random fields in spin-glass models using the replica method. The effect of a random biquadratic coupling was studied in two spin-1 spin-glass models: in one case the interactions occur between pairs of spins, whereas in the second one the interactions occur between p spins and the limit p > oo is considered. Both couplings (spin glass and biquadratic) have zero-mean Gaussian probability distributions. In the first model, the replica-symmetric assumption reveals that the system presents two pha¬ses, namely, paramagnetic and spin-glass, separated by a continuous transition line. The stability analysis of the replica-symmetric solution yields, besides the usual instability associated with the spin-glass ordering, a new phase due to the random biquadratic cou¬plings between the spins. For the case p oo, the replica-symmetric assumption yields again only two phases, namely, paramagnetic and quadrupolar. In both these phases the spin-glass parameter is zero. Besides, it is shown that they are stable under the Almeida-Thouless stability analysis. One of them presents negative entropy at low temperatures. We developed one step of replica simmetry breaking and noticed that a new phase, the biquadratic glass phase, emerge. In this way we have obtained the correct phase diagram, with.three first-order transition lines. These lines merges in a common triple point. The effects of random fields were studied in the Sherrington-Kirkpatrick model consi¬dered in the presence of an external random magnetic field following a trimodal distribu¬tion {P{hi) = p+S(hi - h0) +Po${hi) +pS(hi + h0))- It is shown that the border of the ferromagnetic phase may present, for conveniently chosen values of p0 and hQ, first-order phase transitions, as well as tricritical points at finite temperatures. It is verified that the first-order phase transitions are directly related to the dilution in the fields: the extensions of these transitions are reduced for increasing values of po- In fact, the threshold value pg, above which all phase transitions are continuous, is calculated analytically. The stability analysis of the replica-symmetric solution is performed and the regions of validity of such a solution are identified

Efeito Kerr magneto-óptico; Ressonância ferromagnética; Acoplamento bilinear; Acoplamento biquadrático

In this work, we investigated the magnetic properties of a monocrystalline Fe thin film and of Fe(80 Å)/Cr(t)/Fe(80 Å) tri-layers, with the nonmagnetic metallic Cr spacer layer thickness varying between 9 Å < t < 40 Å. The samples were deposited by the DC Sputtering on Magnesium Oxide (MgO) substrates, with (100) crystal orientation. For this investigation, experimental magneto-optical Kerr effect (MOKE) magnetometry and ferromagnetic resonance (FMR) techniques were employeed. In this case, these techniques allowed us to study the static and dynamical magnetization properties of our tri-layers. The experimental results were interpreted based on the phenomenological model that takes into account the relevant energy terms to the magnetic free energy to describe the system behavior. In the case of the monocrystalline Fe film, we performed an analytical discussion on the magnetization curves and developed a numerical simulation based on the Stoner-Wohlfarth model, that enables the numerical adjustment of the experimental magnetization curves and obtainment of the anisotropy field values. On the other hand, for the tri-layers, we analyzed the existence of bilinear and biquadratic couplings between the magnetizations of adjacent ferromagnetic layers from measurements of magnetization curves. With the FMR fields and line width angular dependencies, information on the anisotropy in three layers was obtained and the effects of different magnetic relaxation mechanisms were evidenced. It was also possible to observe the dependence of the epitaxy of the multilayers with growth and sputtering parameters. Additionally it was developed the technique of AC magnetic susceptibility in order to obtain further information during the investigation of magnetic thin films

Ondas de spin em nanofilmes nagnéticos acoplados quasiperiodicamente

We studied the spin waves modes that can propagate in magnetic multilayers composed of ferromagnetic metallic films in the nanometer scale. The ferromagnetic films (iron) are separated and coupled through the nonmagnetic spacer films (chromium). The films that make up the multilayer are stacked in a quasiperiodic pattern, following the Fibonacci and double period sequences. We used a phenomenological theory taking into account: the Zeeman energy (between the ferromagnetic films and the external magnetic field), the energy of the magneto-crystalline anisotropy (present in the ferromagnetic films), the energy of the bilinear and biquadratic couplings (between the ferromagnetic films) and the energy of the dipole-dipole interaction (between the ferromagnetic films), to describe the system. The total magnetic energy of the system is numerically minimized and the equilibrium angles of the magnetization of each ferromagnetic film are determined. We solved the equation of motion of the multilayer to find the dispersion relation for the system and, as a consequence, the spin waves modes frequencies. Our theoretical results show that, in the case of trilayers (Fe/Cr/Fe), our model reproduces with excellent agreement experimental results of Brillouin light scattering, known from the literature, by adjusting the physical parameters of the nanofilms. Furthermore, we generalize the model to N ferromagnetic layers which allowed us to determine how complex these systems become when we increase the number of components. It is worth noting that our theoretical calculations generalize all the results known from the literature

Static potential in QED(3) with nonminimal coupling

Here we study the effect of the nonminimal coupling j(mu)epsilon(munualpha)partial derivative(nu)A(alpha) on the static potential in multiflavor QED(3). Both cases of four and two components fermions are studied separately at leading order in the 1/N expansion. Although a nonlocal Chern-Simons term appears, in the four components case the photon is still massless leading to a confining logarithmic potential similar to the classical one. In the two components case, as expected, the parity breaking fermion mass term generates a traditional Chern-Simons term which makes the photon massive and we have a screening potential which vanishes at large intercharge distance. The extra nonminimal couplings have no important influence on the static potential at large intercharge distances. However, interesting effects show up at finite distances. In particular, for strong enough nonminimal coupling we may have a new massive pole in the photon propagator, while in the opposite limit there may be no poles at all in the irreducible case. We also found that, in general, the nonminimal couplings lead to a finite range repulsive force between charges of opposite signs.

Confinement of spinless particles by Coulomb potentials in two-dimensional space-time

The problem of confinement of spinless particles in 1 + 1 dimensions is approached with a linear potential by considering a mixing of Lorentz vector and scalar couplings. Analytical bound-states solutions are obtained when the scalar coupling is of sufficient intensity compared to the vector coupling. (c) 2005 Elsevier B.V. All rights reserved.

Restrictions over two-dimensional gauge models with Thirring-like interaction

Some years ago, it was shown how fermion self-interacting terms of the Thirring-type impact the usual structure of massless two-dimensional gauge theories [1]. In that work only the cases of pure vector and pure chiral gauge couplings have been considered and the corresponding Thirring term was also pure vector and pure chiral respectively, such that the vector ( or chiral) Schwinger model should not lose its chirality structure due to the addition of the quartic interaction term. Here we extend this analysis to a generalized vector and axial coupling both for the gauge interaction and the quartic fermionic interactions. The idea is to perform quantization without losing the original structure of the gauge coupling. In order to do that we make use of an arbitrariness in the definition of the Thirring-like interaction.

Confinement of fermions by mixed vector-scalar linear potentials in two-dimensional space-time

The problem of confinement of fermions in 1 + 1 dimensions is approached with a linear potential in the Dirac equation by considering a mixing of Lorentz vector and scalar couplings. Analytical bound-states solutions are obtained when the scalar coupling is of sufficient intensity compared to the vector coupling. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Estados estacionários de partículas sem spin em potenciais quadrados

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