Self-assembly of metallosupramolecules directed by (N-H)(2)center dot center dot center dot SCN-M (M = Co, Ni), C-H center dot center dot center dot pi and pi-pi synthons

This work deals with the synthesis, spectroscopic and structural investigation of pyrazolyl complexes of the type trans-[M(NCS)(2)(HPz)(4)] {M=Co (1), Ni (2); HPz=pyrazole}. Single crystal X-ray studies on 1 and 2 reveal the formation of similar supramolecular arrangements derived from self-assembly of monomers linked together through intermolecular N-H center dot center dot center dot SCN hydrogen bonds, C-H center dot center dot center dot pi interactions and pi-pi stacking. (c) 2005 Elsevier B.V. All rights reserved.

Improvement of the dielectric and ferroelectric properties in superlattice structure of Pb(Zr,Ti)O-3 thin films grown by a chemical solution route

Making heterolayered perovskite materials constitutes an approach for the creation of better dielectric and ferroelectric properties. In the experiment reported here, heterolayered PZT40/PZT60 films were grown on Pt/Ti/SiO2/Si (100) by a chemical solution deposition. The dielectric constant of the heterolayered thin film was significantly enhanced compared with that of pure PZT40 and PZT60 thin films. A dielectric constant of 701 at 100 kHz was observed for a stacking periodicity of six layers having a total thickness of 150 nm. The heterolayered film exhibited greater remanent polarization than PZT60 and PZT40 films. The values of remanent polarization were 7.9, 18.5, and 31 muC/cm(2), respectively, for pure PZT60, PZT40, and heterolayered thin films, suggesting that the superior dielectric and ferroelectric properties of the heterolayered thin film resulted from a cooperative interaction between the ferroelectric phases made from alternating tetragonal and rhombohedral phases of PZT, simulating the morphotropic phase boundary of this system. (C) 2004 American Institute of Physics.

Charge-orbital ordering and phase separation in the two-orbital model for manganites: Roles of Jahn-Teller phononic and Coulombic interactions

The main properties of realistic models for manganites are studied using analytic mean-field approximations and computational numerical methods, focusing on the two-orbital model with electrons interacting through Jahn-Teller (JT) phonons and/or Coulombic repulsions. Analyzing the model including both interactions by the combination of the mean-field approximation and the exact diagonalization method, it is argued that the spin-charge-orbital structure in the insulating phase of the purely JT-phononic model with a large Hund couphng J(H) is not qualitatively changed by the inclusion of the Coulomb interactions. As an important application of the present mean-held approximation, the CE-type antiferromagnetic state, the charge-stacked structure along the z axis, and (3x(2) - r(2))/(3y(2) - r(2))-type orbital ordering are successfully reproduced based on the JT-phononic model with large JH for the half-doped manganite, in agreement with recent Monte Carlo simulation results. Topological arguments and the relevance of the Heisenberg exchange among localized t(2g) spins explains why the inclusion of the nearest-neighbor Coulomb interaction does not destroy the charge stacking structure. It is also verified that the phase-separation tendency is observed both in purely JT-phononic (large JH) and purely Coulombic models in the vicinity of the hole undoped region, as long as realistic hopping matrices are used. This highlights the qualitative similarities of both approaches and the relevance of mixed-phase tendencies in the context of manganites. In addition, the rich and complex phase diagram of the two-orbital Coulombic model in one dimension is presented. Our results provide robust evidence that Coulombic and JT-phononic approaches to manganites are not qualitatively different ways to carry out theoretical calculations, but they share a variety of common features.

Analysis of the ethidium bromide bound to DNA by photoacoustic and FTIR spectroscopy

Under physiological conditions B-form DNA is an exceedingly stable structure. However, experimental evidences obtained through nuclear magnetic resonance and fluorescence anisotropy suggest that the structure of the double helix fluctuates substantially. We describe photoacoustic phase modulation frequency measurements of ethidium bromide (Eb) with calf thymus, DNA. As in fluorescence phase modulation measurements, we used an intercalating dye as a probe; however, we monitored the triplet excited state lifetime at different ionic strengths. The triplet lifetime of Eb varied from about 0.30 ms, with no DNA present, to 20 ms, (at a DNA:Eb molar ratio of 5). With salt titration, this value falls, to about 2.0 ms. This result suggests, a strong coupling between the phenantridinium ring of the ethidium and the base pairs because of the stacking movement of the DNA molecule under salt effect. This, effect may be understood considering DNA as a polyelectrolyte. The counterions, in the solution shield the phosphate groups, reducing the electrostatic repulsion force between them, hence compacting the DNA molecule. The results from Fourier transform infrared demonstrated two important bands: 3187 cm(-1) corresponding to the symmetric stretching of the NH group of the bases, and 1225 cm(-1) corresponding to the asymmetric stretching of phosphate groups shifted toward higher wavenumbers, suggesting a proximity between the intercalant and base pairs and a modification of the DNA backbone state, both induced by salt accretion.

A Chloro-Bridged Linear Chain Imine-Copper(II) Complex and Its Application as an Enzyme-Free Amperometric Biosensor for Hydrogen Peroxide

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

Microfacies and sequence stratigraphy of the Amapa Formation, Late Paleocene to Early Eocene, Foz do Amazonas Basin, Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Field profiles of bulk plasmon polariton modes in layered systems containing a metamaterial

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The dielectric suppress and the control of semiconductor non-Ohmic feature of CaCu3Ti4O12 by means of tin doping

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Unfolding of plasmon-polariton modes in one-dimensional layered systems containing anisotropic left-handed materials

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Anderson localization and Brewster anomalies in photonic disordered quasiperiodic lattices

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Crystal structures and magnetic properties of CuX2(pdmp)2 complexes (X = Br, Cl)

We report the synthesis and the structural and magnetic characterization of two new compounds: dibromobis-(pdmp)copper(II), CuBr2C22H24N4 (1), and dichlorobis(pdmp)copper(II), CuCl2C22H24N4 (2), where pdmp = 1-phenyl-3,5-dimethylpyrazole. The structures were refined by full-matrix least-squares techniques to R1 = 0.0620 and 0.0777, respectively. Compound 1 belongs to the space group P21/n with a = 8.165(5) Å, b = 10.432(3) Å, c = 13.385(4) Å, β = 100.12(4)̊, and Z = 2. Compound 2 belongs to the space group P21/c with a = 8.379(2) Å, b = 22.630(2) Å, c = 12.256(2) Å, β= 98.43(3)°, and Z = 4. It has the same molecular formula as a compound reported previously but a different crystal structure. Detailed single-crystal EPR measurements were performed for single-crystal samples of 1 and 2 at 9 and 35 GHz and at room temperature. The positions and line widths of the EPR lines were measured as a function of the magnetic field orientation in three orthogonal planes. The data were used to study the electronic properties of the copper ions and to evaluate the exchange interactions between them. Our results are discussed in terms of the electronic pathways for superexchange between copper ions, which are provided by the stacking of pyrazole and phenyl rings of neighboring molecules and by hydrogen-halogen bonds. © 1999 American Chemical Society.

The use of shallow seismic reflection technique in near surface exploration of urban sites: An evaluation in the city of SãO Paulo, Brazil

In order to evaluate the use of shallow seismic technique to delineate geological and geotechnical features up to 40 meters depth in noisy urban areas covered with asphalt pavement, five survey lines were conducted in the metropolitan area of São Paulo City. The data were acquired using a 24-bit, 24-channel seismograph, 30 and 100 Hz geophones and a sledgehammer-plate system as seismic source. Seismic reflection data were recorded using a CMP (common mid point) acquisition method. The processing routine consisted of: prestack band-pass filtering (90-250 Hz); automatic gain control (AGC); muting (digital zeroin) of dead/noisy traces, ground roll, air-wave and refracted-wave; CMP sorting; velocity analyses; normal move-out corrections; residual static corrections; f-k filtering; CMP stacking. The near surface is geologically characterized by unconsolidated fill materials and Quaternary sediments with organic material overlying Tertiary sediments with the water table 2 to 5 m below the surface. The basement is composed of granite and gneiss. Reflections were observed from 40 milliseconds to 65 ms two-way traveltime and were related to the silt clay layer and fine sand layer contact of the Tertiary sediments and to the weathered basement. The CMP seismic-reflection technique has been shown to be useful for mapping the sedimentary layers and the bedrock of the São Paulo sedimentary basin for the purposes of shallow investigations related to engineering problems. In spite of the strong cultural noise observed in these urban areas and problems with planting geophones we verified that, with the proper equipment, field parameters and particularly great care in data collection and processing, we can overcome the adverse field conditions and to image reflections from layers as shallow as 20 meters.

Nanoscale effects and polaronic relaxation in CaCu3Ti 4O12 compounds

In the present communication, by using dielectric spectroscopy measurement, the correlations between Nanosized Barrier Layer Capacitance (NBLC) (Bueno et al. (2009) [7]) and the high frequency polaronic near-Debye dipolar relaxation found in CaCu3Ti4O12 compounds was discussed. The polaronic process was confirmed to be closely associated with the ultrahigh dielectric features of CaCu3Ti4O12 materials and its concomitant dielectric loss. Herein, the shift in relaxation frequency as a function of temperature was used for calculating the activation energy for hopping electronic conduction. The value obtained was 33 meV, an energy whose magnitude is compatible and confirmed the hypothesis of polaronic features for this high frequency dipolar relaxation process. Furthermore, it is shown that the nanosized barrier inferred from the NBLC model has a polaronic feature with dielectric permittivity exiting orthogonally to dielectric loss, a phenomenological pattern that contradicts the normally observed behavior for traditional dielectrics but explain the dielectric and conductivity feature of CaCu3Ti4O12 compounds. © 2010 Elsevier Ltd. All rights reserved.

Detection of buried pipes using a shear wave ground surface vibration technique

A major UK initiative, entitled 'Mapping the Underworld', is seeking to address the serious social, environmental and economic consequences arising from an inability to locate the buried utility service infrastructure without resorting to extensive excavations. Mapping the Underworld aims to develop and prove the efficacy of a multi-sensor device for accurate remote buried utility service detection, location and, where possible, identification. One of the technologies to be incorporated in the device is low-frequency vibro-acoustics, and the application of this technology for detecting buried infrastructure is currently being investigated. Here, a shear wave ground vibration technique for detecting buried pipes is described. For this technique, shear waves are generated at the ground surface, and the resulting ground surface vibrations measured, using geophones, along a line traversing the anticipated run of the pipe. Measurements were made at a test site with a single pressurized polyethylene mains water pipe. Time-extended signals were employed to generate the illuminating wave. Cross-correlation functions between the measured ground velocities and a reference measurement adjacent to the excitation were then calculated and summed using a stacking method to generate a cross-sectional image of the ground. The wide cross-correlation peaks caused by high ground attenuation were partially compensated for by using a generalized cross-correlation function called the smoothed coherence transform. To mitigate the effects of other potential sources of vibration in the vicinity, the excitation signal was used as an additional reference when calculating the generalized cross-correlation functions. For two out of three tests, the pipe was detected, indicating that this technique will be a valuable addition to the Mapping the Underworld armoury.

XAS/WAXS time-resolved phase speciation of chlorine LDH thermal transformation: Emerging roles of isovalent metal substitution

The XAS/WAXS time-resolved method was applied for unraveling the complex mechanisms arising from the evolution of several metastable intermediates during the degradation of chlorine layered double hydroxide (LDH) upon heating to 450 °C, i.e., Zn2Al(OH)6·nH2O, ZnCuAl(OH)6·nH2O, Zn2Al 0.75Fe0.25(OH)6·nH2O, and ZnCuAl0.5Fe0.5(OH)6·nH2O. After a contraction of the interlamellar distance, attributed to the loss of intracrystalline water molecules, this distance experiences an expansion (T > 175-225 °C) before the breakdown of the lamellar framework around 275-295 °C. Amorphous prenucleus clusters with crystallo-chemical local order of zinc-based oxide and zinc-based spinel phases, and if any of copper-based oxide, are formed at T > 175-225 °C well before the loss of stacking of LDH layers. This distance expansion has been ascribed to the migration of Zn II from octahedral layers to tetrahedral sites in the interlayer space, nucleating the nano-ZnO or nano-ZnM2O4 (M = Al or Fe) amorphous prenuclei. The transformation of these nano-ZnO clusters toward ZnO crystallites proceeds through an agglomeration process occurring before the complete loss of layer stacking for Zn2Al(OH)6· nH2O and Zn2Al0.75Fe0.25(OH) 6·nH2O. For ZnCuAl(OH)6·nH 2O and ZnCuAl0.5Fe0.5(OH)6· nH2O, a cooperative effect between the formation of nano-CuO and nano-ZnAl2O4 amorphous clusters facilitates the topochemical transformation of LDH to spinel due to the contribution of octahedral CuII vacancy to ZnII diffusion. © 2013 American Chemical Society.