Crystal structures and phonon modes of Ba(Ca1/2W1/2)O3, Ba(Ca1/2Mo1/2)O3 and Ba(Sr1/2W1/2)O3 complex perovskites investigated by Raman scattering

This work investigates the crystal structures and phonon modes of Ba(Ca_1/2W_1/2)O₃, Ba(Ca_1/2Mo_1/2)O₃ and Ba(Sr_1/2W_1/2)O₃ perovskites by Raman spectroscopy. The samples were produced by conventional solid‐state processing at 1200 °C. X‐ray diffraction showed that single‐phase homogeneous materials were produced, which are cubic or pseudo‐cubic in symmetry. The existing controversies in the literature for these complex perovskites were investigated by comparing experimental Raman data with group‐theory analysis. Ceramics with Ca and W or Mo were found to be cubic, space group Fm3 m. For these materials, four Raman‐active bands were observed and the fitting parameters showed that the Ba(Ca_1/2Mo_1/2)O₃ ceramic presents bands at lower wavenumbers if compared with the Ba(Ca_1/2W_1/2)O₃ sample. For the Ba(Sr_1/2W_1/2)O₃ material, two hypotheses were investigated for monoclinic or triclinic structures. The experimental results showed 12 Raman‐active modes for this ceramic, which is in perfect agreement with the theoretical predictions for a monoclinic (I2/m) structure. Copyright © 2009 John Wiley & Sons, Ltd.     

Thermal tool to evaluate essential oil composition of different Eucalyptus genotypes in relation to Glycaspis brimblecombei susceptibility (Hemiptera: Aphalaridae)

Journal of Thermal Analysis and Calorimetry - Eucalyptus spp. (Myrtaceae) is economically important worldwide and is native from Australia. Glycaspis brimblecombei (Hemiptera: Aphalaridae) is an...     

A numerical study on heat transfer of a ferrofluid flow in a square cavity under simultaneous gravitational and magnetic convection

Theoretical and Computational Fluid Dynamics - Thermomagnetic convection is based on the use of external magnetic fields to better control heat transfer fluxes in ferrofluids, finding important...     

Incipient crystallization of transition-metal tungstates under microwaves probed by Raman scattering and transmission electron microscopy

Microwave synthesis was used to produce nanosized transition-metal tungstates in environmentally friendly conditions not yet reported by the literature: 110 and 150 °C, for times of 10 and 20 min. X-ray diffraction evidenced incipient crystallized materials, while transmission electron microscopy indicates nanostructured regions of about 2–5 nm inside an amorphous matrix. Raman spectroscopy was used to probe short-range ordering in the achieved samples and also to obtain a reliable set of spectra containing all the Raman-active bands predicted by group-theory calculations. The vibrational spectra showed no extra feature, indicating that the microwave processing was able to produce short-range ordered materials without tetrahedral distortions. These distortions are frequently reported when commercially modified kitchen microwave units are employed. In this work, the syntheses were conducted in a commercial apparatus especially designed for fully controlled temperature–time–pressure conditions.     

Monitoring the 1160 cm band of pyridazine to investigate complexes with formamide

Hydrogen bonding between pyridazine (PRD) and formamide (FA) molecules has been investigated both experimentally by Raman spectroscopy on their binary mixtures and theoretically by DFT calculations on various gas-phase PRD:FA clusters. The band at 1160 cm⁻¹ of PRD was used for the first time as a marker for monitoring the degree of complexation. Upon dilution with FA, a new band at 1169 cm⁻¹ is observed and attributed to hydrogen-bonded PRD. The Raman experiments were complemented by DFT calculations and the corresponding structures, vibrational spectra and binding energies were determined. The most stable species were found to be the 1:2 PRD:FA complexes and such stoichiometry is in excellent agreement with the experimental determination. The shift to higher frequency observed to the prominent modes of PRD may be related to a shortening of the NC and CC bonds, upon complexation, which causes a decrease in the electron delocalization in PRD ring.     

Oxazolidine copper complexes: Synthesis,characterization and superoxide dismutase activity of copper(II) complexes with oxazolidine ligands derived from hydroxyquinoline carboxaldehyde

This work describes the synthesis of copper(II) complexes, their identification using spectroscopic and electrochemical methods, structural characterization with X‐ray diffraction and density functional theory calculations (DFT), as well as their catalytic activity mimicking that of superoxide dismutase. Structural analysis revealed the formation of complexes with cyclization of ligands L1 and L2 with the formation of a heterocycle, 1,3‐oxazolidine. The DFT calculations confirmed this trend by stabilizing with lower energy. In addition, evaluations of mimetic enzymatic activity of complexes C1, C2, C3 and C4 revealed promising IC₅₀ values compared to other results seen in the literature (IC₅₀ = 0.22, 0.328, 0.55 and 0.92). Also, calf thymus DNA interactive experiments using UV–visible spectroscopy were conducted in the presence of the copper(II) complexes.     

Tunable second harmonic generation by phase-modulated ultrashort laser pulses

We report on the generation of tunable light around 400?nm by frequency-doubling ultrashort laser pulses whose spectral phase is modulated by a sum of sinusoidal functions. The linewidth of the ultraviolet band produced is narrower than 1?nm, in contrast to the 12?nm linewidth of the non-modulated incident spectrum. The influence of pixellation of the liquid crystal spatial light modulator on the efficiency of the phase-modulated second harmonic generation is discussed.     

Particle Detachment Under Velocity Alternation During Suspension Transport in Porous Media

Flow of suspensions in porous media with particle capture and detachment under alternate flow rates is discussed. The mathematical model contains the maximum retention concentration function of flow velocity that governs the particle release and is used instead of equation for particle detachment kinetics from the classical filtration model. An analytical model for suspension injection with alternate rates was derived, and a coreflood by suspension with alternate rates was carried out. The modelling and laboratory data are in a good agreement, which validates the modified particle detachment model with the maximum retention function.