Theoretical investigation of Mössbauer hyperfine interactions in ordered FeNi and disordered Fe–Ni alloys

Electronic structure spin-polarized calculations were performed for 79-atoms embedded clusters representing the ordered intermetallic compound FeNi, the fcc Fe-rich disordered alloy Fe₈₅Ni₁₅ in an antiferromagnetic (AFM) configuration, and the ferromagnetic (FM) disordered alloy Fe₅₀Ni₅₀. The spin-polarized discrete variational method (DVM) in Density Functional theory was employed. Spin magnetic moments, as well as the ⁵⁷Fe Mössbauer hyperfine parameters isomer shift and magnetic hyperfine fields, were obtained from the calculations. For FM Fe₅₀Ni₅₀, the effect of pressure on the hyperfine field and on the isomer shift was investigated, for three different local atomic configurations surrounding the ⁵⁷Fe probe atom. In the case of the isomer shift, the calculated values were compared to reported experimental data.     

Fluence Rate Determines PDT Efficiency in Breast Cancer Cells Displaying Different GSH Levels

Photodynamic therapy (PDT) appears as a promising alternative in the treatment of breast cancer since it can be highly effective in curing cancer while preserving normal tissue. However, predicting outcomes in PDT still constitutes a great challenge. One of the parameters that are usually empirically determined is the rate of photon flux delivered to the tissue (light fluence rate). In the present study, we intended to understand why monolayers of human cells derived from mammary adenocarcinomas (MDA-MB-231 and MCF-7) respond quite differently to fluence rates (cells were irradiated either for 6 or for 16 min) at a fixed light dose (4.5 J cm⁻²) delivered with an array of LEDs in a typical methylene blue PDT protocol. While death rates of MDA-MB-231 cells were insensitive to the fluence rate, MCF-7 cells showed a quite impressive (three times) decrease in cell death levels in the shorter irradiation protocol. Independent on cell type cell death was invariably correlated with the depletion of reduced glutathione intracellular levels and consequently with widespread redox misbalance. Our data show the potential to optimize fluence rates to provide exhaustion of the cell antioxidant responses in order to circumvent therapy resistance of breast tumors.     

Structural and galvanomagnetic properties of CuInS2 films

Thin copper-indium-disulphide films were prepared by thermal evaporation technique. X-ray diffraction analysis of the compound used for evaporation showed a tetragonal polycrystalline structure. Differential Thermal Analysis (DTA) of this compound showed two exothermic peaks at 585 and 632 °C. Thin films with thicknesses of 0.14 and 0.27 nm have a deposition rate 10 nm/min, while those with thicknesses of 0.54 and 0.56 nm have a deposition rate 48 nm/min. The obtained films have polycrystalline structure as shown from the electron diffraction study. A growth process was detected in the films by transmission electron microscopy as the film thickness increases. The surface topography was revealed by scanning electron microscopy. The variations of Hall mobility and carrier concentration with magnetic induction were studied. The resistivity-temperature relationship was investigated, from which the activation energies before and after annealing were found to be 0.2, 0.3 and 0.055 eV, respectively.     

A theoretical and experimental study of lead substitution in calcium hydroxyapatite

Characterization of lead substitution for calcium in hydroxyapatite (CaHA) is carried out, using experimental techniques and Density Functional theoretical (DFT) analyses. Theoretical modeling is used to obtain information of the Pb chemical environment for occupancy at either Ca(I) or Ca(II) sites of CaHA. Effects of the larger ionic radius of Pb(+2) compared to Ca(+2) are apparent in embedded cluster calculations of local chemical bonding properties. DFT periodic planewave pseudopotential studies are used to provide first-principles predictions of local structural relaxation and site preference for Pb(x)Ca(10-x)HA over the composition range x< or = 6. General characteristics of the polycrystalline material are verified by X-ray diffraction and FTIR analysis, showing the presence of a single phase of CaHA structure. A short range structure around lead is proposed in order to interpret the Pb L-edge EXAFS spectrum of the solid solution Ca(6.6)Pb(3.4)HA. In this concentration we observe that lead mainly occupies Ca(II) sites; the EXAFS fit slightly favors Pb clustering, while theory indicates the importance of Pb-Pb avoidance on site (II).     

(InSb/GaAs)-Au hybrid macro-structure prepared by flash evaporation

n-Type indium antimonide-Au hybrid macro-structure was successfully fabricated on p-GaAs substrate by a simple and economic flash evaporation technique. The elemental composition of the prepared InSb film was confirmed by energy dispersive X-ray spectroscopy microanalysis (EDX). The surface topography and crystal structure of the InSb film was characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The magnetoresistance of the prepared hybrid macro-structure was measured and discussed in terms of the model of current redistribution.     

Production of Cellulolytic Enzymes by <Emphasis Type="Italic">Aspergillus phoenicis</Emphasis> in Grape Waste using Response Surface Methodology

The production of cellulolytic enzymes by the fungus Aspergillus phoenicis was investigated. Grape waste from the winemaking industry was chosen as the growth substrate among several agro-industrial byproducts. A 2 × 2 central composite design was performed, utilizing the amount of grape waste and peptone as independent variables. The fungus was cultivated in submerged fermentation at 30 °C and 120 rpm for 120 h, and the activities of total cellulases, endoglucanases, and β-glucosidases were measured. Total cellulases were positively influenced by the linear increase of peptone concentration and decrease at axial concentrations of grape waste and peptone. Maximum activity of endoglucanase was observed by a linear increase of both grape waste and peptone concentrations. Concentrations of grape waste between 5 and 15 g/L had a positive effect on the production of β-glucosidase; peptone had no significant effects. The optimum production of the three cellulolytic activities was observed at values near the central point. A. phoenicis has the potential for the production of cellulases utilizing grape waste as the growth substrate.     

119Sn-Mössbauer spectroscopic studies on organoheterobimetallic half sandwich ruthenium–tin containing derivatives

A series of heterobimetallic complexes containing Ru–Sn bonds, of general formula [RuCp(L)₂SnX₂Y] [L = PPh₃, 1/2 dppe = 1,2-bis(diphenylphosphino)ethane; X, Y = F, Cl and Br], was prepared and studied by elemental analysis, ¹¹⁹Sn-Mössbauer spectroscopy, i.r. and ¹H-, ¹³C-, ¹⁹F-, ³¹P- and ¹¹⁹Sn-n.m.r. spectroscopy. ¹¹⁹Sn-Mössbauer studies allowed determination of the coordination number of the Sn^II center as well as the group electronegativity of the organometallic fragment [RuCp(L)₂]⁺. These results, supported by multinuclear n.m.r. data suggested that the electronic charge distribution between the Ru^II and Sn^II centers are strongly dependant upon the nature of L and the electronegativity of X and Y.     

Down-conversion process in Tb3+–Yb3+ co-doped Calibo glasses

The down-conversion process in Tb³⁺–Yb³⁺ co-doped Calibo glasses was studied. The emission, excitation and time-resolved measurements indicated the existence of an energy conversion through the excitation of Tb³⁺ ions to near-infrared emission by Yb³⁺ ions. The emission intensity dependence on excitation power confirms that the one-photon process is responsible for the Yb³⁺ emission. An enhanced Yb³⁺ emission was observed with Yb³⁺ doping and an optimal energy transfer efficiency of 32% was obtained before reaching near-infrared emission quenching. The mechanism of the non-resonant energy transfer from Tb³⁺ to Yb³⁺ is discussed in terms of the Tb³⁺–Yb³⁺ cross-relaxation and multiphonon decay processes.     

Birkhoffian Systems in Infinite Dimensional Manifolds

We generalize the theory of Kobayashi and Oliva (On the Birkhoff Approach to Classical Mechanics. Resenhas do Instituto de Matemática e Estatística da Universidade de São Paulo, 2003) to infinite dimensional Banach manifolds with a view towards applications in partial differential equations.