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.     

Homodiselenacalix[4]arenes: Molecules with Unique Channelled Crystal Structures

A synthetic route towards homodiselenacalix[4]arene macrocycles is presented, based on the dynamic covalent chemistry of diselenides. The calixarene inner rim is decorated with either alkoxy or tert‐butyl ester groups. Single‐crystal X‐ray analysis of two THF solvates with methoxy and ethoxy substituents reveals the high similarity of their molecular structures and alterations on the supramolecular level. In both crystal structures, solvent channels are present and differ in both shape and capacity. Furthermore, the methoxy‐substituted macrocycle undergoes a single‐crystal‐to‐single‐crystal transformation during which the molecular structure changes its conformation from 1,3‐alternate (loaded with THF/water) to 1,2‐alternate (apohost form). Molecular modelling techniques were applied to explore the conformational and energetic behaviour of the macrocycles.     

Synthesis and metal complexation studies of [2n]thiacalix[m]arene[m]pyrazine

Novel [2_n]thiacalixarenepyrazine and [2_n]thiacalixarenetriazine systems were synthesised by one-pot S_NAr reactions. A screening of the metal-complexing ability of [2₆]hexathiacalix[3]arene[3]pyrazine revealed its affinity for Cu^I, Cu^II and Ag^I metal salts.     

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 investigation on PEO-based polymer electrolytes dispersed with Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles

Thin solid polymer electrolytes based on polyethylene oxide (PEO) and silver triflate (AgCF₃SO₃) dispersed with various concentrations of aluminum oxide (Al₂O₃) nanoparticles have been prepared by solution casting technique. These thin polymer films are found to have thickness of the order of 30 to 100 μm. The X-ray diffraction (XRD) patterns have indicated the amorphous nature of the polymer electrolyte. The differential scanning calorimeter (DSC) traces showed slight change in the glass transition temperature (T _g) whereas the degree of crystallization (X _c) decreases markedly due to the addition of alumina nanoparticles. Fourier transform infrared (FTIR) spectral analysis of all these samples has revealed the presence of absorption bands around 1,000 cm⁻¹; thus indicating the complexation of silver ions with oxygen in PEO. Employing the Wagner’s polarization technique as the standard method, the total ionic transference number for the complexed polymer electrolyte was found to be approximately unity thereby revealing that the significant contribution to electrical conduction was due to ions only. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, December 7–9, 2006     

UV-responsive polymeric superamphiphile based on a complex of malachite green derivative and a double hydrophilic block copolymer

We have prepared a UV-responsive polymeric superamphiphile, formed by a malachite green derivative and the double hydrophilic block copolymer methoxy-poly(ethylene glycol)(114)-block-poly(l-lysine hydrochloride)(200) (PEG-b-PLKC) on the basis of electrostatic interactions. The malachite green derivative undergoes photo-ionization upon UV irradiation, which makes it more hydrophilic, resulting in changes in the self-assembly behavior of the polymeric superamphiphile. For this reason, the polymeric superamphiphile originally self-assembles to form sheetlike aggregates, which disassemble after UV irradiation because of the increased solubility of the malachite green derivative. By use of Nile red as a probe, the polarity of the polymeric superamphiphile solution is confirmed to be increased after UV irradiation by fluorescence spectra, which also explains the disassembly of the polymeric superamphiphile.     

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.