Formation of an extended CoSi2 thin nanohexagons array coherently buried in silicon single crystal

A Co-doped silica film was deposited on the surface of a Si(100) wafer and isothermally annealed at 750 degrees C to form spherical Co nanoparticles embedded in the silica film and a few atomic layer thick CoSi2 nanoplatelets within the wafer. The structure, morphology, and spatial orientation of the nanoplatelets were characterized. The experimental results indicate that the nanoplatelets exhibit hexagonal shape and a uniform thickness. The CoSi2 nanostructures lattice is coherent with the Si lattice, and each of them is parallel to one of the four planes belonging to the {111} crystallographic form of the host lattice. (C) 2012 American Institute of Physics. [doi:10.1063/1.3683493]

From pyridoxalrhodanine to a novel 7-azacoumarin complex of dimethylthallium(III) in a one-pot synthesis

The hydrolysis of pyridoxalrhodanine in a basic medium containing the dimethylthallium(III) cation afforded the compound [TlMe2(L)]center dot H2O (1.H2O) [HL = 5-(hydroxymethyl)-8-methyl-3-thiol-7-azacoumarin]. This compound was characterized in solid state by IR spectroscopy and in solution by H-1 and C-13{H-1} NMR spectrometry. X-ray diffraction showed that the crystal consists of associated TlMe2(L) units and hydrogen bonded water molecules. The L- anion is bound to the metal mainly by a bridging S atom [Tl-S = 2.9458(18) angstrom; 2.9616(16) angstrom], although secondary interactions through O atoms (Tl-O: 2.861(5); 2.900(5) angstrom)] are also present. The longer Tl-O interaction and the hydrogen bonds of the water molecules give rise to a tridimensional polymeric structure. (C) 2012 Elsevier B.V. All rights reserved.

Liquid Crystal Nanodispersions Enable the Cutaneous Delivery of Photosensitizer for Topical PDT: Fluorescence Microscopy Study of Skin Penetration

Topical photodynamic therapy (PDT) has been applied to almost all types of nonmelanoma skin cancer and numerous superficial benign skin disorders. Strategies to improve the accumulation of photosensitizer in the skin have been studied in recent years. Although the hydrophilic phthalocyanine zinc compound, zinc phthalocyanine tetrasulfonate (ZnPcSO4) has shown high photodynamic efficiency and reduced phototoxic side effects in the treatment of brain tumors and eye conditions, its use in topical skin treatment is currently limited by its poor skin penetration. In this study, nanodispersions of monoolein (MO)-based liquid crystalline phases were studied for their ability to increase ZnPcSO4 uptake by the skin. Lamellar, hexagonal and cubic crystalline phases were prepared and identified by polarizing light microscopy, and the nanodispersions were analyzed by dynamic light scattering. In vitro skin penetration studies were performed using a Franz's cell apparatus, and the skin uptake was evaluated in vivo in hairless mice. Aqueous dispersions of cubic and hexagonal phases showed particles of nanometer size, approximately 224 +/- 10 nm and 188 +/- 10 nm, respectively. In vitro skin retention experiments revealed higher fluorescence from the ZnPcSO4 in deeper skin layers when this photosensitizer was loaded in the hexagonal nanodispersion system when compared to both the cubic phase nanoparticles and the bulk crystalline phases (lamellar, cubic and hexagonal). The hexagonal nanodispersion showed a similar penetration behavior in animal tests. These results are important findings, suggesting the development of MO liquid crystal nanodispersions as potential delivery systems to enhance the efficacy of topical PDT.

Relationship between Crystal Shape, Photoluminescence, and Local Structure in SrTiO3 Synthesized by Microwave-Assisted Hydrothermal Method

This paper describes the effect of using different titanium precursors on the synthesis and physical properties of SrTiO3 powders obtained by microwave-assisted hydrothermal method. X-ray diffraction measurements, X-ray absorption near-edge structure (XANES) spectroscopy, field emission scanning electron microscopy (FE-SEM), and high-resolution transmission electron microscopy (HRTEM) were carried out to investigate the structural and optical properties of the SrTiO3 spherical and cubelike-shaped particles. The appropriate choice of the titanium precursor allowed the control of morphological and photoluminescence (PL) properties of SrTiO3 compound. The PL emission was more intense in SrTiO3 samples composed of spherelike particles. This behavior was attributed to the existence of a lower amount of defects due to the uniformity of the spherical particles.

Synthesis, crystal structure and magnetic properties of the helical oxalate-bridged copper(II) chain {[(CH3)(4)N](2)[Cu(C2O4)(2)] center dot H2O}(n)

The preparation, crystal structure and magnetic properties of a new oxalate-containing copper(II) chain of formula {[(CH3)(4)N](2)]Cu(C2O4)(2)] center dot H2O}(n) (1) [(CH3)(4)N+ = tetramethylammonium cation] are reported. The structure of 1 consists of anionic oxalate-bridged copper(II) chains, tetramethylammoniun cations and crystallization water molecules. Each copper(II) ion in 1 is surrounded by three oxalate ligands, one being bidentate and the other two exhibiting bis-bidenate coordination modes. Although all the tris-chelated copper(H) units from a given chain exhibit the same helicity, adjacent chains have opposite helicities and then an achiral structure results. Variable-temperature magnetic susceptibility measurements of 1 show the occurrence of a weak ferromagnetic interaction through the oxalate bridge [J = +1.14(1)cm(-1), the Hamiltonian being defined as H = -J Sigma nm S-i . S-j]. This value is analyzed and discussed in the light of available magnetostructural data for oxalate-bridged copper(H) complexes with the same out-of-plane exchange pathway. (C) 2012 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.

Enhancement of the Nonlinear Optical Absorption of the E7 Liquid Crystal at the Nematic-Isotropic Transition

We present an experimental study of the nonlinear optical absorption of the eutectic mixture E7 at the nematic-isotropic phase transition by the Z-scan technique, under continuous-wave excitation at 532 nm. In the nematic region, the effective nonlinear optical coefficient beta, which vanishes in the isotropic phase, is negative for the extraordinary beam and positive for an ordinary beam. The parameter , whose definition in terms of the nonlinear absorption coefficient follows the definition of the optical-order parameter in terms of the linear dichroic ratio, behaves like an order parameter with critical exponent 0.22 +/- 0.05, in good agreement with the tricritical hypothesis for the nematic-isotropic transition.

Terbium(III) and dysprosium(III) 8-connected 3D networks containing 2,5-thiophenedicarboxylate anion: Crystal structures and photoluminescence studies

Two novel coordination polymers with the formula {[Ln(2)(2,5-tdc)(3)(dmso)(2)].H2O}(n) (Ln = Tb(III) for (1) and Dy(III) for (2)), (2,5-tdc(2-) = 2,5-thiophenedicarboxylate and dmso = dimethylsulfoxide) have been synthesized by the diffusion method and characterized by thermal analysis, vibrational spectroscopy and single crystal X-ray diffraction analysis. Structure analysis reveals that 2,5-tdc(2-) play a versatile role toward different lanthanide ions to form three-dimensional metal-organic frameworks (MOFs) in which the lanthanides ions are heptacoordinated. Photophysical properties were studied using excitation and emission spectra, where the photoluminescence data show the high emission intensity of the characteristic transitions D-5(4 ->) F-7(J) (J= 6, 5, 4 and 3) for (1) and (F9/2 -> HJ)-F-4-H-6 (J = 15/2, 13/2 and 11/2) for (2), indicating that 2,5-tdc(2-) is a good sensitizer. (C) 2012 Elsevier Ltd. All rights reserved.

TL dating of pottery fragments from four archaeological sites in Taquari Valley, Brazil

Sixty-three pottery fragments from four archaeological sites, numbered RST110, RST101, RST114 and RST114, in the Taquari Valley, vicinity of the city of Lajeado, Rio Grande do Sul state, southern Brazil, have been dated by the thermoluminescence method. Some of them from RST110 and RST101 are as old as 1400-1200 years, whereas those from RST114 and RST107 are younger than 800 years. This result indicates that RST101 and RST110 were peopled earlier than RST114 and RST107. The recent dates found are 302, 295 and 146 years and they are possible, since the first German immigrants who arrived in this region encountered Tupi-Guarani Indians still living there. One interesting result refers to the glow curves of quartz grains RST110, RST101 and RST114 that differ from the glow curves of RST107 quartz grains.

Color Dependence on Thickness in Topaz Crystal from Brazil

It is well known that crystals of topaz from the Eastern Brazilian Pegmatite Province may turn blue by the irradiation with Co-60 gamma rays followed by heat treatment. Also, it is known that the sensation of color changes with the thickness of these crystals. The dependence of the color, given by 1931 CIE chromaticity coordinates, with the thickness of the crystal was analyzed. The absorbance used in the calculation of these coordinates was given by the sum of Gaussian lines. The parameters of these lines were determined through the decomposition of the optical absorption spectra in the ultraviolet and visible regions. The decomposition revealed several lines, whose assignment was made considering studies in spodumene and beryl crystals and highly accurate quantum mechanical calculations. The transmittance becomes very narrow with increasing thickness, and the CIE chromaticity coordinates converge to the borderline of the CIE Chromaticity Diagram at the wavelength of maximum transmittance. Furthermore, the purity of color increases with increasing thickness, and the dominant wavelength reaches the wavelength of maximum transmittance.

Dependence of brittle-to-ductile transition on crystallographic direction in diamond turning of single-crystal silicon

The objective of this paper is to show the dependence relationship between the crystallographic orientations upon brittle-to-ductile transition during diamond turning of monocrystalline silicon. Cutting tests were performed using a -5 degrees rake angle round nose diamond tool at different machining scales. At the micrometre level, the feedrate was kept constant at 2.5 micrometres per revolution (mu m/r), and the depth of cut was varied from 1 to 5 mu m. At the submicrometre level, the depth of cut was kept constant at 500 nm and the feedrate varied from 5 to 10 mu m/r. At the micrometre level, the uncut shoulder generated with an interrupted cutting test procedure provided a quantitative measurement of the ductile-to-brittle transition. Results show that the critical chip thickness in silicon for ductile material removal reaches a maximum of 285 nm in the [100] direction and a minimum of 115 nm in the [110] direction, when the depth of cut was 5 mu m. It was found that when a submicrometre depth of cut was applied, microcracks were revealed in the [110] direction, which is the softer direction in silicon. Micro Raman spectroscopy was used to estimate surface residual stress after machining. Compressive residual stress in the range 142 MPa and smooth damage free surface finish was probed in the [100] direction for a depth of cut of 5 mu m, whereas residual stresses in the range 350 MPa and brittle damage was probed in the [110] direction for a depth of cut of 500 nm.

Spectroscopic characterization and crystal structure of cis-Bis(N-(2-benzoyl)-N ',N '-diphenylthioureato-k O-2,S)nickel(II)

The title compound [Ni(C20H15N2OS)(2)] is prepared by the reaction of metal acetate with the corresponding acylthiourea derivative. The complex is characterized by elemental analysis, IR, H-1 and C-13 NMR, and its structure is determined by single crystal X-ray diffraction. The Ni(II) ion is coordinated by the S and O atoms of two N-benzoyl-N',N'-diphenylthiourea ligands in a slightly distorted square-planar coordination geometry. The two O and two S atoms are mutually cis to each other. The substance crystallizes triclinic (P-1 space group) with cell dimensions a = 10.7262(9) , b = 12.938(3) , c = 14.2085(12) , alpha = 74.650(4)A degrees, beta = 78.398(4)A degrees, gamma = 68.200(5)A degrees, and two formula units in the unit cell. The structure is very close to the related N-(2-furoyl) Ni complex reported previously.

First measurement of beta decay half-lives in neutron-rich Tl and Bi isotopes

Neutron-rich isotopes around lead, beyond N = 126, have been studied exploiting the fragmentation of an uranium primary beam at the FRS-RISING setup at GSI. For the first time beta-decay half-lives of Bi-219 and Tl-211,Tl-212,Tl-213 isotopes have been derived. The half-lives have been extracted using a numerical simulation developed for experiments in high-background conditions. Comparison with state of the art models used in r-process calculations is given, showing a systematic underestimation of the experimental values, at variance from close-lying nuclei. (c) 2012 Elsevier B.V. All rights reserved.

Tricritical-like behavior of the nonlinear optical refraction at the nematic-isotropic transition in the E7 thermotropic liquid crystal

We use Z-scan technique to investigate the nonlinear optical response of the thermotropic liquid crystal E7 in the neighborhood of the nematic-isotropic phase transition. The analysis of the data for the nonlinear optical birefringence is compatible with an effective critical exponent of the order parameter, beta = 0.28 +/- 0.03, which is close to the classical value, beta = 0.25, for a tricritical point. The nonlinear optical absorption in the nematic range depends on the geometrical configuration of the nematic director with respect to the polarization beam, and vanishes in the isotropic phase.

A comparative study of the thermoluminescence properties of several varieties of Brazilian natural quartz

The following varieties of natural quartz, as the blue, the green, the red, the pink, the black, the sulphurous and the milky quartz, have been investigated concerning their thermoluminescence properties. For comparison sake natural colorless alpha quartz has been include. Since X-rays diffraction analysis has shown that all of them have the same crystal structure as the alpha quartz, it is expected that no great change in the TL property should be found, however, that was not the case. The TL peaks at 110, 175, 220, 325 and 375 degrees C observed in the alpha quartz are not found in all the varieties of quartz, for instance, the sulphurous quartz presented only 110 degrees and 245 degrees peaks, the pink one presented just 110, 220 and 375 degrees C peaks and so on. In respect to TL response as function of gamma ray dose a quite varied behavior has been observed and discussed. (C) 2012 Elsevier B.V. All rights reserved.

Crystal structure of isotibolone: a major degradation product of tibolone

Isotibolone is frequently found as an impurity in tibolone, a drug used for hormone reposition of post-menopause women, due to some inadequate tibolone synthesis or as a result of degradation during drug storage. The presence of isotibolone impurities should be detected and quantified in active pharmaceutical ingredient products of tibolone before its use in the manufacturing of medicaments. The X-ray powder diffraction technique offers the possibility of quantifying isotibolone amounts at different stages of drug production and storage, from the chemical synthesis to the final formulation. In the course of a study involving the quantitative analysis of isotibolone by X-ray powder diffraction, the authors determined the structure of the title compound using a recently developed approach (A. Gomez and S. Kycia, J. Appl. Crystallogr. 2011, 44, 708-713). The structure is monoclinic, space group P2(1) (4), with unit cell parameters a = 6.80704(7) angstrom, b = 20.73858(18) angstrom, c = 6.44900(6) angstrom, beta = 76.4302(5)degrees, V = 884.980(15) angstrom(3) and two molecules per unit cell (Z = 2). The molecules are hydrogen bonded in the ab plane forming layers that are held together in the crystal by van der Waals interactions along the c-axis.