Vanadium complexes with thiosemicarbazones: Synthesis, characterization, crystal structures and anti-Mycobacterium tuberculosis activity

The development of more efficient anti-tuberculosis drugs is of interest. Three oxovanadium(IV) and three cis-dioxovanadium(V) complexes with thiosemicarbazone derivatives bearing moieties with different lipophilicity have been prepared and had their inhibitory activity against Mycobacterium tuberculosis H(37)Rv ATCC 27294 evaluated. The analytical methods used by the complexes` characterization included IR, EPR, (1)H, (13)C and (51)V NMR spectroscopies, elemental analysis, cyclic voltammetry, magnetic susceptibility measurement and single crystal X-ray diffractometry. [VO(acac)(aptsc)], [VO(acac)(apmtsc)] and [VO(acac)(apptsc)] (acac = acetylacetonate; Haptsc = 2-acetylpyridinethiosemicarbazone; Hapmtsc = 2-acetylpyridine-N(4)-methyl-thiosemicarbazone and Happtsc = 2-acetylpyridine-N(4)-phenyl-thiosemicarbazone) are paramagnetic and their EPR spectra are consistent with the monoanionic N,N,S-tridentate coordination of the thiosemicarbazone ligands, resulting in octahedral structures of rhombic symmetry and with the oxidation state +IV for the vanadium atom. As result of oxidation of the vanadium(IV) complexes above, the diamagnetic cis-dioxovanadium(V) complexes [VO(2)(aptsc)[, [VO(2)(apmtsc)[ and [VO(2)(apptsc)] are formed. Their (1)H, (13)C and (51)V NMR spectra were acquired and support a distorted square pyramidal geometry for them, in accord with the solid state X-ray structures determined for [VO(2)(aptsc)] and [VO(2)(apmtsc)]. In general, the vanadium compounds show comparable or larger anti-M. tuberculosis activities than the free thiosemicarbazone ligands, with MIC values within 62.5-1.56 (mu g/mL). (C) 2008 Elsevier Ltd. All rights reserved.

Synthesis, characterization, crystal structure, and biological studies of vanadium complexes with glycolic acid

Synthesis, characterization, crystal structure, and biological studies of two complexes with glycolic acid are described. The solid complexes were formulated as K2[VO(C2H2O3)(C2H3O3)2] H2O (1) and K2[{VO2(C2H2O3)}2] (2) and characterized by X-ray studies, Fourier transform infrared spectroscopy (FTIR), Electron paramagnetic resonance (EPR), and magnetic susceptibility. Conversion of 1 to 2 was studied in aqueous solution by UV-Vis spectroscopy and in the solid state by diffuse reflectance spectroscopy. Complex 2 contains dinuclear [{VO2(C2H2O3)}2]2- anions in which glycolate(2-) is a five-membered chelating ring formed by carboxylate and -hydroxy groups. The geometry around the vanadium in 2 was interpreted as intermediate between a trigonal bipyramid and a square pyramid. Vanadium(IV) is pentacoordinate in 1 as a distorted square pyramid. Complex 1 contains a vanadyl group (V=O) surrounded by two oxygens from deprotonated carboxylate and hydroxy groups forming a five-membered ring. Two oxygens from different glycolates(1-) are bonded to the (V=O) also. Biological analysis for potential cytotoxic effects of 1 was performed using Human Cervix Adenocarcinoma (HeLa) cells, a human cervix adenocarcinoma-derived cell line. After incubation for 48 h, 1 causes 90 and 95% of HeLa cells death at 20 and 200 mol L-1, respectively.

Temperature dependence of molecular dynamics and supramolecular aggregation in MEH-PPV films: A solid-state NMR, X-ray and fluorescence spectroscopy study

This article presents an investigation of the temperature induced modification in the microstructure and dynamics of poly[2-methoxy-5-(2`-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) cast films using Wide-Angle X-ray Scattering (WAXS), solid-state Nuclear Magnetic Resonance (NMR), and Fluorescence Spectroscopy (PL). MEH-PPV chain motions were characterized as a function of temperature by NMR. The results indicated that the solvent used to cast the films influences the activation energy of the side-chain motions. This was concluded from the comparison of the activation energy of the toluene cast film, E(a) = (54 +/- 8) kJ/mol, and chloroform cast film, E(a) = (69 +/- 5) kJ/mol, and could be attributed to the higher side-chain packing provided by chloroform, that preferentially solvates the side chain in contrast to toluene that solvates mainly the backbone. Concerning the backbone mobility, it was observed that the torsional motions in the MEH-PPV have average amplitude of similar to 10 degrees at 300 K, which was found to be independent of the solvent used to cast the films. In order to correlate the molecular dynamics processes with the changes in the microstructure of the polymer, in situ WAXS experiments as a function of temperature were performed and revealed that the interchain spacing in the MEH-PPV molecular aggregates increases as a function of temperature, particularly at temperatures where molecular relaxations occur. It was also observed that the WAXS peak associated with the bilayer spacing becomes narrower and its intensity increases whereas the peak associated with the inter-backbone planes reduces its intensity for higher temperatures. This last result Could be interpreted as a decrease in the number of aggregates and the reduction of the interchain species during the MEH-PPV relaxation processes. These WAXS results were correlated with PL spectra modifications observed upon temperature treatments. (C) 2008 Elsevier Ltd. All rights reserved.

Solid state NMR as a new approach for the structural characterization of rare-earth doped lead lanthanum zirconate titanate laser ceramics

To facilitate the design of laser host materials with optimized emission properties, detailed structural information at the atomic level is essential, regarding the local bonding environment of the active ions (distribution over distinct lattice sites) and their extent of local clustering as well as their population distribution over separate micro- or nanophases. The present study explores the potential of solid state NMR spectroscopy to provide such understanding for rare-earth doped lead lanthanum zirconate titanate (PLZT) ceramics. As the NMR signals of the paramagnetic dopant species cannot be observed directly, two complementary approaches are utilized: (1) direct observation of diamagnetic mimics using Sc-45 NMR and (2) study of the paramagnetic interaction of the constituent host lattice nuclei with the rare-earth dopant, using Pb-207 NMR lineshape analysis. Sc-45 MAS NMR spectra of scandium-doped PLZT samples unambiguously reveal scandium to be six-coordinated, suggesting that this rare-earth ion substitutes in the B site. Static Pb-207 spin echo NMR spectra of a series of Tm-doped PLZT samples reveal a clear influence of paramagnetic rare-earth dopant concentration on the NMR lineshape. In the latter case high-fidelity spectra can be obtained by spin echo mapping under systematic incrementation of the excitation frequency, benefiting from the signal-to-noise enhancement afforded by spin echo train Fourier transforms. Consistent with XRD data, the Pb-207 NMR lineshape analysis suggests that statistical incorporation into the PLZT lattice occurs at dopant levels of up to 1 wt.% Tm3+, while at higher levels the solubility limit is reached. (C) 2008 Elsevier Masson SAS. All rights reserved.

Solid-state NMR characterization of a series of copolymers containing fluorene, phenylene and thiophene units

Fluorene and thiophene units are commonly used in polymeric materials for electro-optical applications. Due to differences in reactivity, the final composition of polymers containing these components often differs from that used in their preparation. This contribution describes the synthesis of PPV type terpolymers built by fluorene, phenylene and thiophene units and their quantification by CPMAS NMR. The similarity of the three aromatic co-monomers makes it difficult to separate the analytical responses that would allow quantification of each copolymer unit in the chain. In this sense, we show that the combination of dipolar dephased CPMAS with radiofrequency ramp and proper spectral treatment allows a good estimation and quantification of the copolymer constitution. (C) 2011 Elsevier Ltd. All rights reserved.

Crystal structure of garciniaphenone and evidences on the relationship between keto-enol tautomerism and configuration

Garciniaphenone (=rel-(1R,5R,7R)-3-benzoyl-4-hydroxy-8,8-dimethyl-1,7-bis(3-methylbut-2-en-1-yl)bicyclo[3.3.1]non-3-ene-2,9-dione; 1). a novel natural product, was isolated from a hexane extract of Garcinia brasiliensis fruits. The crystal structure of 1 as well as the selected geometrical and Configurational features were compared with those of known related polyprenylated benzophenones. Garciniaphenone is the first representative of polyprenylated benzophenones without a prenyl substituent at C(5). Notably, the absence of a 5-prenyl substituent has an impact on the molecular geometry. The tautomeric form of 1 in the solid state was readily established by a residual-electronic-density map generated by means of a difference Fourier analysis, and there is an entirely delocalized six-membered chelate ring encompassing the keto-enol moiety. The configuration at C(7) was used to rationalize the nature of the keto-enol tautomeric form within 1. The intermolecular array in the network is maintained by nonclassical intermolecular H-bonds.

Pseudo-nonlinear and athermal lensing effects on transverse properties of Cr(3+) based solid-state lasers

Several experiments (time-resolved Z-scan experiments based on pulsed and CW pump lasers, time-resolved divergence diagnostics) have been performed to examine and clarify the question of the converging or diverging population lensing effect occurring in a Cr(3+):Al(2)O(3) ruby laser. The dynamics of the laser far-field divergence of such a laser indeed indicated initially a diverging effect while Z-scan measurements conclude to a converging one. The origin of this discrepancy is thus analysed and elucidated here by introducing the general concept of correlation collapse between the centre and the wings of a laser beam having some clipping. (C) 2010 Elsevier B.V. All rights reserved.

Glass-to-Vitroceramic Transition in the Yttrium Aluminoborate System: Structural Studies by Solid-State NMR

The crystallization of laser glasses in the system (B(2)O(3))(0.6){(Al(2)O(3))(0.4-y)(Y(2)O(3))(y)} (0.1 <= y <= 0.25) doped with different levels of ytterbium oxide has been investigated by X-ray powder diffraction, differential thermal analysis, and various solid-state NMR techniques. The homogeneous glasses undergo major phase segregation processes resulting in crystalline YBO(3), crystalline YAI(3)(BO(3))(4), and residual glassy B(2)O(3) as the major products. This process can be analyzed in a quantitative fashion by solid-state (11)B, (27)Al, and (89)Y NMR spectroscopies as well as (11)B{(27)Al} rotational echo double resonance (REDOR) experiments. The Yb dopants end up in both of the crystalline components, producing increased line widths of the corresponding (11)B, (27)Al, and (89)Y NMR resonances that depend linearly on the Yb/Y substitution ratio. A preliminary analysis of the composition dependence suggests that the Yb(3+) dopant is not perfectly equipartitioned between both crystalline phases, suggesting a moderate preference of Yb to substitute in the crystalline YBO(3) component.

The effects of anticalcification treatments and hydration on the molecular dynamics of bovine pericardium collagen as revealed by (13)C solid-state NMR

This article describes a solid-state NMR (SSNMR) investigation of the influence of hydration and chemical cross-linking on the molecular dynamics of the constituents of the bovine pericardium (BP) tissues and its relation to the mechanical properties of the tissue. Samples of natural phenetylamine-diepoxide (DE)- and glutaraldehyde (GL)-fixed BP were investigated by (13)C cross-polarization SSNMR to probe the dynamics of the collagen, and the results were correlated to the mechanical properties of the tissues, probed by dynamical mechanical analysis. For samples of natural BP, the NMR results show that the higher the hydration level the more pronounced the molecular dynamics of the collagen backbone and sidechains, decreasing the tissue`s elastic modulus. In contrast, in DE- and GL-treated samples, the collagen molecules are more rigid, and the hydration seems to be less effective in increasing the collagen molecular dynamics and reducing the mechanical strength of the samples. This is mostly attributed to the presence of cross-links between the collagen plates, which renders the collagen mobility less dependent on the water absorption in chemically treated samples. Copyright (C) 2010 John Wiley & Sons, Ltd.

Development of zirconia-magnesia/zirconia-yttria composite solid electrolytes

Composite solid electrolytes were prepared by thoroughly mixing ZrO2:8 mol% MgO (Z8Mg) and ZrO(2):3 mol% Y(2)O(3) (Z3Y) ceramic powders followed by pressing and sintering at 1500 degrees C/1 h. The properties of the sintered pellets were studied by X-ray diffraction for evaluation of the structural phases by the Rietveld method, by high-temperature dilatometry for analysis of the thermal shrinkage/expansion behavior, and by impedance spectroscopy for determination of the oxide ion conductivity. The x(Z8Mg)+(1-x)(Z3Y) specimens, x= 0.2, 0.4, 0.5, 0.6, 0.8 and 1.0, are partially stabilized (monoclinic, cubic and tetragonal phases) with density >94% of the theoretical density and show thermal shock resistance and electrical conductivity values suitable for high-temperature oxygen gas detection. One-end closed tube samples of the composite solid electrolytes were assembled in Pt/Z8Mg+Z3Y/Cr+Cr(2)O(3)/Pt electrochemical cells for exposure to different levels of oxygen in the 1-850 ppm range. The total electrical conductivity increases for increasing the relative Z3Y content. Addition of Z3Y to Z8Mg (80 wt.%-20 wt.%) suppresses the electronic contribution to the electrical conductivity at 620 degrees C. (c) 2008 Elsevier B.V. All rights reserved.

Crystal structure of the (Mg,Fe)[UO2(P,As)O-4](2) center dot 10H(2)O solid solution - A novel mineral variety of saleeite

The crystal structure of a novel variety {[(Mg0.81Fe0.19)(H2O)(6)](H2O)(4)}{(UO2)[(P0.67As0.33)O-4]}(2) of the mineral saleeite is determined using X-ray diffraction (Bruker Smart diffractometer, lambda MoK alpha, graphite monochromator, 2 theta(max) = 56.62 degrees, R = 0.0321 for 2317 reflections, T = 100 K). The main crystal data are as follows: a = 6.952(6) angstrom, b = 19.865(5) , angstrom, c = 6.969(2) angstrom, beta = 90.806(4)degrees, space group P12(l)/n1, Z = 2, and P-calcd = 3.34 g/cm(3). It is shown that the structure is formed by alternating (along the [010] direction) anionic layers, which are composed of uranium bipyramids and T(P,As) tetrahedra, and cation layers consisting of M(Mg, Fe) octahedra and water molecules, which are joined through a system of asymmetric hydrogen bonds. The hydrogen atoms are located, the scheme of hydrogen bonds is established, and their geometric characteristics are calculated.

An algorithm for automatic checking of exercises in a dynamic geometry system: iGeom

One of the key issues in e-learning environments is the possibility of creating and evaluating exercises. However, the lack of tools supporting the authoring and automatic checking of exercises for specifics topics (e.g., geometry) drastically reduces advantages in the use of e-learning environments on a larger scale, as usually happens in Brazil. This paper describes an algorithm, and a tool based on it, designed for the authoring and automatic checking of geometry exercises. The algorithm dynamically compares the distances between the geometric objects of the student`s solution and the template`s solution, provided by the author of the exercise. Each solution is a geometric construction which is considered a function receiving geometric objects (input) and returning other geometric objects (output). Thus, for a given problem, if we know one function (construction) that solves the problem, we can compare it to any other function to check whether they are equivalent or not. Two functions are equivalent if, and only if, they have the same output when the same input is applied. If the student`s solution is equivalent to the template`s solution, then we consider the student`s solution as a correct solution. Our software utility provides both authoring and checking tools to work directly on the Internet, together with learning management systems. These tools are implemented using the dynamic geometry software, iGeom, which has been used in a geometry course since 2004 and has a successful track record in the classroom. Empowered with these new features, iGeom simplifies teachers` tasks, solves non-trivial problems in student solutions and helps to increase student motivation by providing feedback in real time. (c) 2008 Elsevier Ltd. All rights reserved.

Decay of geometry for Fibonacci critical covering maps of the circle

We study the growth of Df `` (f(c)) when f is a Fibonacci critical covering map of the circle with negative Schwarzian derivative, degree d >= 2 and critical point c of order l > 1. As an application we prove that f exhibits exponential decay of geometry if and only if l <= 2, and in this case it has an absolutely continuous invariant probability measure, although not satisfying the so-called Collet-Eckmann condition. (C) 2009 Elsevier Masson SAS. All rights reserved.

Periodic geodesics and geometry of compact Lorentzian manifolds with a Killing vector field

We study the geometry and the periodic geodesics of a compact Lorentzian manifold that has a Killing vector field which is timelike somewhere. Using a compactness argument for subgroups of the isometry group, we prove the existence of one timelike non self-intersecting periodic geodesic. If the Killing vector field is nowhere vanishing, then there are at least two distinct periodic geodesics; as a special case, compact stationary manifolds have at least two periodic timelike geodesics. We also discuss some properties of the topology of such manifolds. In particular, we show that a compact manifold M admits a Lorentzian metric with a nowhere vanishing Killing vector field which is timelike somewhere if and only if M admits a smooth circle action without fixed points.

COMPARISON RESULTS FOR CONJUGATE AND FOCAL POINTS IN SEMI-RIEMANNIAN GEOMETRY VIA MASLOV INDEX

We prove an estimate on the difference of Maslov indices relative to the choice of two distinct reference Lagrangians of a continuous path in the Lagrangian Grassmannian of a symplectic space. We discuss some applications to the study of conjugate and focal points along a geodesic in a semi-Riemannian manifold.