Microstructural, structural and dielectric properties of Er(3+)-modified BaTi(0.85)Zr(0.15)O(3) ceramics

The (micro)structural and electrical properties of undoped and Er(3+)-doped BaTi(0.85)Zr(0.15)O(3) ceramics were studied in this work for both nominal Ba(2+) and Ti(4+) substitution formulations. The ceramics were produced from solid-state reaction and sintered at 1400 degrees C for 3 h. For those materials prepared following the donor-type nominal Ba(1-x)Er(x)(Ti(0.85)Zr(0.15))O(3) composition, especially, Er(3+) however showed a preferential substitution for the (Ti,Zr)(4+) lattice sites. This allowed synthesis of a finally acceptor-like, highly resistive Ba(Ti,Zr,Er)O(3-delta)-like system, with a solubility limit below but close to 3 cat.% Er(3+). The overall phase development is discussed in terms of the amphoteric nature of Er(3+), and appears to mainly or, at least, partially also involve a minimization of stress effects from the ion size mismatch between the dopant and host cations. Further results presented here include a comparative analysis of the behavior of the materials` grain size, electrical properties and nature of the ferroelectric-to-paraelectric phase transition upon variation of the formulation and Er(3+) content. (C) 2008 Elsevier Ltd. All rights reserved.

Raman spectroscopy analysis of structural photoinduced changes in GeS(2) + Ga(2)O(3) thin films

Photoexpansion and photobleaching effects have been observed in amorphous GeS(2) + Ga(2)O(3) (GGSO) thin films, when their surfaces were exposed to UV light. The photoinduced changes on the surface of the samples are indications that the structure has been changed as a result of photoexcitation. In this paper, micro-Raman, energy dispersive X-ray analysis (EDX) and backscattering electrons (BSE) microscopy were the techniques used to identify the origin of these effects. Raman spectra revealed that these phenomena are a consequence of the Ge-S bonds` breakdown and the formation of new Ge-O bonds, with an increase of the modes associated with Ge-O-Ge bonds and mixed oxysulphide tetrahedral units (S-Ge-O). The chemical composition measured by EDX and BSE microscopy images indicated that the irradiated area is oxygen rich. So, the present paper provides fundamental insights into the influence of the oxygen within the glass matrix on the considered photoinduced effects. (C) 2010 Elsevier B.V. All rights reserved.

Preparation and structural characterization of rare-earth doped lead lanthanum zirconate titanate ceramics

A new preparation route towards rare-earth (RE) doped polycrystalline lead lanthanum zirconate titanate (PLZT) ceramics (RE = Y(3+), Nd(3+), Yb(3+)), based on the use of doped lanthanum oxide or zirconia, is reported. Structural characterization by X-ray powder diffraction reveals that secondary phase formation can be substantially diminished in comparison to conventional preparation methods. The distribution of the rare-earth dopants was investigated as a function of concentration by static (207)Pb spin echo NMR spectra, using Fourier Transformation of Carr-Purcell-Meiboom-Gill spin echo trains. For the Nd- and Yb-doped materials, the interaction of the (207)Pb nuclei with the unpaired electron spin density results in significant broadening and shifting of the NMR signal, whereas these effects are absent in the diamagnetic Y(3+) doped materials. Based on different concentration dependences of the NMR lineshape parameters, we conclude that the structural role of the Nd(3+) dopants differs significantly from that of Yb(3+). While the Nd(3+) ions appear to be statistically distributed in the PLZT lattice, incorporation of Yb(3+) into PLZT appears to be limited by the appearance of doped cubic zirconia as a secondary phase. (C) 2009 Elsevier Masson SAS. All rights reserved.

Structural and spectroscopic characterization of poly(styrene sulfonate) films doped with neodymium ions

This work reports the structural and spectroscopy characterization of poly(styrene sulfonate) (PSS) films doped with neodymium (Nd) ions. Nd-PSS films were processed using the acid of poly(styrene sulfonate) - H-PSS and neodymium nitrate - Nd(NO(3))(3); the maximum incorporation of Nd ions in the polymeric matrix was equal 19.3%. The absorption in the UV-Vis-NIR spectral region presents typical electronic transitions of Nd 3, ions, with well resolved peaks. The infrared spectra present the transition bands of PSS with characteristic line shape broadening, and the presence of vibrational modes of N-O groups in the range of 1400-720 cm(-1), prove the permanence of Nd(NO(3))(x), with x = 1, 2 and/or 3. in the H-PSS matrix. UV-Vis site selective photoluminescence data indicate that the incorporation of Nd 31 introduces a blue shift in PSS emission (325-800 nm), decreasing the interaction between adjacent PSS lateral groups (aromatic rings). Nd(3+) reabsorption and energy transfer effects between the PSS matrix and Nd(3+) were also observed. The IR emission of Nd-PSS films at 1076 rim ((4)F(3/2) -> (4)I(11/2)) present constant efficiency, independent on Nd(3+) concentration. The Judd-Ofelt theory was employed to analyze radiative properties. The excitation spectra prove the energy transfer between the polymeric matrix and Nd(3+). Complex impedance data was used to probe relaxation processes during the charge transport within the polymeric matrix. (C) 2008 Elsevier B.V. All rights reserved.

Combined Crystallographic and Solution Molecular Dynamics Study of Allosteric Effects in Ester and Ketone p-tert-Butylcalix[4]arene Derivatives and Their Complexes with Acetonitrile, Cd(II), and Pb(II)

We describe here a procedure to bridge the gap in the field of calixarene physicochemistry between solid-state atomic-resolution structural information and the liquid-state low-resolution thermodynamics and spectroscopic data. We use MD simulations to study the kinetics and energetics involved in the complexation of lower rim calix[4]arene derivatives (L), containing bidentate ester (1) and ketone (2) pendant groups, with acetonitrile molecule (MeCN) and Cd2+ and Pb2+ ions (M2+) in acetonitrile solution. On one hand, we found that the prior inclusion of MeCN into the calix to form a L(MeCN) adduct has only a weak effect in preorganizing the hydrophilic cavity toward metal ion binding. On the other hand, the strong ion-hydrophilic cavity interaction produces a wide open calix which enhances the binding of one MeCN molecule (allosteric effect) to stabilize the whole (M2+)1(MeCN) bifunctional complex. We reach two major conclusions: (i) the MD results for the (M2+)1(MeCN) binding are in close agreement with the ""endo"", fully encapsulated, metal complex found by X-ray diffraction and in vacuo MD calculations, and (ii) the MD structure for the more flexible 2 ligand, however, differs from the also endo solid-state molecule. In fact, it shows strong solvation effects at the calixarene lower bore by competing MeCN molecules that share the metal coordination sphere with the four C=O oxygens of an ""exo"" (M2+)2(MeCN) complex.

The Crystal Complex of Phosphofructokinase-2 of Escherichia coli with Fructose-6-phosphate KINETIC AND STRUCTURAL ANALYSIS OF THE ALLOSTERIC ATP INHIBITION

Substrate inhibition by ATP is a regulatory feature of the phosphofructokinases isoenzymes from Escherichia coli (Pfk-1 and Pfk-2). Under gluconeogenic conditions, the loss of this regulation in Pfk-2 causes substrate cycling of fructose-6-phosphate (fructose-6-P) and futile consumption of ATP delaying growth. In the present work, we have broached the mechanism of ATP-induced inhibition of Pfk-2 from both structural and kinetic perspectives. The crystal structure of Pfk-2 in complex with fructose-6-P is reported to a resolution of 2 angstrom. The comparison of this structure with the previously reported inhibited form of the enzyme suggests a negative interplay between fructose-6-P binding and allosteric binding of MgATP. Initial velocity experiments show a linear increase of the apparent K(0.5) for fructose-6-P and a decrease in the apparent k(cat) as a function of MgATP concentration. These effects occur simultaneously with the induction of a sigmoidal kinetic behavior (n(H) of approximately 2). Differences and resemblances in the patterns of fructose-6-P binding and the mechanism of inhibition are discussed for Pfk-1 and Pfk-2, as an example of evolutionary convergence, because these enzymes do not share a common ancestor.

Analysis of Agonist and Antagonist Effects on Thyroid Hormone Receptor Conformation by Hydrogen/Deuterium Exchange

Thyroid hormone receptors (TRs) are ligand-gated transcription factors with critical roles in development and metabolism. Although x-ray structures of TR ligand-binding domains (LBDs) with agonists are available, comparable structures without ligand (apo-TR) or with antagonists are not. It remains important to understand apo-LBD conformation and the way that it rearranges with ligands to develop better TR pharmaceuticals. In this study, we conducted hydrogen/deuterium exchange on TR LBDs with or without agonist (T(3)) or antagonist (NH(3)). Both ligands reduce deuterium incorporation into LBD amide hydrogens, implying tighter overall folding of the domain. As predicted, mass spectroscopic analysis of individual proteolytic peptides after hydrogen/deuterium exchange reveals that ligand increases the degree of solvent protection of regions close to the buried ligand-binding pocket. However, there is also extensive ligand protection of other regions, including the dimer surface at H10-H11, providing evidence for allosteric communication between the ligand-binding pocket and distant interaction surfaces. Surprisingly, C-terminal activation helix H12, which is known to alter position with ligand, remains relatively protected from solvent in all conditions suggesting that it is packed against the LBD irrespective of the presence or type of ligand. T(3), but not NH(3), increases accessibility of the upper part of H3-H5 to solvent, and we propose that TR H12 interacts with this region in apo-TR and that this interaction is blocked by T(3) but not NH(3.) We present data from site-directed mutagenesis experiments and molecular dynamics simulations that lend support to this structural model of apo-TR and its ligand-dependent conformational changes. (Molecular Endocrinology 25: 15-31, 2011)

Electronic Structure and Spectro-Structural Correlations of Fe(III)Zn(II) Biomimetics for Purple Acid Phosphatases: Relevance to DNA Cleavage and Cytotoxic Activity

Purple acid phosphatases (PAPs) are a group of metallohydrolases that contain a dinuclear Fe(II)M(II) center (M(II) = Fe, Mn, Zn) in the active site and are able to catalyze the hydrolysis of a variety of phosphoric acid esters. The dinuclear complex [(H(2)O)Fe(III)(mu-OH)Zn(II)(L-H)](CIO(4))(2) (2) with the ligand 2-[N-bis(2-pyridylmethyl)aminomethyl]-4-methyl-6-[N-(2-pyridylmethyl)(2-hydroxybenzyl) aminomethyl]phenol (H(2)L-H) has recently been prepared and is found to closely mimic the coordination environment of the Fe(III)Zn(II) active site found in red kidney bean PAP (Neves et al. J. Am. Chem. Soc. 2007, 129, 7486). The biomimetic shows significant catalytic activity in hydrolytic reactions. By using a variety of structural, spectroscopic, and computational techniques the electronic structure of the Fe(III) center of this biomimetic complex was determined. In the solid state the electronic ground state reflects the rhombically distorted Fe(III)N(2)O(4) octahedron with a dominant tetragonal compression align ad along the mu-OH-Fe-O(phenolate) direction. To probe the role of the Fe-O(phenolate) bond, the phenolate moiety was modified to contain electron-donating or -withdrawing groups (-CH(3), -H, -Br, -NO(2)) in the 5-position. Tie effects of the substituents on the electronic properties of the biomimetic complexes were studied with a range of experimental and computational techniques. This study establishes benchmarks against accurate crystallographic struck ral information using spectroscopic techniques that are not restricted to single crystals. Kinetic studies on the hydrolysis reaction revealed that the phosphodiesterase activity increases in the order -NO(2)<- Br <- H <- CH(3) when 2,4-bis(dinitrophenyl)phosphate (2,4-bdnpp) was used as substrate, and a linear free energy relationship is found when log(k(cat)/k(0)) is plotted against the Hammett parameter a. However, nuclease activity measurements in the cleavage of double stranded DNA showed that the complexes containing the electron-withdrawing -NO(2) and electron-donating CH3 groups are the most active while the cytotoxic activity of the biomimetics on leukemia and lung tumoral cells is highest for complexes with electron-donating groups.

Fluorescent AlPO(4) gels and glasses doped with Rhodamine 6G: Preparation, structural and optical characterization

Fluorescent AlPO(4) xerogels doped with different amounts of Rhodamine 6G (Rh6G) laser dye were prepared by a one-step sal-gel process. In addition, mesoporous AlPO(4) glasses obtained from undoped gels were loaded with different amounts of Rh6G by wet impregnation. Optical excitation and emission spectra of both series of samples show significant dependences on Rh6G concentration, revealing the influence of dye molecular aggregation. At comparable dye concentrations the aggregation effects are found to be significantly stronger in the gels than in the mesoporous glasses. This effect might be attributed to stronger interactions between the dye molecules and the glass matrix, resulting in more efficient dye dispersion in the latter. The interaction of Rh6G with the glassy AlPO(4) network has been probed by (27)Al and (31)P solid-state NMR techniques. New five- and six-coordinated aluminum environments have been observed and characterized by advanced solid-state NMR techniques probing (27)Al-(1)H and (27)Al-(31)P internuclear dipole couplings. The fractional area of these new Al sites is correlated with the combined fractional area of two new Q(3Al)((0)) and Q(2Al)((0)) phosphate species observed in the (31)P MAS NMR spectra. Based on this correlation as well as detailed composition dependent studies, we suggest that the new signals arise from the breakage of Al-O-P linkages associated with the insertion process. (C) 2010 Elsevier B.V. All rights reserved.

The effects of temperature on the molecular orientation of zinc phthalocyanine films

Phthalocyanine compounds have been widely investigated as candidate materials for technological applications, which is mainly due to their thermal stability and possibility of processing in the form of thin films. In most applications, the controlled growth of thin films with high crystalline quality is essential. In this study, zinc phthalocyanine (ZnPc) thin films were prepared by evaporation on glass and Au-coated glass substrates with subsequent annealing at different temperatures in ambient atmosphere. The morphological and structural features of 80 nm thick zinc phthalocyanine films were investigated, evidencing an alpha -> beta phase transformation after annealing the films at 200 A degrees C, as indicated by UV-Vis spectroscopy and FTIR analyses. A better uniformity of the annealed films was also evidenced via AFM analysis, which may be of importance for applications where film homogeneity and excellent optical quality are required.

A physical organic chemistry approach to dissolution of cellulose: effects of cellulose mercerization on its properties and on the kinetics of its decrystallization

The effects of alkali treatment on the structural characteristics of cotton linters and sisal cellulose samples have been studied. Mercerization results in a decrease in the indices of crystallinity and the degrees of polymerization, and an increase in the alpha-cellulose contents of the samples. The relevance of the structural properties of cellulose to its dissolution is probed by studying the kinetics of cellulose decrystallization, prior to its solubilization in LiCl/N,N-dimethylacetamide (DMAc). Our data show that the decrystallization rate constants and activation parameters are only slightly dependent on the physico-chemical properties of the starting celluloses. This multi-step reaction is accompanied by a small enthalpy and large, negative, entropy of activation. These results are analyzed in terms of the interactions within the biopolymer chains during decrystallization, as well as those between the two ions of the electrolyte and both DMAc and cellulose.

Effects of hydroxyl group distribution on the reactivity, stability and optical properties of fullerenols

We investigate the impact of hydroxyl groups on the properties of C(60)(OH)(n) systems, with n = 1, 2, 3, 4, 8, 10, 16, 18, 24, 32 and 36 by means of first-principles density functional theory calculations. A detailed analysis from the local density of states has shown that adsorbed OH groups can induce dangling bonds in specific carbon atoms around the adsorption site. This increases the tendency to form polyhydroxylated fullerenes (fullerenols). The structural stability is analyzed in terms of the calculated formation enthalpy of each species. Also, a careful examination of the electron density of states for different fullerenols shows the possibility of synthesizing single molecules with tunable optical properties.

Synthesis, Structural Characterization, and Biological Evaluation of Oxorhenium(V) Complexes with a Novel Type of Thiosemicarbazones Derived from N-[N `,N `-Dialkylamino(thiocarbonyl)]benzimidoyl Chlorides

Reactions of N-[N`,N`-diethylamino(thiocarbonyl)]benzimidoyl chloride with 4,4-dialkylthiosemicarbazides give a novel class of thiosemicarbazides/thiosemicarbazones, H(2)L, which causes a remarkable reduction of cell growth in in vitro experiments. These strong antiproliferative effects are also observed for oxorhenium(V) complexes of the general composition [ReOCl(L)], which are formed by reactions of the potentially tridentate ligands with (NBu(4))[ReOCl(4)]. A systematic substitution of the alkyl groups in the thiosemicarbazone building blocks of the ligands do not significantly influence the biological activity of the metal complexes, while the replacement of the chloro ligand by a PPh(3) ligand (by the replacement of the oxo unit by a nitrido ligand) completely terminated the cytotoxicity of the metal complexes.

Effects of light-curing time on the cytotoxicity of a restorative composite resin on odontoblast-like cells

This in vitro study evaluated the cytotoxicity of an experimental restorative composite resin subjected to different light-curing regimens. METHODS: Forty round-shaped specimens were prepared and randomly assigned to four experimental groups (n=10), as follows: in Group 1, no light-curing; in Groups 2, 3 and 4, the composite resin specimens were light-cured for 20, 40 or 60 s, respectively. In Group 5, filter paper discs soaked in 5 µL PBS were used as negative controls. The resin specimens and paper discs were placed in wells of 24-well plates in which the odontoblast-like cells MDPC-23 (30,000 cells/cm²) were plated and incubated in a humidified incubator with 5% CO2 and 95% air at 37ºC for 72 h. The cytotoxicity was evaluated by the cell metabolism (MTT assay) and cell morphology (SEM). The data were analyzed statistically by Kruskal-Wallis and Mann-Whitney tests (p<0.05). RESULTS: In G1, cell metabolism decreased by 86.2%, indicating a severe cytotoxicity of the non-light-cured composite resin. On the other hand, cell metabolism decreased by only 13.3% and 13.5% in G2 and G3, respectively. No cytotoxic effects were observed in G4 and G5. In G1, only a few round-shaped cells with short processes on their cytoplasmic membrane were observed. In the other experimental groups as well as in control group, a number of spindle-shaped cells with long cytoplasmic processes were found. CONCLUSION: Regardless of the photoactivation time used in the present investigation, the experimental composite resin presented mild to no toxic effects to the odontoblast-like MDPC-23 cells. However, intense cytotoxic effects occurred when no light-curing was performed.

Effects of a novel calcium aluminate cement on the early events of the progression of osteogenic cell cultures

The present study evaluated the progression of osteogenic cell cultures exposed to a novel calcium aluminate cement (CAC+) in comparison with the gold standard mineral trioxide aggregate (MTA). Cells were enzimatically isolated from newborn rat calvarial bone, plated on glass coverslips containing either CAC+ or a control MTA samples in the center, and grown under standard osteogenic conditions. Over the 10-day culture period, roundening of sample edges was clearly noticed only for MTA group. Although both cements supported osteogenic cell adhesion, spreading, and proliferation, CAC+-exposed cultures showed significantly higher values in terms of total cell number at days 3 and 7, and total protein content and alkaline phosphatase activity at day 10. The present in vitro results indicate that the exposure to CAC+ supports a higher differentiation of osteogenic cells compared with the ones exposed to MTA. Further experimental studies should consider CAC+ as a potential alternative to MTA when the repair of mineralized tissues is one of the desired outcomes in endodontic therapy.