Cu-II-Azide Polymers of Cu-3 and Cu-6 Building Units: Synthesis,Structures, and Magnetic Exchange Mechanism

Two new neutral copper-azido polymers [Cu-3(N-3)(6)(tmen)(2)](n)(1)and [Cu-6(N-3)(12)(deen)(2)](n) (2) [tmen = N,N,N, N-tetramethylethylenediamine and deen = N,N-diethylethylenediamine] have been synthesized by using lower molar equivalents of the chelating diamine ligands with Cu(NO3)(2)center dot 3H(2)O and an excess of NaN3. The single crystal X-ray structure shows that in the basic unit of the 1D complex 1, the three Cu-II ions are linked by double end-on azido bridges with Cu-N-EO-Cu angles on both sides of the magnetic exchange critical angle of 108 degrees. Complex 2 is a 3D framework of a basic u-6 cluster. Cryomagnetic susceptibility measurements over a wide range of temperature exhibit dominant ferromagnetic behavior in both the complexes. Density functional theory calculations (B3LYP functional) have been performed on the trinuclear unit to provide a qualitative theoretical interpretation of the overall ferromagnetic behavior shown by the complex 1.

Taxonomy and redescription of the Swamp Antechinus, Antechinus minimus (E. Geoffroy) (Marsupialia: Dasyuridae)

We provide a taxonomic redescription of the dasyurid marsupial Swamp Antechinus, Antechinus minimus (Geoffroy, 1803). In the past, A. minimus has been classified as two subspecies: the nominate A. minimus minimus (Geoffroy, 1803), which is found throughout much of Tasmania (including southern Bass Strait islands) and A. minimus maritimus (Finlayson, 1958), which is found on mainland Australia (as well as some near-coastal islands) and is patchily distributed in mostly coastal areas between South Gippsland (Victoria) and Robe (South Australia). Based on an assessment of morphology and DNA, we conclude that A. minimus is both distinctly different from all extant congeners and that the two existing subspecies of Swamp Antechinus are appropriately taxonomically characterised. In our genetic phylogenies, the Swamp Antechinus was monophyletic with respect to all 14 known extant congeners; moreover, A. minimus was well-positioned in a large clade, together with all four species in the Dusky Antechinus complex, to the exclusion of all other antechinus. Within A. minimus, between subspecies there were subtle morphological differences (A. m. maritimus skulls tend to be broader, with larger molar teeth, than A. m. minimus, but these differences were not significant); there was distinct, but only moderately deep genetic differences (3.9–4.5% at mtDNA) between A. minimus subspecies. Comparatively, across Bass Strait, the two subspecies of A. minimus are morphologically and genetically markedly less divergent than recently recognised species pairs within the Dusky Antechinus complex, found in Victoria (A. mimetes) and Tasmania (A. swainsonii) (9.4–11.6% divergent at mtDNA)

Synthesis of mesoporous TiO2/SiO2 hybrid films as an efficient photocatalyst by polymeric micelle assembly

Thermally stable mesoporous TiO2/SiO2 hybrid films with pore size of 50 nm have been synthesized by adopting the polymeric micelle-assembly method. A triblock copolymer, poly(styrene-b-2-vinyl pyridine-b-ethylene oxide), which serves as a template for the mesopores, was utilized to form polymeric micelles. The effective interaction of titanium tetraisopropoxide (TTIP) and tetraethyl orthosilicate (TEOS) with the polymeric micelles enabled us to fabricate stable mesoporous films. By changing the molar ratio of TEOS and TTIP, several mesoporous TiO2/SiO2 hybrid films with different compositions can be synthesized. The presence of amorphous SiO2 phase effectively retards the growth of anatase TiO2 crystal in the pore walls and retains the original mesoporous structure, even at higher temperature (650 °C). These TiO2/SiO2 hybrid films are of very high quality, without any cracks or voids. The addition of SiO2 phase to mesoporous TiO2 films not only adsorbs more organic dyes, but also significantly enhances the photocatalytic activity compared to mesoporous pure TiO2 film without SiO2 phase.

Synthesis, spectral characterization, in-vitro microbiological evaluation and cytotoxic activities of novel macrocyclic bis hydrazone

A macrocyclic hydrazone Schiff base was synthesized by reacting 1,4-dicarbonyl phenyl dihydrazide with 2,6-diformyl-4-methyl phenol and a series of metal complexes with this new Schiff base were synthesized by reaction with Co(II), Ni(II) and Cu(II) metal salts. The Schiff base and its complexes have been characterized by elemental analyses, IR, H-1 NMR, UV-vis, FAB mass, ESR spectra, fluorescence, thermal, magnetic and molar conductance data. The analytical data reveal that the Co(II), Ni(II) and Cu(II) complexes possess 2:1 metal-ligand ratios. All the complexes are non-electrolytes in DMF and DMSO due to their low molar conductance values. Infrared spectral data suggest that the hydrazone Schiff base behaves as a hexadentate ligand with NON NON donor sequence towards the metal ions. The ESR spectral data shows that the metal-ligand bond has considerable covalent character. The electrochemical behavior of the copper(II) complex was investigated by cyclic voltammetry. The Schiff base and its complexes have also been screened for their antibacterial (Escherichia coli, Staphylococcus aureus, Shigella dysentery, Micrococcus, Bacillus subtilis, Bacillus cereus and Pseudomonas aeruginosa) and antifungal activities (Aspergillus niger, Penicillium and Candida albicans) by MIC method. The brine shrimp bioassay was also carried out to study their in-vitro cytotoxic properties. (C) 2009 Elsevier Masson SAS. All rights reserved.

Evolution of nanocrystalline BaBi2Nb2O9 in Li2B4O7 BaO-Bi(2)O3-Nb2O5 glass system

Transparent glasses and glass nano crystal composites (GNCs) of various compositions in the system (100 - x)Li2B4O7-x (BaO-Bi2O3-Nb2O5) (where x = 10, 20, and 30 in molar ratio) were fabricated via splat-quenching technique. The glassy nature of the as quenched samples was established by differential thermal analyses. X-ray powder diffraction and transmission electron microscopic (TEM) studies confirmed the formation of layered perovskite BBN via a fluorite like phase. TEM studies revealed the presence of 10 nm sized spherical crystallites of fluorite like BaBi2Nb2O9 phase in the glassy matrix of Li2B4O7 (LBO). The influence of composition on the dielectric and the optical properties (transmission, optical band gap) of these samples has been investigated. (c) 2007 Elsevier B.V. All rights reserved.

Bond-order wave phase, spin solitons, and thermodynamics of a frustrated linear spin-1/2 Heisenberg antiferromagnet

The linear spin-1/2 Heisenberg antiferromagnet with exchanges J(1) and J(2) between first and second neighbors has a bond-order wave (BOW) phase that starts at the fluid-dimer transition at J(2)/J(1)=0.2411 and is particularly simple at J(2)/J(1)=1/2. The BOW phase has a doubly degenerate singlet ground state, broken inversion symmetry, and a finite-energy gap E-m to the lowest-triplet state. The interval 0.4 < J(2)/J(1) < 1.0 has large E-m and small finite-size corrections. Exact solutions are presented up to N = 28 spins with either periodic or open boundary conditions and for thermodynamics up to N = 18. The elementary excitations of the BOW phase with large E-m are topological spin-1/2 solitons that separate BOWs with opposite phase in a regular array of spins. The molar spin susceptibility chi(M)(T) is exponentially small for T << E-m and increases nearly linearly with T to a broad maximum. J(1) and J(2) spin chains approximate the magnetic properties of the BOW phase of Hubbard-type models and provide a starting point for modeling alkali-tetracyanoquinodimethane salts.

ZnO nanocrystalline thin films: a correlation of microstructural, optoelectronic properties

The compositional, structural, microstructural, dc electrical conductivity and optical properties of undoped zinc oxide films prepared by the sol-gel process using a spin-coating technique were investigated. The ZnO films were obtained by 5 cycle spin-coated and dried zinc oxide films followed by annealing in air at 600 A degrees C. The films deposited on the platinum coated silicon substrate were crystallized in a hexagonal wurtzite form. The energy-dispersive X-ray (EDX) spectrometry shows Zn and O elements in the products with an approximate molar ratio. TEM image of ZnO thin film shows that a grain of about 60-80 nm in size is really an aggregate of many small crystallites of around 10-20 nm. Electron diffraction pattern shows that the ZnO films exhibited hexagonal structure. The SEM micrograph showed that the films consist in nanocrystalline grains randomly distributed with voids in different regions. The dc conductivity found in the range of 10(-5)-10(-6) (Omega cm)(-1). The optical study showed that the spectra for all samples give the transparency in the visible range.

Characterisation of cellulose- and lignin-based materials using x-ray scattering methods

Wood is an important material for the construction and pulping industries. Using x-ray diffraction the microfibril angle of Sitka spruce wood was studied in the first part of this thesis. Sitka spruce (Picea sitchensis [Bong.] Carr.) is native to the west coast of North America, but due to its fast growth rate, it has also been imported to Europe. So far, its nanometre scale properties have not been systematically characterised. In this thesis the microfibril angle of Sitka spruce was shown to depend significantly on the origin of the tree in the first annual rings near the pith. Wood can be further processed to separate lignin from cellulose and hemicelluloses. Solid cellulose can act as a reducer for metal ions and it is also a porous support for nanoparticles. By chemically reducing nickel or copper in the solid cellulose support it is possible to get small nanoparticles on the surfaces of the cellulose fibres. Cellulose supported metal nanoparticles can potentially be used as environmentally friendly catalysts in organic chemistry reactions. In this thesis the size of the nickel and copper containing nanoparticles were studied using anomalous small-angle x-ray scattering and wide-angle x-ray scattering. The anomalous small-angle x-ray scattering experiments showed that the crystallite size of the copper oxide nanoparticles was the same as the size of the nanoparticles, so the nanoparticles were single crystals. The nickel containing nanoparticles were amorphous, but crystallised upon heating. The size of the nanoparticles was observed to be smaller when the reduction of nickel was done in aqueous ammonium hydrate medium compared to reduction made in aqueous solution. Lignin is typically seen as the side-product of wood industries. Lignin is the second most abundant natural polymer on Earth, and it possesses potential to be a useful material for many purposes in addition to being an energy source for the pulp mills. In this thesis, the morphology of several lignins, which were produced by different separation methods from wood, was studied using small-angle and ultra small-angle x-ray scattering. It was shown that the fractal model previously proposed for the lignin structure does not apply to most of the extracted lignin types. The only lignin to which the fractal model could be applied was kraft lignin. In aqueous solutions the average shape of the low molar mass kraft lignin particles was observed to be elongated and flat. The average shape does not necessarily correspond to the shape of the individual particles because of the polydispersity of the fraction and due to selfassociation of the particles. Lignins, and especially lignosulfonate, have many uses as dispersants, binders and emulsion stabilisers. In this thesis work the selfassociation of low molar mass lignosulfonate macromolecules was observed using small-angle x-ray scattering. By taking into account the polydispersity of the studied lignosulfonate fraction, the shape of the lignosulfonate particles was determined to be flat by fitting an oblate ellipsoidal model to the scattering intensity.

Elastic properties of fast ion conducting lithium based borate glasses

Elastic properties of Li2O-PbO-B2O3 glasses have been investigated using sound velocity measurements at 10 MHz. Four series of glasses have been investigated with different concentrations of Li2O, PbO and B2O3. The variations of molar volume have been examined for the influences of Li2O and PbO. The elastic moduli reveal trends in their compositional dependence. The bulk and shear modulus increases monotonically with increase in the concentration of tetrahedral boron which increases network dimensionality. The variation of bulk moduli has also been correlated to the variation in energy densities. The Poisson's ratio found to be insensitive to the concentration of tetrahedral boron in the structure. The experimental Debye temperatures are in good agreement with the expected theoretical values. Experimental observations have been examined in view, the presence of borate network and the possibility of non-negligible participation of lead in network formation. (c) 2005 Elsevier B.V. All rights reserved.

Dielectric properties of (100-x)Li2B4O7-x(Ba5Li2Ti2Nb8O30) glasses and glass nanocrystal composites

Transparent glasses of various compositions in the system (100 -x)(Li2B4O7)-x(Ba5Li2Ti2Nb8O30) (5 <= x <= 20, in molar ratio) were fabricated by splat quenching technique. The glassy nature of the as-quenched samples was established by differential thermal analyses (DTA). X-ray powder diffraction studies confirmed the as-quenched glasses to be amorphous and the heat-treated to be nanocrystalline. Controlled heat-treatment of the as-quenched glasses at 500 degrees C for 8 h yielded nanocrystallites embedded in the glass matrix. High Resolution Transmission Electron Microscopy (HRTEM) of these samples established the size of the crystallites to be in the nano-range and confirmed the phase to be that of Ba5Li2Ti2Nb8O30 (BLTN) which was, initially, identified by X-ray powder diffraction. The frequency, temperature and compositional dependence of the dielectric constant and the electrical conductivity of the glasses and glass nanocrystal composites were investigated in the 100 Hz to 10 MHz frequency range. Electrical relaxations were analyzed using the electric modulus formalisms. The imaginary part of electric modulus spectra was modeled using an approximate solution of Kohlrausch-Williams-Watts relation. The frequency dependent electrical conductivity was rationalized using Jonscher's power law. The activation energy associated with the dc conductivity was ascribed to the motion of Li+ ions in the glass matrix. The activation energy associated with dielectric relaxation was almost equal to that of the dc conductivity, indicating that the same species took part in both the processes. (C) 2010 Elsevier B.V. All rights reserved.

Korkean lämpötilan vaikutus hiiren poskihampaan kiilteen kehitykseen in vitro

Tutkimuksen tarkoituksena oli selvittää kuumetta vastaavan elinviljelylämpötilan vaikutusta hiiren poskihampaiden kiilteen kehittymiseen. Tutkimus tehtiin in vitro ja siinä käytettiin E18- hiiriä, joiden hampaita kasvatettiin ´kuumeessa´ (39 °C) kolmannesta kasvatuspäivästä lähtien, osaa viisi ja osaa kolme päivää. Kontrollihampaita kasvatettiin 37 °C:ssa. Hampaita kasvatettiin yhteensä 11 päivää ja lopuksi ne kuvattiin. Stereomikroskooppikuvista mitattiin kiilteen korkeus ja kruunun korkeus ja laskettiin näiden suhde. Hampaat demineralisoitiin, valettiin parafiiniin, leikattiin leikkeiksi ja värjättiin HE-värjäyksellä. Leikkeistä mitattiin kiilteen paksuus ja kiilteen ja dentiinin yhteispaksuus ja laskettiin näiden suhde. Arvoja verrattiin kasvatusryhmien kesken. Tulokset analysoitiin Mann-Whitney-testillä. Kiilteen paksuus suhteessa kiilteen ja dentiinin yhteispaksuuteen oli pienempi ´kuumehampaissa´. Viisi tai kolme päivää ´kuumeessa´kasvatettujen hampaiden välillä ei ollut juurikaan eroja. Kiilteen korkeus suhteessa kruunun korkeuteen oli pienempi ´kuumehampaissa´ kuin kontrollihampaissa. Korkea lämpötila ei muutoin näyttänyt vaikuttavan hampaiden kehitykseen. Tutkimuksen perusteella voidaan sanoa, että kasvatuslämpötilan nosto kuumeen tasolle aiheuttaa hiiren molaarihampaan kiilteen kehityksen häiriintymistä. Tulos tukee kliinisiä havaintoja, joiden mukaan korkea kuume lapsella voi aiheuttaa kiilteen kehityshäiriöitä.

Compressibility of dilute solutions of sulphuric acid

By employing Carstensen's phase-comparison pulse method for measuring ultrasonic velocity-differences, the compressibility of sulphuric acid has been studied anew, the special interest being in the low concentration region. Sulphuric acid is found to show at first a decrease in velocity with increasing concentration and then an increase. The curve representing the apparent molal compressibility Φ(κ̄2) against the square root of the molar concentration c, shows a maximum and a minimum. This anomalous behaviour is interesting in view of the extreme anomalies in other colligative properties of sulphuric acid. A qualitative explanation of the observed maximum and minimum has been suggested.

Role of entropy in the stability of cobalt titanates

The standard molar Gibbs free energy of formation of Co2TiO4, CoTiO3,and CoTi2O5 as a function of temperature over an extended range (900 to 1675) K was measured using solid-state electrochemical cells incorporating yttria-stabilized zirconia as the electrolyte, with CoO as reference electrode and appropriate working electrodes. For the formation of the three compounds from their component oxides CoO with rock-salt and TiO2 with rutile structure, the Gibbs free energy changes are given by:Delta(f)G degrees((ox))(Co2TiO4) +/- 104/(J . mol(-1)) = -18865 - 4.108 (T/K)Delta(f)G degrees((ox))(CoTiO3) +/- 56/(J . mol(-1)) = -19627 + 2.542 (T/K) Delta(f)G degrees((ox))(CoTi2O5) +/- 52/(J . mol(-1)) = -6223 - 6.933 (T/K) Accurate values for enthalpy and entropy of formation were derived. The compounds Co2TiO4 with spinel structure and CoTi2O5 with pseudo-brookite structure were found to be entropy stabilized. The relatively high entropy of these compounds arises from the mixing of cations on specific crystallographic sites. The stoichiometry of CoTiO3 was confirmed by inert gas fusion analysis for oxygen. Because of partial oxidation of cobalt in air, the composition corresponding to the compound Co2TiO4 falls inside a two-phase field containing the spinet solid solution Co2TiO4-Co3O4 and CoTiO3. The spinel solid solution becomes progressively enriched in Co3O4 with decreasing temperature. (c) 2010 Elsevier Ltd. All rights reserved.

Structural and optical properties of (100-x)Li2B4O7 center dot x(Ba5Li2Ti2Nb8O30) glasses and glass nanocrystal composites

Optically clear glasses of various compositions in the system (100-x)Li2B4O7 center dot x(Ba5Li2Ti2Nb8O30) (5 <= x <= 20, in molar ratio) were fabricated by splat quenching technique. Controlled heat-treatment of the as-quenched glasses at 500 degrees C for 8 h yielded nanocrystallites embedded in the glass matrix. High Resolution Transmission Electron Microscopy (HRTEM) of these samples established the composition of the nano-crystallites to be that of Ba5Li2Ti2Nb8O30. B-11 NMR studies revealed the transformation of BO4 structural units into BO3 units owing to the increase in TiO6 and NbO6 structural units as the composition of Ba5Li2Ti2Nb8O30 increased in the glass. This, in turn, resulted in an increase in the density of the glasses. The influence of the nominal composition of the glasses and glass nanocrystal composites on optical band gap (E-opt), Urbach energy (Delta E), refractive index (n), molar refraction (R-m), optical polarizability (alpha(m)) and third order non-linear optical susceptibility (chi(3)) were studied.

Synthesis and Densification of Monolithic Zirconium Carbide by Reactive Hot Pressing

Synthesis and densification of monolithic zirconium carbide (ZrC) has been carried out by reactive hot pressing of zirconium (Zr) and graphite (C) powders in the molar ratios 1:1, 1.25:1, 1.5:1, and 2:1 at 40 MPa, 1200 degrees-1600 degrees C. Monolithic ZrC could be synthesized with a C/Zr ratio similar to 0.5-1.0 and the post heat-treated samples have the lattice parameter in the range 4.665 to 4.698 A. Densification improves with an increasing deviation from the stoichiometry. Fine-grained (similar to 1 mu m) and nearly fully dense material (99% RD) could be obtained at a temperature as low as 1200 degrees C with C/Zr similar to 0.67. Microstructural and XRD observations suggest that densification occurred at low temperatures with nonstoichiometric Zr-C powder mixtures.