The chemistry of ceramic glazes

The development of ideas and theories concerning the structure of glazes, as one of the glassy materials, are reviewed in the general introduction. The raw materials and the manufacturing process for glazes are described (Chapter One). A number of new vanadyl(IV) dipyridylamine and tripyrldylamine complexes have been prepared, various spectroscopic techniques are used in the investigation of the vanadyl ion in a weak ligand field, the situation of those found in a glaze environment (Chapter Three). In glaze recipes containing silica, potash feldspar, china clay, MO(M= Ca, Sr, Sa, Ti and Zn) and NiO, the ligand field theory is used in the elucidation of the effect of M (in MO) on the absorption spectra and coordination behaviour of Ni(II) in glazes. The magnetic and visible spectral results are reviewed in terms of Dietzel's idea of field strength of M and also in terms of Shteinberg's theory of glaze structure. X-ray diffraction is used for the identification of various species that formed after the firing process of glazes (Chapter Four). In Chapter Five, [] Mossbauer spectroscopy, supplemented by E.S.R., X-ray and visible spectral measurements are used in the investigation of iron in a glaze composition similar to that used in Chapter Four. The Mossbauer results are used in following the influence of; M in MO (M= Sr, Ca and Ba), oxides of titanium(IV) and vanadium(V ), and firing conditions on the chemistry of iron. Generally the iron(II) and iron(III) in the fired glazes are in octahedral sites although there are a range of similar, though not identical environments. A quite noticable influence of M (in MO) on the resonance line width is seen. In one case evidence is found for iron(IV) in an iron/vanadium glaze. E.S.R. of vanadium containing glazes indicate that vanadium is present as V02+ in a highly distorted tetragonal environment .

Development and evaluation of a novel intranasal spray for the delivery of amantadine

The aim of this study was to develop and characterize an intranasal delivery system for amantadine hydrochloride (AMT). Optimal formulations consisted of a thermosensitive polymer Pluronic® 127 and either carboxymethyl cellulose or chitosan which demonstrated gel transition at nasal cavity temperatures (34 ± 1°C). Rheologically, the loss tangent (Tan δ) confirmed a 3-stage gelation phenomena at 34 ± 1°C and non-Newtonian behavior. Storage of optimized formulation carboxymethyl cellulose and optimal formulation chitosan at 4°C for 8 weeks resulted in repeatable release profiles at 34°C when sampled, with a Fickian mechanism earlier on but moving toward anomalous transport by week 8. Polymers (Pluronic® 127, carboxymethyl cellulose, and chitosan) demonstrated no significant cellular toxicity to human nasal epithelial cells up to 4 mg/mL and up to 1 mM for AMT (IC50: 4.5 ± 0.05 mM). Optimized formulation carboxymethyl cellulose and optimal formulation chitosan demonstrated slower release across an in vitro human nasal airway model (43%-44% vs 79 ± 4.58% for AMT). Using a human nasal cast model, deposition into the olfactory regions (potential nose-to-brain) was demonstrated on nozzle insertion (5 mm), whereas tilting of the head forward (15°) resulted in greater deposition in the bulk of the nasal cavity.

Characterization and cytotoxicity studies of thiol-modified polystyrene microbeads doped with [(Mo6X8)(NO3)6]2- (X=Cl, Br, I)

Halide octahedral molybdenum clusters [(Mo6X8)L6]n- possess luminescence properties that are highly promising for biological applications. These properties are rather dependent on the nature of both the inner ligands X (i.e. Cl, Br, or I) and the apical organic or inorganic ligands L. Herein, the luminescence properties and the toxicity of thiol-modified polystyrene microbeads (PS-SH) doped with [(Mo6X8)(NO3)6]2- (X=Cl, Br, I) were studied and evaluated using human epidermoid larynx carcinoma (Hep2) cell cultures. According to our data, the photoluminescence quantum yield of (Mo6I8)@PS-SH is significantly higher (0.04) than that of (Mo6Cl8)@PS-SH (6Br8)@PS-SH (6X8)@PS-SH showed that all three types of doped microbeads had no significant effect on the viability and proliferation of the cells.

The magnetic exchange interactions in chromium chalcogenide spinels

The chromium chalcogenide spinels, MCr2X4 (M = Zn, Cd, Hg; X = O, S, Se), have been the subject of considerable interest in recent years. In each case the crystal structure is that of a normal spinel with the chromium ions exclusively occupying the octahedral (B) sites, so that when diamagnetic ions are located at the tetrahedral (A) sites the only magnetic interactions present are those between B-site ions. Despite such apparently simple circumstances a rich variety of magnetic behaviour is exhibited. For the oxides the ground state spin configurations are antiferromagnetic whilst for the selenides ferromagnetic interactions dominate and several authors have drawn attention to the fact that the nature of the dominant interaction is a function of the nearest neighbour chromium - chromium separation. However, at least two of the compounds exhibit spiral structures and it has been proved difficult to account for the various spin configurations within a unified theory of the magnetic interactions involved. More recently, the possibility of formulating a simplified interpretation of the magnetic interactions has been provided by the discovery that the crystal struture of spinels does not always conform to the centrosymmetrical symmetry Fd3m that has been conventionally assumed. The deviation from this symmetry is associated with small < 111> displacements of the octahedrally coordinated metal ions and the structures so obtained are more correctly referred to the non-centrosymmetrical space group F43m. In the present study, therefore, extensive X-ray diffraction data have been collected from four chromium chalcogenide specimens and used to refine the corresponding structural parameters assuming F43m symmetry and also with conventional symmetry. The diffracted intensities from three of the compounds concerned cannot be satisfactorily accounted for on the basis of conventional symmetry and new locations have been found for the chromium ions in these cases. It is shown, however, that these displacements in chromium positions only partially resolve the difficulties in interpreting the magnetic behaviour. A re-examination of the magnetic data from different authors indicates much greater uncertainty in their measurements than they had claimed. By taking this into consideration it is shown that a unified theory of magnetic behaviour for the chromium chalcogenide spinels is a real possibility.

Studies on the thermal decomposition behaviour, kinetics and electrical conductivity of the non-isothermal decomposition of pyridine mono carboxylic acids and some of their transition metal complexes

The thesis is divided into four chapters. They are: introduction, experimental, results and discussion about the free ligands and results and discussion about the complexes. The First Chapter, the introductory chapter, is a general introduction to the study of solid state reactions. The Second Chapter is devoted to the materials and experimental methods that have been used for carrying out tile experiments. TIle Third Chapter is concerned with the characterisations of free ligands (Picolinic acid, nicotinic acid, and isonicotinic acid) by using elemental analysis, IR spectra, X-ray diffraction, and mass spectra. Additionally, the thermal behaviour of free ligands in air has been studied by means of thermogravimetry (TG), derivative thermogravimetry (DTG), and differential scanning calorimetry (DSC) measurements. The behaviour of thermal decomposition of the three free ligands was not identical Finally, a computer program has been used for kinetic evaluation of non-isothermal differential scanning calorimetry data according to a composite and single heating rate methods in comparison with the methods due to Ozawa and Kissinger methods. The most probable reaction mechanism for the free ligands was the Avrami-Erofeev equation (A) that described the solid-state nucleation-growth mechanism. The activation parameters of the decomposition reaction for free ligands were calculated and the results of different methods of data analysis were compared and discussed. The Fourth Chapter, the final chapter, deals with the preparation of cobalt, nickel, and copper with mono-pyridine carboxylic acids in aqueous solution. The prepared complexes have been characterised by analyses, IR spectra, X-ray diffraction, magnetic moments, and electronic spectra. The stoichiometry of these compounds was ML2x(H20), (where M = metal ion, L = organic ligand and x = water molecule). The environments of cobalt, nickel, and copper nicotinates and the environments of cobalt and nickel picolinates were octahedral, whereas the environment of copper picolinate [Cu(PA)2] was tetragonal. However, the environments of cobalt, nickel, and copper isonicotinates were polymeric octahedral structures. The morphological changes that occurred throughout the decomposition were followed by SEM observation. TG, DTG, and DSC measurements have studied the thermal behaviour of the prepared complexes in air. During the degradation processes of the hydrated complexes, the crystallisation water molecules were lost in one or two steps. This was also followed by loss of organic ligands and the metal oxides remained. Comparison between the DTG temperatures of the first and second steps of the dehydration suggested that the water of crystallisation was more strongly bonded with anion in Ni(II) complexes than in the complexes of Co(II) and Cu(II). The intermediate products of decomposition were not identified. The most probable reaction mechanism for the prepared complexes was also Avrami-Erofeev equation (A) characteristic of solid-state nucleation-growth mechanism. The tempemture dependence of conductivity using direct current was determined for cobalt, nickel, Cl.nd copper isonicotinates. An activation energy (ΔΕ), the activation energy (ΔΕ ) were calculated.The ternperature and frequency dependence of conductivity, the frequency dependence of dielectric constant, and the dielectric loss for nickel isonicotinate were determined by using altemating current. The value of s paralneter and the value of'density of state [N(Ef)] were calculated. Keyword Thermal decomposition, kinetic, electrical conduclion, pyridine rnono~ carboxylic acid, cOlnplex, transition metal compJex.

Crystallographic studies of magnetite and titanomaghemite

The crystal structure of natural magnetite has been investigated on the basis of previously published X-ray intensity data and a newly acquired, more extensive data base. Both investigations show that the structure does not conform to the centrosymmetrical space group Fd3m, as is normally assumed, but the non-centrosymmetrical space group F43m. The structure refinement provides values for the atom positions, anisotropic thermal parameters and bond lengths. A study of Friedel related pairs of X-ray intensities shows that Friedel's law is violated in magnetite, further confirming that the space group is non-centrosymmetrical. It was found that the octahedral site cations in magnetite do not occupy special positions at the centres of the octahedral interstices as they should under the space group Fd3m, but are displaced along <111 > directions leading to F43m symmetry. A mechanism is known for the origin of these displacements and the likelihood of similar displacements occurring in other natural and synthetic spinels is discussed. The crystal structure of a natural titanomaghemite was determined by a combination of X-ray diffraction and Mõssbauer spectroscopy. This was confirmed as possessing a primitive cubic Bravais lattice with the space group P4332 and the structural formula: Fe3+.0.96 0 0.04 [Fe2+0.23 Fe3+0.99 Ti4+0.42 0 0.37 ] 042 - where 0 represents a cation vacancy. As the above formula shows, there are cation vacancies on both tetrahedral arrl octahedral sites, the majority being restricted to octahedral sltes. No tetrahedral site Fe2+ or Ti4+ was observed. Values for the atom positions, anisotropic thermal parameters and bond lengths have been determined for this particular specimen.

Deformation microstructures and recrystallization in heavily worked copper

Deformation microstructures in two batches of commercially pure copper (A and B) of allnost similar composition have been studied after rolling reductions from 5% to 95%. X- ray diffraction, optical metallography, scanning electron microscopy in the back-scattered mode, transmission and scanning electron microscopy have been used to examine the deformation microstructure. At low strains (~10 %) the deformation is accommodated by uniform octahedral slip. Microbands that occur as sheet like features usually on the {111} slip planes are formed after 10% reduction. The misorientations between rnicrobonds ond the matrix are usually small (1 - 2° ) and the dislocations within the bands suggest that a single slip system has been operative. The number of microbands increases with strain, they start to cluster and rotate after 60% reduction and, after 90 %, they become almost perfectly aligned with the rolling direction. There were no detectable differences in deformation microstructure between the two materials up to a deformation level of 60% but subsequently, copper B started to develop shear bands which became very profuse by 90% reduction. By contrast, copper A at this stage of deformation developed a smooth laminated structure. This difference in the deformation microstructures has been attributed to traces of unknown impurity in D which inhibit recovery of work hardening. The preferred orientations of both were typical of deformed copper although the presence of shear bands was associated wth a slightly weaker texture. The effects of rolling temperature and grain size on deformation microstructure were also investigated. It was concluded that lowering the rolling temperature or increasing the initial grain size encourages the material to develop shear bands after heavy deformation. Recovery and recrystallization have been studied in both materials during annealing. During recrystallization the growth of new grains showed quite different characteristics in the two cases. Where shear bands were present these acted as nucleation sites and produced a wide spread of recrystallized grain orientations. The resulting annealing textures were very weak. In the absence of shear bands, nucleation occurs by a remarkably long range bulging process which creates the cube orientation and an intensely sharp annealing texture. Cube oriented regions occur in long bands of highly elongated and well recovered cells which contain long range cumulative micorientations. They are transition bands with structural characteristics ideally suited for nucleation of recrystallization. Shear banding inhibits the cube texture both by creating alternative nuclei and by destroying the microstructural features necessary for cube nucleation.

Synthetic, crystallographic, and computational study of copper(II) complexes of ethylenediaminetetracarboxylate ligands

Copper(II) complexes of hexadentate ethylenediaminetetracarboxylic acid type ligands Heda3p and Heddadp (Heda3p = ethylenediamine-N-acetic-N,N',N'-tri-3-propionic acid; H eddadp = ethylenediamine-N,N'-diacetic-N,N'-di-3- propionic acid) have been prepared. An octahedral trans(O) geometry (two propionate ligands coordinated in axial positions) has been established crystallographically for the Ba[Cu(eda3p)]·8HO compound, while Ba[Cu(eddadp)]·8HO is proposed to adopt a trans(O ) geometry (two axial acetates) on the basis of density functional theory calculations and comparisons of IR and UV-vis spectral data. Experimental and computed structural data correlating similar copper(II) chelate complexes have been used to better understand the isomerism and departure from regular octahedral geometry within the series. The in-plane O-Cu-N chelate angles show the smallest deviation from the ideal octahedral value of 90°, and hence the lowest strain, for the eddadp complex with two equatorial ß-propionate rings. A linear dependence between tetragonality and the number of five-membered rings has been established. A natural bonding orbital analysis of the series of complexes is also presented.

The structure and dynamics of 2-dimensional fluids in swelling clays

The interlayer pores of swelling 2:1 clays provide an ideal 2-dimensional environment in which to study confined fluids. In this paper we discuss our understanding of the structure and dynamics of interlayer fluid species in expanded clays, based primarily on the outcome of recent molecular modelling and neutron scattering studies. Counterion solvation is compared with that measured in bulk solutions, and at a local level the cation-oxygen coordination is found to be remarkably similar in these two environments. However, for the monovalent ions the contribution to the first coordination shell from the clay surfaces increases with counterion radius. This gives rise to inner-sphere (surface) complexes in the case of potassium and caesium. In this context, the location of the negative clay surface charge (i.e. arising from octahedral or tetrahedral substitution) is also found to be of major importance. Divalent cations, such as calcium, eagerly solvate to form outer-sphere complexes. These complexes are able to pin adjacent clay layers together, and thereby prevent colloidal swelling. Confined water molecules form hydrogen bonds to each other and to the clays' surfaces. In this way their local environment relaxes to close to the bulk water structure within two molecular layers of the clay surface. Finally, we discuss the way in which the simple organic molecules methane, methanol and ethylene glycol behave in the interlayer region of hydrated clays. Quasi-elastic neutron scattering of isotopically labelled interlayer CH 3OD and (CH2OD)2 in deuterated clay allows us to measure the diffusion of the CH3- and CH2-groups in both clay and liquid environments. We find that in both the one-layer methanol solvates and the two-layer glycol solvates the diffusion of the most mobile organic molecules is close to that in the bulk solution.

Structure and physical properties of [µ-Tris(1,4-bis(tetrazol-1-yl)butane-N4,N4‘')iron(II)] Bis(hexafluorophosphate), a new Fe(II) spin-crossover compound with a three-dimensional threefold interlocked crystal lattice

[μ-Tris(1,4-bis(tetrazol-1-yl)butane-N4,N4‘)iron(II)] bis(hexafluorophosphate), [Fe(btzb)3](PF6)2, crystallizes in a three-dimensional 3-fold interlocked structure featuring a sharp two-step spin-crossover behavior. The spin conversion takes place between 164 and 182 K showing a discontinuity at about T1/2 = 174 K and a hysteresis of about 4 K between T1/2 and the low-spin state. The spin transition has been independently followed by magnetic susceptibility measurements, 57Fe-Mössbauer spectroscopy, and variable temperature far and midrange FTIR spectroscopy. The title compound crystallizes in the trigonal space group P30¯(No. 147) with a unit cell content of one formula unit plus a small amount of disordered solvent. The lattice parameters were determined by X-ray diffraction at several temperatures between 100 and 300 K. Complete crystal structures were resolved for 9 of these temperatures between 100 (only low spin, LS) and 300 K (only high spin, HS), Z = 1 [Fe(btzb)3](PF  6)2:  300 K (HS), a = 11.258(6) Å, c = 8.948(6) Å, V = 982.2(10) Å3; 100 K (LS), a = 10.989(3) Å, c = 8.702(2) Å, V = 910.1(4) Å3. The molecular structure consists of octahedral coordinated iron(II) centers bridged by six N4,N4‘ coordinating bis(tetrazole) ligands to form three 3-dimensional networks. Each of these three networks is symmetry related and interpenetrates each other within a unit cell to form the interlocked structure. The Fe−N bond lengths change between 1.993(1) Å at 100 K in the LS state and 2.193(2) Å at 300 K in the HS state. The nearest Fe separation is along the c-axis and identical with the lattice parameter c.

Fe III in a low-spin state in caesium bis[3-ethoxysalicylaldehyde 4-methylthiosemicarbazonato(2–)-κ3O2,N1,S]ferrate(III) methanol monosolvate

The synthesis and crystal structure (at 100K) of the title compound, Cs[Fe(C11H13N3O2S2) 2] CH3OH, is reported. The asymmetric unit consists of an octahedral [FeIII(L)2]- fragment, where L 2- is 3-ethoxysalicylaldehyde 4-methylthiosemicarbazonate(2-) {systematic name: [2-(3-ethoxy-2-oxidobenzylidene)hydrazin-1-ylidene] (methylamino)methanethiolate}, a caesium cation and a methanol solvent molecule. Each L2- ligand binds through the thiolate S, the imine N and the phenolate O atoms as donors, resulting in an FeIIIS2N 2O2 chromophore. The O,N,S-coordinating ligands are orientated in two perpendicular planes, with the O and S atoms in cis positions and the N atoms in trans positions. The FeIII cation is in the low-spin state at 100K. © 2014 International Union of Crystallography.

InAs/AlSb widely tunable external cavity quantum cascade laser around 3.2 μm

Room temperature, tunable, external-cavity short-wavelength InAs/AlSb quantum cascade laser (QCL) is reported. Wavelength tuning of 85 nm for the spectral range between 3190 nm and 3275 nm has been achieved by rotating the diffraction grating forming the external cavity. To suppress lasing inside the QCL cavity, its ridge was tilted by 7° at the external cavity end. The optimal tilting angle of the laser ridge was chosen by careful consideration of the return losses of the TM-polarized waveguide mode from the diffraction grating in a quasi-Littrow configuration and the Fabry-Pérot feedback from the tilted laser facet. No antireflection coating was used. © 2013 American Institute of Physics.

Copper(II) complexes with unsymmetrical pentadentate ed3a-type diamino-tricarboxylate ligands. Crystal structures, configurational analysis and DFT study of complexes

The O–O–N–N–O-type pentadentate ligands H3ed3a, H3pd3a and H3pd3p (H3ed3a stands ethylenediamine-N,N,N′-triacetic acid; H3pd3a stands 1,3-propanediamine-N,N,N′-triacetic acid and H3pd3p stands 1,3-propanediamine-N,N,N′-tri-3-propionic acid) and the corresponding novel octahedral or square-planar/trigonal-bipyramidal copper(II) complexes have been prepared and characterized. H3ed3a, H3pd3a and H3pd3p ligands coordinate to copper(II) ion via five donor atoms (three deprotonated carboxylate atoms and two amine nitrogens) affording octahedral in case of ed3a3− and intermediate square-pyramidal/trigonal-bipyramidal structure in case of pd3a3− and pd3p3−. A six coordinate, octahedral geometry has been established crystallographically for the [Mg(H2O)6][Cu(ed3a)(H2O)]2 · 2H2O complex and five coordinate square-pyramidal for the [Mg(H2O)5Cu(pd3a)][Cu(pd3a)] · 2H2O. Structural data correlating similar chelate Cu(II) complexes have been used for the better understanding the pathway: octahedral → square-pyramidal ↔ trigonal- bipyramid geometry. An extensive configuration analysis is discussed in relation to information obtained for similar complexes. The infra-red and electronic absorption spectra of the complexes are discussed in comparison with related complexes of known geometries. Molecular mechanics and density functional theory (DFT) programs have been used to model the most stable geometric isomer yielding, at the same time, significant structural data. The results from density functional studies have been compared with X-ray data.

Studies on the relative stabilities of Mn(II) and Mn(III) in complexes with N4O2 donor environments:crystal structures of [Mn(pybzhz)2] and [Mn(Ophsal)(imzH)2] ClO4 (pybzhz = N-(benzoyl)-N-(picolinylidene) hydrazine, Ophsal = N,N-o-phenylenebis(salicylideneimine), imzH = imidazole)

Five manganese complexes in an N 4O 2 donor environment have been prepared. Four of the compounds involve aroyl hydrazone as ligands and manganese is in a +2 oxidation state. The fifth compound was prepared using N,Nprime-o-phenylenebis(salicylideneimine) and imidazole as ligands where manganese is present in +3 oxidation state. X-ray crystal structure of one Mn +2 compound and the Mn +3 compound was determined. The relative stabilities of the Mn +2 and Mn +3 oxidation states were analyzed using the structural data and MO calculations. Manganese(II) complexes of four aroyl hydrazone ligands were prepared and characterized by different physicochemical techniques. The complexes are of the type Mn(L) 2, where L stands for the deprotonated hydrazone ligand. One of the compounds, Mn(pybzhz) 2, was also characterized by single crystal structure determination. In all these complexes, the Mn(II) is in an N 4O 2 donor environment and the Mn(II) center cannot be oxidized either chemically or electrochemically. However, when another ligand Ophsal is used to give the compound [Mn(Ophsal)(imzH) 2]ClO 4, which was also characterized by X-ray crystal structure determination, manganese can easily avail the +3 oxidation state. The relative stabilities of the +2 and +3 oxidation states of manganese were analyzed and it was concluded that the extent of distortion from the perfect octahedral geometry is the main controlling factor in these cases. © 2004 Elsevier B.V. All rights reserved.

The topography of transmembrane segment six is altered during the catalytic cycle of P-glycoprotein

Structural evidence has demonstrated that P-glycoprotein (P-gp) undergoes considerable conformational changes during catalysis, and these alterations are important in drug interaction. Knowledge of which regions in P-gp undergo conformational alterations will provide vital information to elucidate the locations of drug binding sites and the mechanism of coupling. A number of investigations have implicated transmembrane segment six (TM6) in drug-P-gp interactions, and a cysteine-scanning mutagenesis approach was directed to this segment. Introduction of cysteine residues into TM6 did not disturb basal or drug-stimulated ATPase activity per se. Under basal conditions the hydrophobic probe coumarin maleimide readily labeled all introduced cysteine residues, whereas the hydrophilic fluorescein maleimide only labeled residue Cys-343. The amphiphilic BODIPY-maleimide displayed a more complex labeling profile. The extent of labeling with coumarin maleimide did not vary during the catalytic cycle, whereas fluorescein maleimide labeling of F343C was lost after nucleotide binding or hydrolysis. BODIPY-maleimide labeling was markedly altered during the catalytic cycle and indicated that the adenosine 5'-(beta,gamma-imino)triphosphate-bound and ADP/vanadate-trapped intermediates were conformationally distinct. Our data are reconciled with a recent atomic scale model of P-gp and are consistent with a tilting of TM6 in response to nucleotide binding and ATP hydrolysis.