Near-edge X-ray absorption fine structure study of disordering in Gd2(Ti1-yZry)2O7 pyrochlores

Disorder in Gd2(Ti(1-y)Zry)2O7 pyrochlores, for y = 0.0-1.0, is investigated by Ti 2p and O 1s near-edge X-ray absorption fine structure spectroscopy. Ti(4+) ions are found to occupy octahedral sites in Gd2Ti2O7 with a tetragonal distortion induced by vacant oxygen sites. As Zr substitutes for Ti, the tetragonal distortion decreases, and Zr coordination increases from 6 to 8. The migration of oxygen ions from 48f or 8b sites to vacant 8a sites compensate for the increased Zr coordination, thereby reducing the number of vacant 8a sites, which further reduces the tetragonal distortion and introduces more disorder around Ti. This is evidence for simultaneous cation disorder with anion migration.     

Dosimetric concepts in photobiology

Abstract —The effectiveness of an irradiation at non-ionizing wavelengths for producing photochemical changes in a transparent sample can be characterized by any one of four different quantities. The utility of each depends on the information available about the sample and the kind of analysis intended. Nomenclature for these quantities is troubled. All four have been called “dose” in the literature, with or without modifying adjectives. In addition, incompatibility between the terminology for ionizing and non-ionizing radiations leaves the concept of “dose” ambiguous in the vacuum ultraviolet. Rather than abandon the term altogether, nomenclature restricting its use is suggested here, together with measurement units and symbols for the quantities. The use of dosimetric quantities implies certain assumptions about the system being irradiated which are not always fulfilled.     

A study on the interaction of cationized chitosan with cellulose surfaces

This investigation describes the interaction of trimethyl chitosans (TMCs) with surfaces of cellulose thin films. The irreversible deposition/adsorption of TMCs with different degrees of cationization was studied with regards to the salt concentration and pH. As substrates, cellulose thin films were prepared by spin coating from trimethylsilyl cellulose and subsequent regeneration to pure cellulose. The pH-dependent zeta potential of cellulose thin films and the charge of TMCs were determined by streaming potential and potentiometric charge titration methods. A quartz crystal microbalance with dissipation monitoring was further used as a nanogram sensitive balance to detect the amount of deposited TMCs and the swelling of the bound layers. The morphology of the coatings was additionally characterized by atomic force microscopy and related to the adsorption results. A lower degree of cationization leads to higher amounts of deposited TMCs at all salt concentrations. Higher amounts of salt increase the deposition of TMCs. Protonation of primary amino groups results in the immobilization of less material at lower pH values. The results from this work can further be extended to the modification of regenerated cellulosic materials to obtain surfaces, with amino- and trimethylammonium moieties.     

Approximate bandpass and frequency response models of the difference of Gaussian filter

The Difference of Gaussian (DOG) filter is widely used in optics and image processing as, among other things, an edge detection and correlation filter. It has important biological applications and appears to be part of the mammalian vision system. In this paper we analyse the filter and provide details of the full width half maximum, bandwidth and frequency response in order to aid the full characterisation of its performance.     

On the spectrum of tridiagonal operators and the support of orthogonalization measures

We investigate the support of the orthogonalization measure π of a large class of orthogonal polynomial sequences based on the parameters of the three-term recurrence relation. Our main result is the characterization when the possible right end-point 1 is a member of supp π.     

Raman spectroscopic investigations of natural jennite from Maroldsweisach,Bavaria, Germany

A full‐range pattern (100–3700 cm⁻¹) analysis of natural jennite was performed for the first time by Raman spectroscopy, applying a polarized laser at a wavelength of 532 nm. A prominent structural feature of jennite is the preferred orientation of Si‐tetrahedron and Ca‐octahedron chains parallel [010]. The latter ones are additionally coupled to H₂O molecules and OH groups. This arrangement leads to a strong dependence on orientation for the intensity ratios of mainly three different regions in the Raman spectra: 180–210, 950–1050 and 3100–3650 cm⁻¹. These sections can be assigned to Ca–O lattice vibrations, Q² Si–tetrahedron stretching and O–H vibrations of H₂O molecules and Ca–OH structures, respectively. Copyright © 2015 John Wiley & Sons, Ltd.     

Adsorption of plasmid DNA on ceramic hydroxyapatite chromatographic materials

The adsorption of plasmid DNA onto two different types of ceramic hydroxyapatite beads with a particle diameter of 20 μm, namely Ceramic Hydroxyapatite Type II and the Type III, which is not commercially available, were investigated. Type II and the Type III have a pore diameter of 80 and 240 nm, respectively. Equilibrium and dynamic binding capacity for a 4.9 kbp model plasmid on Ceramic Hydroxyapatite Type II and Type III were enhanced by addition of NaCl to the adsorption buffer. This result indicates that the adsorption mechanism cannot be solely explained by electrostatic interaction. The affinities of plasmid DNA for Ceramic Hydroxyapatite Type II (with a K(D) of ≈0.005 mg/mL) and to Hydroxyapatite Type III (with a K(D) of ≈0.045 mg/mL) were not affected by NaCl, whereas the binding capacity was. This observation corroborates the assumption that a change of the shape of the plasmid molecule is affected and could be the reason for increased binding capacity with salt. The maximal binding capacity shows that at least a part of the CHT II bead must be accessible for the plasmid, whereas CHT III can be saturated with the plasmid. In both cases, an extremely hindered transport takes place.     

Palladium-mediated fragmentation reactions of meta photocycloadducts to afford arylated or oxidatively cyclised products

Whilst seeking to improve the yield of a Heck-style arylation/fragmentation reaction using a silyloxy substituted meta photocycloadduct, an alternative reaction pathway was discovered that led to the formation of the unique oxidatively cyclised compound 8. This tricyclic ether is believed to form as the result of the meta photocycloadduct structure fragmenting to give a π-allyl palladium species and then subsequently being displaced by a neighbouring hydroxyl group. An attempt to develop an enantioselective version of this reaction via the desymmetrisation of a meso π-allyl palladium intermediate was made using the meta photocycloadduct derived from anisole and Z-but-2-ene-1,4-diol, however no enantioenrichment of the products could be detected.     

An in situ Al K-edge XAS investigation of the local environment of H+- and Cu+-exchanged USY and ZSM-5 zeolites

Aluminum coordination in the framework of USY and ZSM-5 zeolites containing charge-compensating cations (NH4+, H+, or Cu+) was investigated by Al K-edge EXAFS and XANES. This work was performed using a newly developed in-situ cell designed especially for acquiring soft X-ray absorption data. Both tetrahedrally and octahedrally coordinated Al were observed for hydrated H-USY and H-ZSM-5, in good agreement with 27Al NMR analyses. Upon dehydration, water desorbed from the zeolite, and octahedrally coordinated Al was converted progressively to tetrahedrally coordinated Al. These observations confirmed the hypothesis that the interaction of water with Br?nsted acid protons can lead to octahedral coordination of Al without loss of Al from the zeolite lattice. When H+ is replaced with NH4+ or Cu+, charge compensating species that absorb less water, less octahedrally coordinated Al was observed. Analysis of Al K-edge EXAFS data indicates that the Al-O bond distance for tetrahedrally coordinated Al in dehydrated USY and ZSM-5 is 1.67 angstroms. Simulation of k3chi(k) for Cu+ exchanged ZSM-5 leads to an estimated distance between Cu+ and framework Al atoms of 2.79 angstroms.