Far infrared (THz) absorption spectra for the quantitative differentiation of calcium carbonate crystal structures: Exemplified in mixtures and in paper coatings

In this paper, far-infrared (FIR) spectroscopic techniques have been employed to detect different calcium carbonate crystal concentrations in powder mixtures. We have compared absorption spectral features of both pure and mixtures of natural ground calcium carbonate (GCC) and synthetic precipitated calcium carbonate (PCC). It is evident that the absorbance data differentiate clearly and unequivocally between calcite and aragonite in the spectral range of 2–18 THz. Also, from the absorbance measurement of two sets of mixtures, we have revealed a linear relationship between the ratio of some selected absorbance peaks of the mixtures and concentration of a particular pigment within the mixture. This innovative technique could be a novel, practicable technique for quality control or for analyzing coating and/or filler pigments and extenders in the paper making and printing industries. Finally, we have proven in the case of paper that, surface roughness and print color play no role as far as the locations and magnitudes of the absorbance spectral features are concerned.     

Formation of alumina-ceria mixed oxide in model systems

Interaction of aluminium with cerium oxide was studied by photoelectron spectroscopy of Al/CeO₂(1 1 1) and CeO₂/Al(1 1 1) model systems. It was found in both cases that metallic aluminium was immediately oxidized, CeO₂ was partially reduced and a mixed oxide with cerium present as Ce³⁺ was formed. The compound is probably cerium aluminate CeAlO₃ mixed with Al₂O₃ or Ce₂O₃. In both cases the intermixing was limited by the diffusion of aluminium into ceria. The excess of deposited material above this limit formed AlO_x and CeO₂ overlayers on the top of the mixed oxide + aluminate/CeO₂ and mixed oxide + aluminate/Al films, respectively.     

Niobium diffusion in niobium-doped titanium dioxide

The present work studied the self-diffusion coefficient of ⁹³Nb in Nb-doped TiO₂ single crystal (4.3 at.% Nb) at high oxygen activity [p(O₂) = 21 kPa] over the temperature range 1,073 to 1,573 K. The diffusion-induced ⁹³Nb concentration profile was determined by using secondary ion mass spectrometry (SIMS). The subsequently determined self-diffusion coefficient of ⁹³Nb exhibits the following temperature dependence:. This study builds upon a similar study performed previously for ⁹³Nb tracer diffusion in undoped TiO₂, and identifies the effect of compositional change on self-diffusion behaviour. The obtained activation energy has been considered in terms of migration and formation enthalpies of titanium vacancies. The present work is dedicated to Professor John Bockris on the occasion of his 85th birthday. His contribution to the progress of modern electrochemistry is well-known to several generations of students and researchers who have been using his textbooks. His specific contribution to the theory of photoelectrochemical water splitting is known to all working in this fascinating area.     

Electronic structure study by means of x-ray spectroscopy and theoretical calculations of the "ferric star" single molecule magnet

The electronic structure of the single molecule magnet system {M[Fe(L(1))(2)](3)}4CHCl(3) [M=Fe,Cr;L(1)=CH(3)N(CH(2)CH(2)O)(2) (2-)] has been studied using x-ray photoelectron spectroscopy, x-ray-absorption spectroscopy, soft-x-ray emission spectroscopy, as well as theoretical density-functional-based methods. There is a good agreement between theoretical calculations and experimental data. The valence band mainly consists of three bands between 2 and 30 eV. Both theory and experiments show that the top of the valence band is dominated by the hybridization between Fe 3d and O 2p bands. From the shape of the Fe 2p spectra it is argued that Fe in the molecule is most likely in the 2+ charge state. Its neighboring atoms (O,N) exhibit a magnetic polarization yielding effective spin S=52 per iron atom, giving a high-spin state molecule with a total S=5 effective spin for the case of M=Fe.     

Interaction of CO with palladium supported on oxidized tungsten

A model catalyst system, palladium on tungsten oxide, has been examined by temperature-programmed desorption and photoemission spectroscopy. The samples were prepared by evaporation of palladium onto an oxidized tungsten foil under ultrahigh vacuum conditions. Mostly three-dimensional (3-D) palladium (Pd) clusters were found to be present on oxidized tungsten (WOx) surfaces at room temperature. Upon annealing to 670 K, the palladium clusters are redispersed and decorated by the WOx surface layer. The nature of the WOx phase on top of the palladium clusters is dependent on the mode of oxidation of the tungsten foil prior to palladium deposition. Mainly W(2+) species decorate palladium deposits on tungsten oxidized at room temperature, while mainly W(4+) species are on top of palladium deposits on the surface oxidized at 1300 K. The appearance of a Pd(n+)-O-W(4+) mixed oxide phase with n < 2 was observed on the oxidized tungsten surface. The substantial reduction (relative to nonannealed samples) of molecular CO coverage induced by annealing is discussed in terms of the changes in chemical composition and morphology of the outermost surface.     

The active site of arsenite oxidase from Alcaligenes faecalis

Arsenite oxidase, a member of the DMSO reductase family of molybdenum enzymes, has two molecules of guanosine dinucleotide molybdenum cofactor coordinating the molybdenum at the active site. X-ray absorption spectroscopy indicates that the Mo-S bonds shorten from 2.47 to 2.37 A upon reduction with the physiological substrate. It also indicates the presence of an oxo ligand at 1.70 A in both oxidized and reduced forms of the enzyme, together with a short, 1.83 A, Mo-O bond in the oxidized form that is lost upon reduction. Resonance Raman spectroscopy indicates that the two pterin dithiolene moieties have different aromaticities, with one, the Q-pterin, having a more discrete dithiolate structure while the other, the P-pterin, has considerable pi-delocalization. Our results indicate that the structure of arsenite oxidase is intermediate between that seen in other molybdenum enzymes, in which one ligand to the metal is provided by the polypeptide (serine, cysteine, or selenocysteine), and tungsten enzymes that lack a peptide ligand.     

Metal ion function in carbonic anhydrase

The purpose of this review is to present an up-to-date account of the chemistry of the metal ion in the enzyme carbonic anhydrase. The interest lies in how the study of the metal may lead to deductions concerning the chemistry of the enzyme's action and in the way that metalloenzyme chemistry seems to demand a new appraisal of some aspects of the established chemistry of metal complexes.