Decoupling of magnetically interacting crystallites of goethite

The magnetic properties of synthetic goethite, precipitated from a SiO₂-containing Fe(III) solution, have been studied. The Mössbauer spectra show the coexistence of a quadrupole doublet and a magnetically split component in a large temperature range. The area ratio of these two components depends strongly on temperature, indicating a normal superparamagnetic behaviour of isolated crystallites. This is in contrast to the behaviour normally exhibited by pure samples of microcrystalline goethite, in which strong magnetic interactions among the crystallites lead to a superferromagnetic behaviour. The results show that the magnetic interactions among the crystallites are drastically diminished when amorphous SiO₂ separates the goethite crystallites.     

Reversible luminescence switching of a redox-active ferrocene-europium dyad

The copper-catalyzed cycloaddition reaction between a propargyl-appended europium complex and azidomethylferrocene yields a d-f dyad whose photophysical properties can be reversibly switched by varying the oxidation state of the ferrocene chromophore.     

Light-induced copper(II) coordination by a bicyclic tetraaza chelator through a ligand-to-metal charge-transfer reaction

To enable utilization of the broad potential of copper isotopes in nuclear medicine, rapid and robust chelation of the copper is required. Bowl adamanzanes (bicyclic tetraaza ligands) can form kinetically stable copper complexes, but they are usually formed at low rates unless high pH values and high temperatures are applied. We have investigated the effects of the variation in the pH, different anions, and UV irradiation on the chelation rate. UV spectra of mixtures of Cu(2+) and [2(4).3(1)]adz in water show the existence of a long-lived two-coordinated copper(II) intermediate (only counting coordinated amine groups) at pH above 6. These findings are supported by pH titrations of mixtures of Cu(2+) and [2(4).3(1)]adz in water. Irradiation of this complex in the ligand-to-metal charge-transfer (LMCT) band by a diode-array spectrophotometer leads to photodeprotonation and subsequently to formation of the four-coordinated copper(II) complex at a rate up to 7800-fold higher at 25 °C than in the dark. Anions in the solution were found to have three major effects: competitive inhibition due to Cu(II) binding anions, inhibition of the photoinduced transchelation from UV-absorbing anions, and photoredox inhibition from acido ligands capable of acting as electron donors in LMCT reactions. Dissolved O(2) was also found to result in photoredox inhibition.     

Photocatalytic methane decomposition over vertically aligned transparent TiO2 nanotube arrays

We report here on a study of vertically aligned TiO(2) nanotube arrays grown by the one-step anodic oxidation technique and their photocatalytic performance for methane decomposition. Quantitative activity data as a function of film thickness is obtained.     

Up to 30 mW of broadly tunable CW green-to-orange light, based on sum-frequency mixing of Cr:forsterite and Nd:YVO4 lasers

Efficient generation of continuous-wave (CW) tunable light in the yellow region is reported. The method is based on sum-frequency mixing of a tunable Cr⁴⁺:forsterite laser with a Nd:YVO₄ laser. A periodically poled lithium niobate crystal was placed intra-cavity in a Nd:YVO₄ laser, and the Cr⁴⁺:forsterite laser was single-passed through the non-linear media. With this setup, it was possible to generate up to 3 mW of yellow light smoothly tunable from 573 to 587 nm. This is the highest output demonstrated to date for a tunable diode pumped solid-state CW laser in this wavelength region. The ways to improve the efficiency further are discussed.     

Surface properties and photocatalytic activity of nanocrystalline titania films

In this work the efficiency and physicochemical details of a thin film produced by help of a microwave assisted sol gel technique is compared to different commercial powders (Degussa P25 and Hombikat UV100) deposited on glass substrates. Furthermore, a supercritical produced TiO₂ powder (SC 134) was included in the comparison.The prepared TiO₂ films were characterized using XRD, XPS, AFM, DSC and DLS. The photocatalytic activity was determined using stearic acid as a model compound. Investigation of the prepared films showed that the Degussa P25 film and the sol–gel film were the most photocatalytic active films. The activity of the films was found to be related to the crystallinity of the TiO₂ film and the amount of surface area and surface hydroxyl groups. Based on the XPS investigation of the films before and after UV irradiation it was suggested that the photocatalytic destruction of organic matter on TiO₂ films proceeds partly through formation of hydroxyl radicals which are formed from surface hydroxyl groups created by interactions between adsorbed water and vacancies on the TiO₂ surface. Furthermore a correlation between the amount of OH groups on the surface of the different TiO₂ films and the photocatalytic activity was found.     

Liquid hydrogen in protonic chabazite

Due to its fully reversible nature, H(2) storage by molecular adsorption could represent an advantage with respect to dissociative processes, where kinetic effects during the charging and discharging processes are present. A drawback of this strategy is represented by the extremely weak interactions that require low temperature and high pressure. High surface area materials hosting polarizing sites can represent a viable way toward more favorable working conditions. Of these, in this contribution, we have studied hydrogen adsorption in a series of zeolites using volumetric techniques and infrared spectroscopy at 15 K. We have found that in H-SSZ-13 zeolite the cooperative role played by high surface area, internal wall topology, and presence of high binding energy sites (protons) allows hydrogen to densify inside the nanopores at favorable temperature and pressure conditions.     

Approximation with wave packets generated by a refinable function

We consider best -term approximation in with wave packets generated by a single refinable function. The main examples of wave packets are orthonormal wavelets, or more generally wavelet frames based on a multiresolution analysis (so-called framelets). The approximation classes associated with best -term approximation in for a large class of wave packets are completely characterized in terms of Besov spaces.

As an application of the main result, we show that for -term approximation in with elements from an oversampled version of a framelet system with compactly supported generators, the associated approximation classes turn out to be (essentially) Besov spaces.

     

Covering homology

We introduce the notion of covering homology of a commutative S-algebra with respect to certain families of coverings of topological spaces. The construction of covering homology is extracted from Bökstedt, Hsiang and Madsen's topological cyclic homology. In fact covering homology with respect to the family of orientation preserving isogenies of the circle is equal to topological cyclic homology. Our basic tool for the analysis of covering homology is a cofibration sequence involving homotopy orbits and a restriction map similar to the restriction map used in Bökstedt, Hsiang and Madsen's construction of topological cyclic homology.Covering homology with respect to families of isogenies of a torus is constructed from iterated topological Hochschild homology. It receives a trace map from iterated algebraic K-theory and there is a hope that the rich structure, and the calculability of covering homology will make it useful in the exploration of J. Rognes' “red shift conjecture”.