Ferritin-supported palladium nanoclusters: selective catalysts for aerobic oxidations in water

Confinement of nanometallic Pd within the core of a hyperthermophilic ferritin cage (from Pyrococcus furiosus) is reported. The resulting nanostructured hybrid catalysts can be used for highly specific aerobic oxidation of alcohols in water.     

Kinetics of Ca2+ complexation with some carbohydrates in aqueous solutions

For solutions of four saccharides in water with alkaline-earth chlorides added ultrasonic attenuation spectra between 100 kHz and 2 GHz are reported and compared to those for carbohydrate solutions without salt. Calcium chloride does not alter the relaxation times in the spectra of D-glucose and D+-maltose solutions, reflecting the exocyclic hydroxymethyl group rotation, a saccharide-saccharide association, and, with the disaccharide, also motions of both rings of a molecule relative to one another. The spectra of D-xylose and D-fructose solutions are substantially changed by the salts. With both saccharides an additional term with relaxation time around some nanoseconds exists which is assigned to a rearrangement of a carbohydrate-cation complex. Other relaxation terms of these saccharide solutions are also subject to noticeable changes by the salt, indicating specific carbohydrate-cation interactions. The ultrasonic spectra show that such interactions may exist also with carbohydrates which do not display the particular hydroxyl group sequences that are considered to promote complexation with cations.     

Concepts in high-frequency EPR — Applications to bio-inorganic systems

In this contribution we describe a high-frequency high-field EPR facility which has been developed at the University of Nijmegen. We present the design of a heterodyne quasi-optical bridge based on a millimeter-wave vector network analyzer as source and detection system. The mm-waves are transported in free-space through Gaussian beam optic elements and through a corrugated guide inside the resonator insert. The Fabri-Pérot (TEM_00n) resonator is coupled through a metallic mesh and because of its bimodal property it can be operated using orthogonal detection leading to substantial improvement in sensitivity. In the first stage of the project, a multifrequency CW-facility is realized covering the 100–500 GHz range. In our initial explorative experiments we demonstrate the advantages of HF-EPR of high-spin systems: Due to the large microwave quantum, transitions which would be undetectable at X-band due to the large zerofield splitting can now be observed in good sensitivity. As a model for biological high-spin systems a sample of metmyoglobin was measured at D-band (130 GHz). Theg = 5.9 perpendicular line from theS = 5/2 ferric heme was detected and its line-width was compared to data previously obtained at Q-, X-, S- and L-band. As a model for biological integer spin systems theS = 1 signal of Ni(II) in nickel Tutton salt (Ni(NH₄)₂(SO₄)₂) was studied at 35 and 130 GHz.     

Exceptional Modules for Tubular Canonical Algebras

Let Λ be a tubular canonical algebra of quiver type over a field. We show that each exceptional Λ-module can be exhibited by matrices involving as coefficients 0, 1 and –1 if Λ is of type (3,3,3), (2,4,4) or (2,3,6) and by matrices involving as coefficients 0, 1, –1, λ, –λ and λ–1 if Λ is of type (2,2,2,2) and defined by a parameter λ. Presented by Claus M. Ringel.     

High average power spectral beam combining of four fiber amplifiers to 8.2 kW

We report on the incoherent beam combination of the four narrow-linewidth fiber amplifier chains running at different wavelengths. Each main amplifier stage consists of a large-mode-area photonic crystal fiber delivering more than 2 kW of optical power. The four output beams are spectrally combined to a single beam with an output power of 8.2 kW using a polarization-independent dielectric reflective diffraction grating mainly preserving the beam quality of the individual fiber amplifiers.     

Mass conservative finite volume discretization of the continuity equations in multi-component mixtures

The Stefan–Maxwell equations for multi-component diffusion result in a system of coupled continuity equations for all species in the mixture. We use a generalization of the exponential scheme to discretize this system of continuity equations with the finite volume method. The system of continuity equations in this work is obtained from a non-singular formulation of the Stefan–Maxwell equations, where the mass constraint is not applied explicitly. Instead, all mass fractions are treated as independent unknowns and the constraint is a result of the continuity equations, the boundary conditions, the diffusion algorithm and the discretization scheme. We prove that with the generalized exponential scheme, the mass constraint can be satisfied exactly, although it is not explicitly applied. A test model from the literature is used to verify the correct behavior of the scheme.     

Analytical theory for permeation of condensable gases in a nanopore

The permeation of a condensable gas mixture in a pressure gradient is examined within a dynamic density functional theory (DDFT). The non-equilibrium density and flux profiles of gas molecules trapped within a nanopore are calculated for each species as a function of feed gas density. Because of important fluid–fluid interaction close to condensation the flux and density gradients are not related by constant transport diffusivities with the thermodynamic correction of uniform density. For long narrow pores the relation of the selectivity to the equilibrium adsorption isotherms is validated. Improved separation is achieved by combining preferential wall interaction and advantageous attraction between gas molecules of different species and examples are discussed. Results from experiments and simulations of permeation in binary mixtures near condensation are still rare and the theory provides a simple basis to study qualitative trends using known parameters.     

Selective self-organization of guest molecules in self-assembled molecular boxes

This article describes the synthesis and binding properties of highly selective noncovalent molecular receptors 1(3).(DEB)6 and 3(3).(DEB)6 for different hydroxyl functionalized anthraquinones 2. These receptors are formed by the self-assembly of three calix[4]arene dimelamine derivative molecules (1 or 3) and six diethylbarbiturate (DEB) molecules to give 1(3).(DEB)6 or 3(3).(DEB)6. Encapsulation of 2 occurs in a highly organized manner; that is, a noncovalent hydrogen-bonded trimer of 2 is formed within the hydrogen-bonded receptors 1(3).(DEB)6 and 3(3).(DEB)6. Both receptors 1(3).(DEB)6 and 3(3).(DEB)6 change conformation from staggered to eclipsed upon complexation to afford a better fit for the 2(3) trimer. The receptor selectivity toward different anthraquinone derivatives 2 has been studied using 1H NMR spectroscopy, X-ray crystallography, UV spectroscopy, and isothermal microcalorimetry (ITC). The pi-pi stacking between the electron-deficient center ring of the anthraquinone derivatives 2a-c and 2e-g and the relatively electron-poor melamine units of the receptor is the driving force for the encapsulation of the guest molecules. The selectivity of the hydrogen-bonded host for the anthraquinone derivatives is the result of steric interactions between the guest molecules and the calix[4]arene aromatic rings of the host.     

Synthesis of N-(Dimethylsulfamoyl)aldimines,a New Type of Aldimine Derivative

N-(Dimethylsulfamoyl)aldimines (3) a new type of shelf-stable aldimine derivatives, are readily prepared from aldehydes and N-(dimethylsulfamoyl)amide (2) in refluxing toluene.