A pulsed EPR method to determine distances between paramagnetic centers with strong spectral anisotropy and radicals: The dead-time free RIDME sequence

Methods to determine distances between paramagnetic metal centers and radicals are scarce. This is unfortunate because paramagnetic metal centers are frequent in biological systems and so far have not been employed much as distance markers. Successful pulse sequences that directly target the dipolar interactions cannot be applied to paramagnetic metal centers with fast relaxation rates and large g-anisotropy, if no echos can be detected and the excitation bandwidth is not sufficient to cover a sufficiently large part of the spectrum. The RIDME method Kulik et al. (2002) [20] circumvents this problem by making use of the T₁-induced spin-flip of the transition-metal ion. Designed to measure distance between such a fast relaxing metal center and a radical, it suffers from a dead time problem. We show that this is severe because the anisotropy of the metal center broadens the dipolar curves, which therefore, only can be analyzed if the full curve is known. Here, we introduce five-pulse RIDME (5p-RIDME) that is intrinsically dead-time free. Proper functioning of the sequence is demonstrated on a nitroxide biradical. The distance between a low-spin Fe(III) center and a spin label in spin-labeled cytochrome f shows the complete dipolar trace of a transition-metal ion center and a spin label, yielding the distance expected from the structure.     

A high-order discontinuous Galerkin method for wave propagation through coupled elastic–acoustic media

We introduce a high-order discontinuous Galerkin (dG) scheme for the numerical solution of three-dimensional (3D) wave propagation problems in coupled elastic–acoustic media. A velocity–strain formulation is used, which allows for the solution of the acoustic and elastic wave equations within the same unified framework. Careful attention is directed at the derivation of a numerical flux that preserves high-order accuracy in the presence of material discontinuities, including elastic–acoustic interfaces. Explicit expressions for the 3D upwind numerical flux, derived as an exact solution for the relevant Riemann problem, are provided. The method supports h-non-conforming meshes, which are particularly effective at allowing local adaptation of the mesh size to resolve strong contrasts in the local wavelength, as well as dynamic adaptivity to track solution features. The use of high-order elements controls numerical dispersion, enabling propagation over many wave periods. We prove consistency and stability of the proposed dG scheme. To study the numerical accuracy and convergence of the proposed method, we compare against analytical solutions for wave propagation problems with interfaces, including Rayleigh, Lamb, Scholte, and Stoneley waves as well as plane waves impinging on an elastic–acoustic interface. Spectral rates of convergence are demonstrated for these problems, which include a non-conforming mesh case. Finally, we present scalability results for a parallel implementation of the proposed high-order dG scheme for large-scale seismic wave propagation in a simplified earth model, demonstrating high parallel efficiency for strong scaling to the full size of the Jaguar Cray XT5 supercomputer.     

A broadband grating-coupled silicon nitride waveguide for the mid-IR: characterization and sensitive measurements using an external cavity quantum cascade laser

We present the design and fabrication of a single-mode slab waveguide structure for mid-infrared spectroscopy optimized for broadband coupling. The sensor uses grating couplers for robust off-axis coupling and a silicon nitride guiding layer for mechanical robustness. An external cavity quantum cascade laser-based transmission method is introduced for characterizing the structure’s broadband coupling behavior. Light from an external cavity quantum cascade laser with a spectral range of 0.5 μm around 6 μm was coupled into the waveguide without the need for moving parts. First spectra taken with this sensor are presented.     

Space-Charge Effects with REXTRAP

The beam quality of radioactive ion beams produced by present target ion source technology is often not sufficient for direct post-acceleration. Furthermore, pulsed beams insure a more efficient use of an accelerator. In the case of REX-ISOLDE, the post accelerator at the CERN ISOLDE facility, a gas-filled Penning trap (REXTRAP) has been chosen for accumulation of the radioactive ions and conversion into cooled bunches. Radial centering of the ions is achieved by applying an rf field with a frequency equal to the cyclotron frequency of the desired ion species. The efficiency achieved in the first tests with different isotopes covering nearly the entire mass range was already >20%. Going to total numbers of >10⁵ stored ions in the trap a shift of the centering frequency could be observed, which is most likely due to space charge effects. Despite this, it was possible to accumulate up to 10⁷ ions and deliver them as cooled bunches. This revised version was published online in July 2006 with corrections to the Cover Date.     

Continuous wave 1.6 μm laser action in Er doped garnets at room temperature⋆

We report on room-temperature cw laser action of Er³⁺: Yttrium-aluminum-garnet (YAG) and Er³⁺: Yttrium-gallium-garnet (YGG) crystals at 1.64 m. The laser operates from the metastable⁴ I _13/2 manifold into an upper Stark level of the⁴ I _15/2 ground-state manifold of Er³⁺. Due to reabsorption losses, the Er³⁺ concentration of the laser crystals must be low. Laser pumping at a wavelength of 647.1 nm yields lowest thresholds around 30 mW and slope efficiencies up to 12.7% for Er:YAG. Laser operation in Er:YGG is achieved with higher thresholds of about 200 mW and smaller slope efficiencies of 0.9%. The effective emission cross section in YAG is estimated to be _e5×10^–21 cm².Dedicated to Prof. Dr. Herbert Welling on the occasion of his 60th birthday     

Controlled release of ketorolac through nanocomposite films of hydrogel and LDH nanoparticles

A novel nanocomposite film for sustained release of anionic ophthalmic drugs through a double-control process has been examined in this study. The film, made as a drug-loaded contact lens, consists principally of a polymer hydrogel of 2-hydroxyethyl methacrylate (HEMA), in whose matrix MgAl-layered double hydroxide (MgAl-LDH) nanoparticles intercalated with the anionic drug are well dispersed. Such nanocomposite films (hydrogel-LDH-drug) contained 0.6–0.8 mg of MgAl-LDH and 0.08–0.09 mg of the ophthalmic drug (ketorolac) in 1.0 g of hydrogel. MgAl-drug-LDH nanoparticles were prepared with the hydrodynamic particle size of 40–200 nm. TEM images show that these nanoparticles are evenly dispersed in the hydrogel matrix. In vitro release tests of hydrogel-LDH-drug in pH 7.4 PBS solution at 32 °C indicate a sustained release profile of the loaded drug for 1 week. The drug release undergoes a rapid initial burst and then a monotonically decreasing rate up to 168 h. The initial burst release is determined by the film thickness and the polymerization conditions, but the following release rate is very similar, with the effective diffusion coefficient being nearly constant (3.0 × 10⁻¹² m²/s). The drug release from the films is mechanistically attributed to anionic exchange and the subsequent diffusion in the hydrogel matrix.     

Shellwise Mackay transformation in iron nanoclusters

Structure and magnetism of iron clusters with up to 641 atoms have been investigated by means of density functional theory calculations including full geometric optimizations. Body-centered cubic (bcc) isomers are found to be lowest in energy when the clusters contain more than about 100 atoms. In addition, another stable conformation has been identified for magic-number clusters, which lies well within the range of thermal energies as compared to the bcc isomers. Its structure is characterized by a close-packed particle core and an icosahedral surface, while intermediate shells are partially transformed along the Mackay path between icosahedral and cuboctahedral geometry. The gradual transformation results in a favorable bcc environment for the subsurface atoms. For Fe55, the shellwise Mackay-transformed morphology is a promising candidate for the ground state.