Cryogenic 35 GHz pulse ENDOR probehead accommodating large sample sizes: Performance and applications

The construction and performance of a cryogenic 35 GHz pulse electron nuclear double resonance (ENDOR) probehead for large samples is presented. The resonator is based on a rectangular TE₁₀₂ cavity in which the radio frequency (rf) B₂-field is generated by a two turn saddle ENDOR coil crossing the resonator along the sample axis with minimal distance to the sample tube. An rf power efficiency factor is used to define the B₂-field strength per square-root of the transmitted rf power over the frequency range 2–180 MHz. The distributions of the microwave B₁- and E₁-field, and the rf B₂-field are investigated by electromagnetic field calculations. All dielectrics, the sample tube, and coupling elements are included in the calculations. The application range of the probehead and the advantages of using large sample sizes are demonstrated and discussed on a number of paramagnetic samples containing transition metal ions.     

Post-treatment of Fungal Biomass to Enhance Pigment Production

Applied Biochemistry and Biotechnology - A new post-treatment method of fungal biomass after fermentation is revealed. The post-treatment strategy was utilized to produce pigments as an additional...     

Positronium formation in NaY-zeolites studied by lifetime, positron beam Doppler broadening and 3-gamma detection techniques

Results of positron annihilation measurements on NaY pressed powders and deposited thin films using slow positron beam and conventional fast positron techniques are presented. In lifetime experiments using an external ²²Na source an averaged long lifetime of 1.8 ns with a sum intensity of 27% was observed in pressed powders in the presence of air at room temperature (RT). In literature this lifetime is ascribed to positrons annihilating in water filled or β cages Habrowska, A.M., Popiel, E.S., 1987. Positron annihilation in zeolite 13X. J. Appl. Phys. 62, 2419. By means of isotopic exchange some of the Na was replaced by ²²Na. These powders showed a long lifetime component of 7–8 ns with an intensity increasing from 1 to 12% when heated under normal atmosphere from RT to 200°C. No significant increase of the shorter (1.5 ns) lifetime was observed, while its intensity dropped from 13.4 to 6.6%. Both effects are ascribed to the loss of water from cages only. The beam experiments revealed a high fraction of 3-gamma annihilations in the pressed powder and thin film samples, indicating the annihilation of o-Ps and thereby the existence of large open volumes.     

Biosynthetic 13C labeling of aromatic side chains in proteins for NMR relaxation measurements

Site-specific 13C labeling offers a desirable means of eliminating unwanted relaxation pathways and coherent magnetization transfer in NMR relaxation experiments. Here we use [1-13C]-glucose as the sole carbon source in the growth media for protein overexpression in Escherichia coli. The approach results in specific incorporation of 13C at isolated positions in the side chains of aromatic amino acids, which greatly simplifies the measurements and interpretation of 13C relaxation rates in these spin systems. The method is well suited for characterization of chemical exchange by CPMG or spin-lock relaxation methods. We validated the method by acquiring 13C rotating-frame relaxation dispersion data on the E140Q mutant of the C-terminal domain of calmodulin, which reveal conformational exchange dynamics with a time constant of 71 mus for Y138.     

In situ formation of ligand and catalyst--application in ruthenium-catalyzed enantioselective reduction of ketones

The direct in situ formation of highly efficient ruthenium-catalysts for the asymmetric reduction of ketones was obtained by combining chiral ligand building blocks with a ruthenium precursor.     

Novel simple and highly modular ligands for efficient asymmetric transfer-hydrogenation of ketones

Novel simple and highly modular dipeptide-analogue ligands combined with [RuCl2(p-cymene)]2 were demonstrated to efficiently catalyze the reduction of ketones under hydrogen transfer conditions with enantioselectivities up to 96%.     

Reentrant phase transition in granular superconductors

The conditions for the appearance of a reentrant superconducting phase in granular materials are studied in mean field approximation applied to periodic models. We assume that the relevant low-lying excitation is the transfer of a Cooper pair from a grain to one of its neighbours, and neglect pair breaking. Both on-grain (U) and nearest neighbour (V) Coulomb interactions are taken into account, and the Coulomb problem is treated in Bethe-Peierls approximation. WhenV/U is not too large, reentrance is predicted ifV/U>(4+3z)^?1/2 wherez is the coordination number. This result is different from a recent criterion suggested by ?imánek, which allows reentrance only in the immediate vicinities of certain discrete values ofV/U. For strong enoughV/U, the models treated here show a transition to an ionic-salt-like charge-ordered state. Reentrant superconductivity is shown to occur also on an ionic background. In actual systems, close-packing effects partially frustrate the ionic ordering and enhance the reentrant feature.     

Synthese und Struktur eines neuen Bis[(trimethylphosphan)titanocen]-Komplexes mit einer verbrückenden C2-Einheit

Bis(trimethylphosphane)titanocene ( 1 ) reacts with 2-methylene-1,1-diphenylcyclopropane ( 2 ) to give red crystalline (η²-2-methylene-1,1-diphenylcyclopropane)(trimethylphosphane)titanocene ( 3 ). In solution complex 3 degrades smoothly to form the new Cp₂Ti(PMe₃) – C₂ – Ti(PMe₃)Cp₂ complex 4 , the crystal structure of which has been elucidated by an X-ray analysis.     

Step Fluctuations for a Faceted Crystal

A statistical mechanics model for a faceted crystal is the 3D Ising model at zero temperature. It is assumed that in one octant all sites are occupied by atoms, the remaining ones being empty. Allowed atom configurations are such that they can be obtained from the filled octant through successive removals of atoms with breaking of precisely three bonds. If V denotes the number of atoms removed, then the grand canonical Boltzmann weight is q ^V , 0<q<1. As shown by Cerf and Kenyon, in the limit q1 a deterministic shape is attained, which has the three facets (100), (010), (001), and a rounded piece interpolating between them. We analyse the step statistics as q1. In the rounded piece it is given by a determinantal process based on the discrete sine-kernel. Exactly at the facet edge, the steps have more space to meander. Their statistics is again determinantal, but this time based on the Airy-kernel. In particular, the border step is well approximated by the Airy process, which has been obtained previously in the context of growth models. Our results are based on the asymptotic analysis for space-time inhomogeneous transfer matrices.