Combinatorial synthesis and characterization of a ternary epitaxial film of Co and Mn doped Ge (0 0 1)

We report combinatorial molecular beam epitaxy synthesis and properties of a ternary epitaxial film of Co and Mn co-doped Ge grown on Ge (0 0 1) substrate. Structural effects were examined in situ by reflection high-energy electron diffraction and ex situ by microbeam X-ray diffraction techniques, and magnetic properties were probed by using magnetooptic Kerr effect. Ternary epitaxial phase diagrams have been studied for total doping concentrations up to 30 at.%, where regions of coherent epitaxy and rough disordered growth and those of near room temperature ferromagnetic ordering have been identified.     

Metallation des halogenures d'aryle par le tributylstannyllithium dans le tetrahydrofuranne

The metallation of aryl halides with tributylstannyllithium in THF proceeds via at least three different mechanisms whose relative rates depend on the nature of the halogen, the substrate and the experimental conditions. In the case of aryl bromides, a halogenmetal exchange (major process) is competing with a radical mechanism. With aryl chlorides, an arynic process, a halogenmetal exchange and a radical mechanism are involved. Finally, with aryl fluorides, the arynic process is usual, but it may be strongly competed by a radical mechanism whenever suitable experimental conditions are arranged.     

Towards clustered carbonyl cations [M3(CO)14]2+ (M = Ru,Os): the need for innocent deelectronation

To access the hitherto almost unknown class of clustered transition metal carbonyl cations, the trimetal dodecacarbonyls M₃(CO)₁₂ (M = Ru, Os) were reacted with the oxidant Ag⁺[WCA]⁻, but yielded the silver complexes [Ag{M₃(CO)₁₂}₂]⁺[WCA]⁻ (WCA = [Al(OR^F)₄]⁻, [F{Al(OR^F)₃}₂]⁻; R^F = –OC(CF₃)₃). Addition of further diiodine I₂ to increase the redox potential led for M = Ru non-specifically to divalent mixed iodo-Ru^II-carbonyl cations. With [NO]⁺, even the N–O bond was cleaved and led to the butterfly carbonyl complex cation [Ru₄N(CO)₁₃]⁺ in low yield. Obviously, ionization of M₃(CO)₁₂ with retention of its pseudo-binary composition including only M and CO is difficult and the inorganic reagents did react non-innocently. Yet, the radical cation of the commercially available perhalogenated anthracene derivative 9,10-dichlorooctafluoroanthracene (anthracene^Hal) is a straightforward accessible innocent deelectronator with a half-wave potential E_1/2 of 1.42 V vs. Fc^0/+. It deelectronates M₃(CO)₁₂ under a CO atmosphere and leads to the structurally characterized cluster salts [M₃(CO)₁₄]²⁺([WCA]⁻)₂ including a linear M₃ chain. The structural characterization as well as vibrational and NMR spectroscopies indicate the presence of three electronically independent sets of carbonyl ligands, which almost mimic M(CO)₅, free CO and even [M(CO)₆]²⁺ in one and the same cation.

Trimeric M₃(CO)₁₂ (M = Ru, Os) reacts with typical inorganic oxidants to unwanted side products. Yet, the 9,10-dichlorooctafluoroanthracene radical cation deelectronates these under CO pressure to give the first homotrimetallic [M₃(CO)₁₄]²⁺ salts.     

Probing the substrate specificity of the catalytically self-sufficient cytochrome P450 RhF from a Rhodococcus sp

Analysis of the substrate specificity of the self-sufficient cytochrome P450 RhF revealed that the enzyme tends to catalyse the dealkylation of substituted alkyl-aryl ethers with shorter alkyl moieties more readily than equivalent compounds with longer alkyl groups.     

Morphological and elemental characterisation with the high-energy ion-nanoprobe LIPSION

This contribution deals with the morphological and elemental characterisation with high-energy (MeV) focused ion beams (in particular protons) with special emphasis on high spatial resolution in the sub-micrometer regime and very low minimum detection limits (sub-ppm) in trace element analysis. The most important methods like particle induced X-ray emission (PIXE), Rutherford backscattering spectrometry (RBS), as well as scanning transmission ion microscopy (STIM) and STIM-tomography will be illustrated by examples from material and life sciences.     

Recent approaches towards the asymmetric synthesis of alpha,alpha-disubstituted alpha-amino acids

The class of alpha,alpha-disubstituted alpha-amino acids has gained considerable attention in the past decades and continues doing so. The ongoing interest in biological and chemical properties of the substance class has inspired the development of many new methodologies for their asymmetric construction, which have not found their way into the general focus of organic chemistry yet. The aim of this review is to provide an overview of the developments in the field since 1998.     

Determining the uncertainty on the total heavy-flavor cross section

We assess the theoretical uncertainties on the total heavy-quark cross section. We discuss the importance of the quark mass, the choice of the scale, the number of light flavors and the parton densities on the estimate of the uncertainty. At first glance, the uncertainty bands on the total charm cross sections obtained by integrating the FONLL inclusive cross section and by integrating the partonic total cross sections appear to be incompatible. We explain how this apparent difference arises and describe how the two results can be reconciled. The small mass of the charm quark amplifies the effect of varying the other parameters in the calculation, making the uncertainty on the total charm cross section difficult to quantify. On the other hand, the bottom-quark total cross section is under much better theoretical control, and differences between the two approaches are small.     

Determination of Formation Regions of Titanium Phosphates; Determination of the Crystal Structure ofβ-Titanium Phosphate, Ti(PO4)(H2PO4), from Neutron Powder Data

The formation region of the various types of layered titanium hydrogen phosphate hydrates was investigated. The materials were prepared by hydrothermal methods, treating amorphous titanium phosphate with phosphoric acid (8 to 16M) in the temperature range 175 to 250°C. The materials obtained were:α-Ti(HPO₄)₂·H₂O,γ-Ti(PO₄)(H₂PO₄)·2H₂O, and its anhydrous formβ-Ti(PO₄)(H₂PO₄). The structure ofβ-Ti(PO₄)(H₂PO₄) has been determined by Rietveld powder refinement of high resolution neutron diffraction data. The structure is refined in the monoclinic space groupP2₁/n(No. 14). The unit cell parameters are:a=18.9503(4) Å,b=6.3127(1) Å,c=5.1391(1) Å,β=105.366(2)°;Z=4. The final agreement factors were:R_p=2.9% andR_wp=3.8%. The structure ofβ-Ti(PO₄)(H₂PO₄) is built from TiO₆octahedra linked together by tertiary phosphate (PO₄) and dihydrogen phosphate ((OH)₂PO₂) tetrahedra. The layers are held together by hydrogen bonds.