Absence of intrinsic ferromagnetic interactions of isolated and paired Co dopant atoms in Zn1-xCoxO with high structural perfection

We report element specific structural and magnetic investigations on Zn(1-x)Co(x)O epitaxial films using synchrotron radiation. Co dopants exclusively occupy Zn sites as revealed by x-ray linear dichroism having an unprecedented degree of structural perfection. Comparative magnetic field dependent measurements by x-ray magnetic circular dichroism and conventional magnetometry consistently show purely paramagnetic behavior for isolated Co dopant atoms with a magnetic moment of 4.8 (mu B). However, the total magnetization is reduced by approximately 30%, demonstrating that Co-O-Co pairs are antiferromagnetically coupled. We find no sign of intrinsic ferromagnetic interactions for isolated or paired Co dopant atoms in Co:ZnO films.     

Annulation of internal alkynes through a hydroamination/aza-Heck reaction sequence for the regioselective synthesis of indoles

Highly regioselective annulation reactions of unsymmetrically substituted alkynes by primary 2-bromo or 2-chloroanilines are achieved with an efficient one-pot protocol, which relies on a regioselective TiCl₄-catalyzed intermolecular hydroamination and a subsequent palladium-catalyzed intramolecular aza-Heck reaction. The use of unsymmetrically substituted alkynes in this strategy enables the synthesis of diversely functionalized indoles, with a regioselectivity that is complementary to the one obtained when employing Larock's annulation reaction.     

Development of a quantitative, validated capillary electrophoresis-time of flight-mass spectrometry method with integrated high-confidence analyte identification for metabolomics

A CE-MS method was developed and validated for the quantitative analysis of negatively charged metabolites by making use of the high mass accuracy and the quantitation capabilities of a TOF mass analyzer in combination with automated feature extraction and database search. Metabolites of the central carbon metabolism were quantified with an LOD and lower LOQ (LLOQ) of 0.2-2 and 1-4 microM, respectively. The method was used to elucidate metabolic changes in the Escherichia coli deletion mutant PntAB-UdhA that lacks nicotinamide nucleotide transhydrogenase function, under both stationary and exponential growth conditions. The reproducibility of metabolite extraction and CE-TOF-MS analysis ranged from 3.7 to 22.7 and 7.9 to 22.6%, respectively, while the biological variance was 3.4-31.3%. We observed significant differences in metabolite abundance, particularly in the citrate cycle, between wild-type and mutant E. coli. Overall, more than 600 features were found by automated feature detection, which resulted in approximately 150 high-confidence metabolite identifications. Concomitant analyses with two different GC-MS methods allowed not only crossvalidation of the quantitative results obtained by the various methods, but also led to a more comprehensive coverage of the E. coli metabolome.     

Hydroaminations of unactivated alkenes with basic alkylamines: group 4 metal halide catalysts and Brønsted-acid organocatalysts

Two distinct economical catalysts for intramolecular hydroaminations of electronically unactivated alkenes with basic amines are described, which are based on (a) group 4 metal halides under basic reaction conditions or (b) Br?nsted-acid organocatalysts.     

Strong enhancement of two-neutron transfer in the system 206Pb+118Sn

One and two neutron transfer has been measured in the heaviest asymmetric nuclear system with semi magic nuclei showing superfluid properties, in ²⁰⁶Pb+¹¹⁸Sn collisions at an energy well below the Coulomb barrier with scattering orbits covering the largest angles. Particle-γ coincidence techniques using 5 Euroball-Cluster detectors (EB) combined in a set-up with the Heidelberg-Darmstadt NaI-Crystal Ball (CB) have been used. Transfer channels are identified with EB via their known γ-decays of the lowest excited states. Using the unique feature of the set-up with the CB, transfer to well defined final states with known quantum numbers (without feeding) are selected using the high efficiency multiplicity filter of the CB (no second γ-ray). The data are analysed using the semiclassical approach and transfer probabilities are obtained. The enhancement for the two-neutron transfer populating the low lying superfluid 2⁺ state in ¹²⁰Sn (and ¹¹⁶Sn), while the Pb-branch is in the groundstate is deduced by comparison with the strongest single neutron transfer transition. Large enhancements (EF ≃ 10³) are observed. This is the first direct measurement of enhancement for a heavy nuclear binary system with experimentally separated levels suggesting a strong contribution from superfluid pair transfer. Received: 18 December 1998 / Revised version: 23 February 1999     

Partially reduced graphite oxide as an electrode material for electrochemical double-layer capacitors

Partially reduced graphite oxide was prepared from graphite oxide by using synthetic graphite as precursor. The reduction of graphite oxide with a layer distance of 0.57?nm resulted in a reduction of the layer distance depending on the degree of reduction. Simultaneously the amount of oxygen functionalities in the graphite oxide was reduced, which was corroborated by elemental analysis and EDX. The electrochemical activation of the partially reduced graphite oxide was investigated for tetraethylammonium tetrafluoroborate in acetonitrile and in propylene carbonate. The activation potential depends significantly on the degree of reduction, that is, on the graphene-layer distance and on the solvent used. The activation potential decreased with increasing layer distance for both positive and negative activation. The resulting capacitance after activation was found to be affected by the layer distance, the oxygen functionalities and the used electrolyte. For a layer distance of 0.43?nm and with acetonitrile as the solvent, a differential capacitance of 220?Fg(-1) was achieved for the discharge of the positive electrode near the open-circuit potential and 195?Fg(-1) in a symmetric full-cell assembly.     

Structural characterization of epitaxial Cr(x)Mo(1-x) alloy thin films

To develop a model system containing regularly spaced misfit dislocations for studies of the radiation resistance of nanoscale defects, epitaxial thin films of Cr, Mo, and Cr(x)Mo(1-x) alloys were deposited on MgO(001) by molecular beam epitaxy. Film compositions were chosen to vary the lattice mismatch with MgO. The film structure was investigated by x-ray diffraction (XRD), Rutherford backscattering spectrometry (RBS) and scanning transmission electron microscopy (STEM). Epitaxial films with reasonably high crystalline quality and abrupt interfaces were achieved at a relatively low deposition temperature, as confirmed by STEM. However, it was found by XRD and RBS in the channeling geometry that increasing the Mo content of the CrMo alloy films degraded the crystalline quality, despite the improved lattice match with MgO. XRD rocking curve data indicated that regions of different crystalline order may be present within the films with higher Mo content. This is tentatively ascribed to spinodal decomposition into Cr-rich and Mo-rich regions, as predicted by the Cr(x)Mo(1-x) phase diagram.