Spin polarized photoemission from NiMnSb

Spin polarized photoemission experiments are reported on NiMnSb which has been predicted to be a halfmetallic ferromagnet. The 100% polarization near photothreshold has not been observed. If an energy gap in the minority electron density-of-states should exist, it will be smaller than 0.5 eV.     

Muon spin relaxation in CeCu2Si2 and muon knight shift in various heavy-fermion systems

Positive muon spin precession has been observed in various heavy-fermion systems in the transverse external magnetic field. In the superconductor CeCu_2.1Si₂, the relaxation rate of muon spins increases rapidly with decreasing temperature below T_C. This is interpreted as the results of the inhomogeneous fields due to the imperfect penetration of the external field into the type-II superconducting state. The magnetic-field penetration depth λ is derived from the observed muon spin relaxation rate. λ is about 1200 ∢ at T∼0.5T_C, and the temperature dependence of λ is consistent with the relation expected for a BCS superconductor. We have also measured the muon Knight shift K_μ in the normal (or paramagnetic) state of various heavy-fermion systems. K_μ is large and negative (about −1000∼−3000 ppm at T=10 K) for CeCu₂Si₂, UPt₃ and CeAl₃, while more complicated signals are measured in CePb₃ and CeB₆. The negative muon Knight shift in the non-magnetic heavy-fermion systems is discussed in terms of the Kondo-coupling between the conduction- and f-electrons.     

Structure and electronic properties of niobium-ruthenium alloys

The electronic specific heat, the Debye temperature, the paramagnetic susceptibility and the superconducting transition temperature have been measured in the niobium-rich region of the Nb-Ru system. Structural investigation proved that the single phase region extends up to at least 45 at. % Ru at low temperatures, with a gradually increasing tetragonal deformation above 37% Ru. The results reveal a flat minimum in the density of states near a concentration of 5.7 valence electrons per atom. Comparison of specific heat and susceptibility data lends support to the suggestion that a van Vleck type paramagnetic contribution might be important in this and related alloy systems. The superconducting transition temperature of very pure niobium was found to be 9.49°K.     

Spezifische Wärme und magnetische Suszeptibilität supraleitender,binärer komplexer Phasen von Übergangsmetallen

Measurements of the electronic specific heat in the normal and superconducting state of 15 superconducting binary complex phases of theσ- andχ-structure are presented. The alloys have been prepared under high vacuum in an electron-beam melting apparatus described in detail. In the investigated range between 6 and 7 valence-electrons, the obvious correlation betweenT _c, the superconducting critical temperature, andγ, the coefficient of the electronic specific heat, leads to agreement with the empirical rules, found byMatthias. Recently,Morel andAnderson andGarland have calculated the values of the deviation of the normal isotope-effect. With these values it is possible to relate the observedT _c-data for most of the transition metal alloys investigated so far to the density of states at the Fermi level and to a systematically varying electron-phonon interaction parameter. In the superconducting state, an exponential dependence of the electronic specific heat on 1/T is found in the range betweenT _c/2 andT _c/6. However the parameters are somewhat different from those predicted by theory. The values ofγ observed also account for the lack of any correlation between the total magnetic susceptibility and the superconducting critical temperature for these phases.     

Bis(glycinato‐κ2N,O)dinitrosylmolybdenum(0) and bis(2‐aminoethanethiolato‐κ2N,S)dinitrosylmolybdenum(0) acetonitrile monosolvate

The title compounds, [Mo(C₂H₄NO₂)₂(NO)₂], (I), and [Mo(C₂H₆NS)₂(NO)₂]·CH₃CN, (II), contain distorted octahedral complexes in which the monoanionic N,S‐ and N,O‐bidentate ligands coordinate the molybdenum centres in different modes. The anionic O atoms of the glycinate ligands in (I) are coordinated trans to the nitrosyl ligands and the amine N atoms are located trans to each other, whereas in (II) the anionic S atoms are coordinated trans to each other and the amine N atoms are located trans to the nitrosyl ligands. Each compound has a single complete complex in the asymmetric unit on a general position. Six N—H...O contacts with N...O distances of less than 3.2 Å are observed in (I) between the amine groups and the nitrosyl and carboxylate O atoms. In the 1:1 solvate (II), the acetonitrile molecule forms short N—H...N contacts (N...N < 3.2 Å) between the solvent N atoms and one of the amine H atoms. In addition, three weak intermolecular N—H...S interactions (N...S > 3.3 Å) contribute to the stabilization of the structure of (II).     

Synthesis and evaluation of potent, highly-selective, 3-aryl-piperazinone inhibitors of protein geranylgeranyltransferase-I

A series of compounds based on the carboxyl-terminal CAAL sequence of PGGTase-I substrates was designed and synthesized. Using piperazin-2-one as a semi-rigid scaffold, we have introduced critical pharmacophores in a well-defined arrangement to mimic the CAAL sequence. High potency and exceptional selectivity were obtained for inhibition of PGGTase-I with structures such as 45 and 70. Potency of this series of GGTIs was dependent on the presence of an L-leucine residue with a free carboxyl terminus, as well as an S configuration of the 3-aryl group. The selectivity was significantly enhanced by 5-methyl substitution on the imidazole ring and fluorine substitution on the 3-aryl group. Modification of the 6-position of the piperazinone scaffold was found to be unfavorable. Compounds 44 and 69, the corresponding methyl esters of 45 and 70, were found to selectively block processing of Rap1A by PGGTase-I in whole cells with IC(50) values of 0.4 microM and 0.7 microM respectively.     

A TRIR, TREPR and computational study on the reactivity and structure of the 2,2,2-trifluoroethoxycarbonyl radical

The 2,2,2-trifluoroethoxycarbonyl radical, 3b, has been generated by pulsed irradiation of 9-fluorenone oxime 2,2,2-trifluoroethyl oxalate 1b in carbon tetrachloride and acetonitrile solution. It was characterized by time-resolved electron paramagnetic resonance spectroscopy (EPR) and infrared spectroscopy. The radical has a lifetime in the range of microseconds and can be detected within the rise time of our time-resolved equipment before undergoing recombination or reactions with the solvent. No decarbonylation or decarboxylation was observed. In the presence of oxygen, the radical is quenched to yield the 2,2,2-trifluoroethoxycarbonylperoxy radical 4b, which has again a lifetime in the range of several microseconds. Time-resolved electron paramagnetic resonance spectroscopy (TREPR) allowed for the detection of a 1 : 1 : 1 triplet of the fluorene-9-iminyl radical 7 at g = 2.0032 and a 1 : 3 : 3 : 1 quartet with additional hyperfine splitting (HFS) due to proton coupling at g = 2.001 for the trifluoroethoxycarbonyl radical 3b. Calculations indicate that alkoxycarbonyl radicals can exist in conformations that are s-trans or s-cis with respect to the R-O-C(O) x dihedral. A comparison of experimental TREPR spectra with simulations indicates that the s-trans conformer is observed in the case of the ethoxycarbonyl radical, 3a. In the case of the trifluorethoxycarbonyl radical, 3b, however, the additional proton HFS observed shows that it is the s-cis conformer that is formed. As calculations give evidence for a fairly high activation enthalpy for s-cis-s-trans interconversion of alkoxycarbonyl radicals, this discrepancy is likely due to differing conformational preferences of the precursor molecules.     

Time-resolved infrared study on the photochemistry of O-fluoroformyl- and O-chlorooxalyl-9-fluorenone oxime: the reactivity of the fluoroformyl radical in acetonitrile solution

This note describes the photochemistry of O-chlorooxalyl- and O-fluoroformyl-9-fluorenone oxime. The solution photochemistry of both precursors was investigated by time-resolved step/scan FTIR spectroscopy. Experiments on O-chlorooxalyl-9-fluorenone oxime only allowed for detection of CO2 and bleaching of the precursor, indicating predominant N-O cleavage. The chlorocarbonyl radical, ClCO*, was not detected. In contrast, TRIR investigations on fluoroformyl oxime 2 gave evidence for formation of the fluoroformyl radical FCO* (3), which rapidly adds to the solvent acetonitrile, yielding a fluoroformyl-functionalized iminyl radical 4. Its reaction with triplet molecular oxygen, on the other hand, is impeded by an activation enthalpy that has been calculated as deltaH# = 3.2 kcal/mol.