Aniline hydrogenolysis on nickel: effects of surface hydrogen and surface structure

Fluorescence yield near-edge spectroscopy (FYNES) above the carbon K edge and temperature programmed reaction spectroscopy (TPRS) have been used as the methods for characterizing the reactivity and structure of adsorbed aniline and aniline derived species on the Ni(100) and Ni(111) surfaces over an extended range of temperatures and hydrogen pressures. The Ni(100) surface shows appreciably higher hydrogenolysis activity towards adsorbed aniline than the Ni(111) surface. Hydrogenolysis of aniline on the Ni(100) surface results in benzene formation at 470 K, both in reactive hydrogen atmospheres and in vacuum. External hydrogen significantly enhances the hydrogenolysis activity for aniline on the Ni(100) surface. Based on spectroscopic evidence, we believe that the dominant aniline hydrogenolysis reaction is preceded by partial hydrogenation of the aromatic ring of aniline in the presence of 0.001 Torr of external hydrogen on the (100) surface. In contrast, very little adsorbed aniline undergoes hydrogen induced C-N bond activation on the Ni(111) surface for hydrogen pressures as high as 10^–7 Torr below 500 K. Thermal dehydrogenation of aniline dominates with increasing temperature on the Ni(111) surface, resulting in the formation of a previously observed polymeric layer which is stable up to 820 K. Aniline is adsorbed at a smaller angle relative to the Ni(111) surface than the Ni(100) surface at temperatures below the hydrogenolysis temperature. We believe that the proximity and strong -interaction between the aromatic ring of the aniline and the surface is one major factor which controls the competition between dehydrogenation and hydrogen addition. In this case the result is a substantial enhancement of aniline dehydrogenation relative to hydrogenation on the Ni(111) surface.     

Absolute interferometric distance measurement using a FM-demodulation technique

We propose an interferometric method for measuring absolute distances larger than the wavelength. A laser diode is used as a light source. The principle of operation is based on multiple-wavelength interferometry that uses a modulated light source. This method uses the fact that the wavelength of light emitted by the laser diode can be varied by means of the injection current. The modulation of the injection current in combination with the optical heterodyne technique causes a high-frequency phase-modulated detector signal. The phase deviation of the signal is a measure of the optical path difference in the interferometer. By FM demodulation of the detector output with a phase-locked loop demodulator, the optical path difference can be determined directly without the classical ambiguity problem of interferometry. The measuring range in the experiments was limited to 50 mm by the maximum travel range of the used specimen translation stage. Because of the inherent light sensitivity of the method described, the rangefinder can be used for three-dimensional profile measurements on a wide variety of objects, even on diffuse scattering surfaces.     

Arginine 206 of the C5a receptor is critical for ligand recognition and receptor activation by C-terminal hexapeptide analogs

C5a is a 74-amino-acid glycoprotein whose receptor is a member of the rhodopsin superfamily. While antagonists have been generated to many of these receptors, similar efforts directed at family members whose natural ligands are proteins have met with little success. The recent development of hexapeptide analogs of C5a has allowed us to begin elucidation of the molecular events that lead to activation by combining a structure/activity study of the ligand with receptor mutagenesis. Removal of the hexapeptide's C-terminal arginine reduces affinity by 100-fold and eliminates the ability of the ligand to activate the receptor. Both the guanidino side chain and the free carboxyl of the arginine participate in the interaction. The guanidino group makes the energy-yielding contact with the receptor, while the free carboxylate negates "electrostatic" interference with Arg-206 of the receptor. It is the apparent movement Arg-206 induced by this set of interactions that is responsible for activation, since conversion of Arg-206 to alanine eliminates the agonist activity of the hexapeptides. Surprisingly, activation is a nearly energy-neutral event and may reflect the binding process rather than the final resting site of the ligand.     

Scanning tunneling spectroscopy studies on YBa2Cu3O7−δ

Scanning Tunneling Spectroscopy (STS) measurements have been carried out on the high T_c superconductor (HTS) YBa₂Cu₃O_7– (YBCO). Using very high quality single crystals as well as hard tips, we obtained differential conductance spectra which showed various conductance features in agreement with other spectroscopic techniques. The reproducibility of our spectra allowed us to map for the first time the vortex lattice on a HTS using a STS technique¹. The vortices are arranged in a short range order oblique lattice, while the cores of the flux lines show an anisotropic shape. These observations can be related to the in-plane anisotropy of YBCO.     

Model Checking Games for the Quantitative μ-Calculus

We investigate quantitative extensions of modal logic and the modal μ-calculus, and study the question whether the tight connection between logic and games can be lifted from the qualitative logics to their quantitative counterparts. It turns out that, if the quantitative μ-calculus is defined in an appropriate way respecting the duality properties between the logical operators, then its model checking problem can indeed be characterised by a quantitative variant of parity games. However, these quantitative games have quite different properties than their classical counterparts, in particular they are, in general, not positionally determined. The correspondence between the logic and the games goes both ways: the value of a formula on a quantitative transition system coincides with the value of the associated quantitative game, and conversely, the values of quantitative parity games are definable in the quantitative μ-calculus.