Methane activation on Ni(1 1 1): Effects of poisons and step defects

We have, theoretically and experimentally, investigated the dissociation of methane on the terraces and steps of a Ni(1 1 1) surface. Using Density Functional Theory (DFT) total energy calculations combined with Ultra High Vacuum (UHV) experiments, we find that the steps exhibit a higher activity than the terraces. We have, furthermore, investigated how carbon and sulfur present on the surface will deactivate the steps, leaving only the terraces active. We find the intrinsic sticking probabilities of methane on the steps and terraces at 500 K to be 2.8 × 10⁻⁷ for the steps and 2.1 × 10⁻⁹ for the terraces, in complete agreement with our calculated difference in activation energy of 17 kJ/mol.     

Homoconjugated ketones with extended unsaturation: Wavelength-selective,regioselective, diastereoselective,and enantiospecific photochemical transformations of methyl 7-oxospiro[5.5]undeca-1,3-and -2,4,-diene-2-carboxylate

The title molecules were shown to photorearrange with remarkable selectivity. Wavelength variation steers the rearrangement modes, of which the [1,2]-acyl shift was found to be largely regioselective, diastereoselective, and enantiospecific. Chemical intercorrelation of products and mechanistic studies were carried out all along. The potential significance of these photochemical processes in selective synthetic schemes is discussed.     

New reals: Can live with them,can live without them

We give a self‐contained proof of the preservation theorem for proper countable support iterations known as “tools‐preservation”, “Case A” or “first preservation theorem” in the literature. We do not assume that the forcings add reals. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electronic Structure and Photophysical Properties of Isoindole and its Benzo[f]- and Dibenzo[e,g]-Derivatives

The synthesis of N-methyl-benz[f]isoindole ( 2 ) and N-methyl-dibenz[e,g]isoindole ( 3 ) is reported. The NMR. spectra of N-methyl-isoindole ( 1 ) and of 2 have been analysed and the implications concerning the alternation of bond lengths are discussed. The photophysical properties of 1 to 3 have been investigated by the following methods: HeI photoelectron (PE.) spectroscopy, UV./VIS. absorption (polarization measurements by the stretched-foil technique) and emission spectroscopy (fluorescence spectra, lifetimes and quantum yields, phosphorescence spectra), and flash spectroscopy (triplet-triplet absorption spectra). The discussion of the results is based on HMO. and PPP SCF CI. calculations and points to the relationship between the heterocycles 1 to 3 and the corresponding benzenoid hydrocarbons obtained by replacement of the ? NMe? subunit by ? CH?CH? . Some comments concerning the ground state properties of isoindole and related compounds are derived from the analysis of their electronic structure.     

Electronic Structure and Photophysical Properties of Planar Conjugated Hydrocarbons with 4n-Membered Rings. I. Photoelectron Spectra of 1,5,9-Tridehydro[12]-annulene and Related Compounds

The HeI photoelectron spectra of the title compound 1 (1,5,9-cyclododecatriene-3,7,11-triyne), 1,5-didehydro[12]annulene (1,3,5,9-cyclododecatetraene-7, 11-diyne ( 2 )), sym-tri-benzotridehydro[12]annulene (tribenzo[a,e,i]-5,6,11,12,17,18-hexadehydrocyclododecene ( 3 )), and sym-dibenzodidehydro[8]annulene (dibenzo[a,e]-5,6,11,12-tetradehydrocyclooctene ( 4 )) have been recorded and analysed on the basis of various semi-empirical model calculations. Despite the distinct bond length alternation in the parent compounds and, apparently, in the radical cations, the first ionization occurs at low energies in these compounds (7.6 ± 0.2 eV). The spectra yield little information with regard to the transannular interactions of the triple bonds.     

The Azo(Azoxy) Functionality as a π2 Component in Photo [2+2] cycloadditions ‘syn’- and ‘anti’-3,4-diazatricyclo[4.2.2.22,5]dodeca-3,7-diene,syntheses, photolyses,X-ray-structure analysis,and PE spectra

The propensity of the N?N bond to undergo photo [2 + 2] cycloadditions has been further explored. In the specifically designed 1,5-azo/enes 1–3 , no [2 + 2] cycloaddition has been observed upon either direct or sensitized excitation with light of various wave lengths at temperatures down to 77 K, in line with expectations based on X-ray ( 1 : d = 2.71 Å, ω = 129°) and PE measurements ( 1 : I₁ = 8.0₀, I₂ = 9.0₅ eV; 2 ; I₁ = 8.0₀, I₂ = 9.2₅eV). The steric/stereoelectronic demands for the participation of the N?N bond in pericyclic reactions are clearly more stringent than those for the C?C bond.     

TOSAR – A Topological Method for the Representation of Synthetic and Analytical Relations of Concepts

In mechanized systems used for searching in literature stores there is a steadily growing necessity not only to be able to formulate concepts as a search condition but also the characteristic connections under which these concepts appear in the inquiry. In this way the precision of the mechanized literature search is considerably increased. TOSAR has been developed in order to improve computerized literature searching in this respect.     

<Emphasis Type="Italic">L</Emphasis>-Carnitine Supplementation: A New Paradigm for its Role in Exercise

Summary. Early research investigating the effects of L-carnitine supplementation has examined its role in substrate metabolism and in acute exercise performance. These studies have yielded equivocal findings, partially due to difficulties in increasing muscle carnitine concentrations. However, recent studies have proposed that L-carnitine may play a different role in exercise physiology, and preliminary results have been encouraging. Current investigations have theorized that L-carnitine supplementation facilitates exercise recovery. Proposed mechanism is as follows: 1) increased serum carnitine concentration enhances capillary endothelial function; 2) increased blood flow and reduced hypoxia mitigate the cascade of ensuing, destructive chemical events following exercise; 3) thus allowing reduced structural damage of skeletal muscle mediated by more intact receptors in muscle needed for improved protein signaling. This paradigm explains decreased markers of purine catabolism, free radical formation, and muscle tissue disruption after resistance exercise and the increased repair of muscle proteins following long-term L-carnitine supplementation.