The adsorption of sulfur on the tungsten (110) surface

The adsorption and desorption of S on a W(110) surface is studied by Auger electron spectroscopy (AES), low energy electron diffraction (LEED), work function change (δφ) measurements and thermal desorption spectroscopy (TDS). The evolution of the structure with coverage θ is quite different from that reported for S on Mo(110) and — at low coverages — from that of Te on W(110). At low coverages the structure indicates complex lateral interactions. The bonding changes with coverage similar to S on W(100). Evidence for more complex desorption kinetics than assumed in the past is presented.     

Fast right-angle spinning EPR on organic radicals: Resolution enhancement and angle determination

Fast right-angle sample spinning (RAS) with rotation frequencies up to 17 kHz at temperatures down to 205 K is applied to electron paramagnetic resonance (EPR) experiments on organic radicals. Echo-detected RAS EPR provides substantial resolution enhancements for the range of anisotropies between 10 and 100 MHz which is not accessible with either magic-angle sample spinning EPR or anisotropy-resolved EPR on the basis of slow rotation. The larger reorientation angles in experiments with fast spinning cause strong phase shifts of the echo, which manifest themselves as regions with negative intensity in the spectrum. These phase shifts and thus the lineshape in echo-detected RAS EPR depend significantly on the relative orientation of theg and hyperfine tensor. For the determination of anisotropies in poorly resolved spectra of organic radicals in disordered solids, we introduce the two-dimensional fixed-angle rotation experiment as an alternative to anisotropy-resolved EPR.     

Statistical analysis of spectra of single impurity molecules and dynamics of disordered solids: I. Distributions of linewidths,moments, and cumulants

A review of recent results of studying the low-temperature dynamics of a disordered solid-state medium that were obtained by the method of single molecule spectroscopy (SMS) is presented. The studies were carried out with the use of the new approach of the statistical analysis of a large number of spectra of single molecules embedded into a medium under study as a microscopic spectral probe. The measurements were performed in the range 2–7 K. The use of SMS allowed us to avoid the information losses connected with the averaging over an ensemble of impurity molecules that is inherent in conventional spectral methods. For the example of the system studied (amorphous polyisobutylene doped with molecules of tetra-tert-butylterrylene), it was shown experimentally that, at low temperatures, the spectra of single impurity molecules in disordered media obey the Levy statistics. New microscopic information on the interaction of two-level systems and quasi-local low-frequency vibrational modes of the matrix with impurity molecules in a disordered medium was obtained.     

Selective Si−C(sp3) Bond Cleavage in (Aminomethyl)silanes by Carbanionic Nucleophiles and Its Stereochemical Course

Selective cleavage of a silicon–carbon bond in tetraorganosilanes is still a great challenge. A new type of Si−C(sp³) bond cleavage in bench-stable (aminomethyl)silanes with common organolithium reagents as nucleophiles has now been identified. Suitable leaving groups are benzyl, allyl, and phenylthiomethyl groups. A β-donor function and polar solvents are essential for the reaction. Simple switching between α-deprotonation and substitution is possible through slight modifications of the reaction conditions. The stereochemical course of the reaction was elucidated by using a silicon-chiral benzylsilane. The new transformation proceeds stereospecifically with inversion of configuration and can be used for the targeted synthesis of enantiomerically pure tetraorganosilanes, which are otherwise difficult to access. Quantum chemical calculations provided insight into the mechanism of the new substitution.     

The Stereostructure of Porphyra‐334: An Experimental and Calculational NMR Investigation. Evidence for an Efficient ‘Proton Sponge’

The mycosporine‐like amino acid (MAA) porphyra‐334 ( 1 ) is subjected to extensive ¹H‐ and ¹³C‐NMR analysis as well as to density‐functional‐theory (DFT) calculations. All ¹H‐ and ¹³C‐NMR signals of 1 are assigned, as well as the resonances of prochiral proton pairs. This is achieved by 500‐MHz standard COSY, HMQC, and HMBC experiments, as well as by one‐dimensional (DPFGSE‐NOE) and two‐dimensional (NOESY) NOE experiments. Diffusion measurements (DOSY) confirm that 1 is monomeric in D₂O solution. DFT Calculations yield ¹³C‐NMR chemical shifts which are in good agreement for species 6 which is the imino N‐protonated form of 1 . An exceptionally high proton affinity of 265.7 kcal/mol is calculated for 1 , indicating that 1 may behave as a very powerful ‘proton sponge’ of comparable strength as synthetic systems studied so far. Predictions of ¹³C‐NMR chemical shifts by the ‘NMRPredict’ software are in agreement with the DFT data. The absolute configuration at the ring stereogenic center of 1 is concluded to be (S) from NOE data as well as from similarities with the absolute configuration (S) found in mycosporine‐glycine 16 . This supports the assumption that 1 is biochemically derived from 3,3‐O‐didehydroquinic acid ( 17 ). The data obtained question the results recently published by a different research group claiming that the configuration at the imino moiety of 1 is (Z), rather than (E) as established by the here presented study.     

Experimental Characterization of Premixed Flame Instabilities of a Model Gas Turbine Burner

In recent years, the NO _x emissions of heavy duty gas turbine burners have been significantly reduced by introducing premixed combustion. These highly premixed burners are known to be prone to combustion oscillations. In this paper, investigations of a single model gas turbine burner are reported focusing on thermo-acoustic instabilities and their interaction with the periodic fluctuations of the velocity and pressure. Phase-locked optical measurement techniques such as LDA and LIF gave insight into the mechanisms.Detailed investigations of a gas turbine combustor rig revealed that the combustor as well as the air plenum oscillate in Helmholtz modes. These instabilities could be attributed to the phase lag of the pressure oscillations between the air plenum and the combustor, which causes an acceleration and deceleration of the air flow through the burner and, therefore, alternating patterns of fuel rich and lean bubbles. When these bubbles reach the reaction zone, density fluctuations are generated which in turn lead to velocity fluctuations and, hence, keep up the pressure oscillations.With increasing the equivalence ratio strong combustion oscillations could be identified at the same frequency. Similarly as with weak oscillations, Helmholtz mode pressure fluctuations are present but the resulting velocity fluctuations in the combustor can be described as a pumping motion of the flow. By the velocity fluctuations the swirl stabilization of the flame is disturbed. At the same time, the oscillating pressure inside the combustor reaches its minimum value. Shortly after the flame expands again, the pressure increases inside the combustor. This phenomenon which is triggered by the pressure oscillations inside the air plenum seems to be the basic mechanism of the flame instability and leads to a significant increase of the pressure amplitudes.