PM-IRRAS mapping of ultrathin molecular films with high spatial resolution

Polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) is a very sensitive technique to characterize the degree of molecular ordering in thin films on metallic surfaces. This is the first report of the coupling of a PM-IRRAS microscope to a free electron laser (FEL), a light source of highest brilliance. Some FELs emit in the infrared region and permit the mapping of molecular properties at high lateral resolution. We studied the molecular orientation of octadecanephosphonic acid (OPA) attached to a gold surface with microstructured aluminum oxide islands on the gold. The spatial resolution achieved is 12 μm which corresponds to the diffraction limit of the infrared light used in this study. This is a substantial improvement compared to previous studies using a PM-IRRA accessory together with a commercial Fourier transform infrared spectrometer, where the lateral resolution is noise-limited rather than diffraction-limited. The spectral maps reveal that OPA is preferably attached to the aluminum oxide islands via the bidentate binding mode whereas the tridentate mode is dominating in case of OPA attached to the gold areas.     

Electric field gradient in nanostructured SnO2 studied by means of PAC spectroscopy using 111Cd or 181Ta as probe nuclei

Electric quadrupole interactions were studied in pure and Mn-doped powder samples and thin films of SnO₂ using perturbed γγ angular correlation spectroscopy (PAC). The powder samples were prepared by Sol gel method and the thin film were prepared on the Si (100) substrate by sputtering technique using Sn in the oxygen atmosphere. The samples were characterized by x-ray diffraction, energy dispersive spectroscopy and scanning electron microscopy. The thickness of the film was 100 nm. The average particle size of the SnO₂ powder samples was determined to be smaller than 60 nm. The radioactive ¹¹¹In and ¹⁸¹Hf tracers were introduced in the powder samples during the sol gel chemical process. Radioactive ¹¹¹In was implanted on the SnO₂ thin films using the University of Bonn ion implanter (BONIS). PAC measurements were carried out in a four BaF₂ detector spectrometer in the temperature range of 77–973 K for samples annealed at different temperatures. The PAC results for both nuclear probes show the presence of two electric quadrupole interactions. The major fractions in both cases correspond to the substitutional sites in the rutile phase of SnO₂. The results are compared with previous PAC measurements.     

Novel triazolopeptides: chirospecific synthesis and conformational studies of proline derived analogs

Replacing the backbone amide function by a heterocyclic bioisostere, [3+2] azide-alkyne cycloaddition has been applied for the construction of biologically relevant peptidomimetics. Starting from aminoalkynoates, triazole formation was accomplished by addition of hydrazoic acid. NMR studies displayed that the newly developed 4,5-triazolopeptides, which incorporate a biomimetic triazole NH-function as polar constraint element, showed a substantially higher tendency to form a cis-prolyl-geometry than a comparable native peptide sequence.     

A contribution to the theory of the capillary viscometer

Summary A general arrangement of a capillary viscometer is examined with a non-steady flow of aNewtonian liquid. The flow is determined by a pressure dependent upon the time. The velocity is found as a function of the pressure gradient or the length coordinate and the time. The result can serve for the determination of the viscosity.Three illustrative examples are given.

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Zusammenfassung Der allgemeine Aufbau eines Kapillar-Viskosimeters wird an Hand des nichtstationären Fließens einer Newtonschen Flüssigkeit überprüft. Das Fließen wird durch einen zeitabhängigen Druck bestimmt. Die Geschwindigkeit ergibt sich danach als Funktion des Druckgradienten oder der Längen-Koordinate und der Zeit. Das Ergebnis kann zur Bestimmung der Viskosität dienen. Drei Beispiele dienen der Erläuterung.

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Tetramethylcyclopentadienyl-supported rare-earth metal bis(tetramethyl)aluminate complexes: Synthesis,structural chemistry,cation formation,and isoprene polymerization

The protonolysis reaction of [Ln(AlMe₄)₃] with H(Cp′) (Cp′ = C₅Me₄H) gives access to half-sandwich complexes [(Cp′)Ln(AlMe₄)₂]. X-ray structure analyses of the samarium, neodymium, and lanthanum derivatives reveal a distinct [AlMe₄] coordination (one η², one bent η²) for the two smaller rare-earth metals. The lanthanum complex displays an unprecedented dimeric structure with two μ₂-η¹:η² coordinating [AlMe₄] ligands in the solid state. Treatment of complexes [(Cp′)Ln(AlMe₄)₂] with perfluorinated organoborates and -boranes produces discrete contact ion-pairs, which are characterized by ¹H, ¹³C, ²⁷Al, ¹⁹F, and ¹¹B NMR spectroscopy and act as efficient initiators for the fabrication of trans-1,4 polyisoprene. The polymerization performance is hereby affected by the rare-earth metal cation size, the type of boron cocatalyst, and the polymerization temperature.     

Hydrology of the lakes in Central Wohlthat Massif, East Antarctica: new results

In 1983/1984, in the course of the 28th Soviet Antarctic Expedition, waterbody, ice cover, and surrounding glaciers of the lakes Untersee and Obersee were sampled along some depth profiles. The geochemical data of those samples, now available, show the homogeneity of both large lakes in vertical (down to the maximum depth) as well as in lateral directions. The comparison of isotope and chemical composition of lake water and adjoining glacier ice suggests strong differences in the long-term evolution between the lakes Untersee and Obersee. First data from a lakelet, embedded in the large morainic area to the west of Lake Untersee, are of special interest: the δ(2)H values of the lakelet water are lower than those of recent regional glacier ice by 50‰ SMOW. This fact indicates that the lakelet is fed episodically by Pleistocene dead ice, covered by the morainic material.     

Efficient high-power frequency doubling of distributed Bragg reflector tapered laser radiation in a periodically poled MgO-doped lithium niobate planar waveguide

We report on efficient single-pass, high-power second-harmonic generation in a periodically poled MgO-doped LiNbO3 planar waveguide using a distributed Bragg reflector tapered diode laser as a pump source. A coupling efficiency into the planar waveguide of 73% was realized, and 1.07 W of visible laser light at 532 nm was generated. Corresponding optical and electro-optical conversion efficiencies of 26% and 8.4%, respectively, were achieved. Good agreement between the experimental data and the theoretical predictions was observed.     

Local stability analysis of a stochastic evolutionary financial market model with a risk-free asset

This paper introduces and analyzes an evolutionary model of a financial market with a risk-free asset. Focus is on the study of local stability of the wealth dynamics through the application of recent results on the linearization and stability of random dynamical systems (Evstigneev et al. Proc Am Math Soc 139:1061–1072, 2011). Conditions are derived for the linearization of the model at an equilibrium state which ensure local convergence of sample paths to this equilibrium. The paper also shows that the concept of local stability is closely related to the notion of evolutionary stability. A locally evolutionarily stable investment strategy in the evolutionary model with a risk-free asset is derived, extending previous research. The method illustrated here is applicable for the analysis of manifold economic and financial dynamic models involving randomness.