Paracyclophanes as model compounds for strongly interacting π-systems, part 3: influence of the substitution pattern on photoabsorption properties

The structures and energetics of the ground and first excited states of [2.2]paracyclophane (PC) and its pseudo-para- (p-DHPC) and pseudo-ortho-dihydroxy (o-DHPC) as well as monohydroxy derivates (MHPC) are investigated by quantum chemical calculations, X-ray crystallography, and resonance-enhanced multiphoton ionization spectroscopy (REMPI) in a free jet. We show that substitution of the aromatic hydrogens in PC causes significant changes of the structure and in particular its change between the ground and the excited state. The structural changes include a breathing mode as well as shift and rotation of the benzene moieties and are rationalized by the electronic structure changes upon excitation. Spin-component-scaled second-order M?ller-Plesset perturbation method (SCS-MP2) reproduces the experimental X-ray structure correctly and performs significantly better than ordinary MP2 and the B3LYP methods. The parent propagation method, SCS-approximate coupled cluster second order (SCS-CC2), yields adiabatic excitation energies within 0.1 eV of the experimental values for PC and the investigated hydroxyl derivates as well as the related aromatic molecules benzene and phenol. It is shown that zero-point vibration energy corrections at the time dependent density functional (B3LYP) level are no more accurate enough for that level of theory and have to be substituted by SCS-CC2 values. While the structures of PC and o-DHPC are only slightly modified upon excitation, p-DHPC changes its structural parameters substantially. This is in line with [1 + 1] REMPI-spectra of these substances, which are interpreted with the help of Franck-Condon simulations.     

Polymer-and Glass-based Fluorescence Standards for the Near Infrared (NIR) Spectral Region

The widespread use and acceptance of fluorescence techniques especially in regulated areas like medical diagnostics is closely linked to standardization concepts that guarantee and improve the comparability and reliability of fluorescence measurements. At the core of such concepts are dependable fluorescence standards that are preferably certified. The ever rising interest in fluorescence measurements in the near-infrared (NIR) spectral region renders the availability of spectral and intensity standards for this wavelength region increasingly important. This encouraged us to develop approaches to solid NIR standards based upon dye-doped polymers and assess their application-relevant properties in comparison to metal ion-doped glasses. The overall goal is here to provide inexpensive, easily fabricated, and robust internal and external calibration tools for a broad variety of fluorescence instruments ranging e.g. from spectrofluorometers over fluorescence microscopes to miniaturized fluorescence sensors.     

Self-organized synchronization and voltage stability in networks of synchronous machines

The integration of renewable energy sources in the course of the energy transition is accompanied by grid decentralization and fluctuating power feed-in characteristics. This development raises novel challenges for power system stability and design. We investigate power system stability from the viewpoint of self-organized synchronization aspects. In this approach, the power grid is represented by a network of synchronous machines. We supplement the classical Kuramoto-like network model, which assumes constant voltages, with dynamical voltage equations, and thus obtain an extended model, that incorporates the coupled categories voltage stability and rotor angle synchronization. We compare disturbance scenarios in small systems simulated on the basis of both classical and extended model and we discuss resultant implications and possible applications to complex modern power grids.     

Vibrations of Rotors Supported on Nonlinear Bearings

Rotors in electrical machines are supported by various types of bearings. In general, the rotor bearings have nonlinear stiffness properties and they influence the rotor vibrations significantly. In this work, this influence of these nonlinearities is investigated. A simplified finite element model using Timoshenko beam elements is set up for the heterogeneous structure of the rotor. A transversally isotropic material model is adopted for the rotor core stack. Imposing the nonlinear bearing stiffnesses on the model, the Newton-Raphson procedure is used to carry out a run up simulation. The spectral content of these results shows nonlinear effects due to the bearings. The rotor vibrations are further investigated in detail for various constant speeds. These results show non-harmonic vibrations of the rotor in a section of the investigated speed range. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

A Lipschitz metric for the Hunter–Saxton equation

We analyze stability of conservative solutions of the Cauchy problem on the line for the (integrated) Hunter–Saxton (HS) equation. Generically, the solutions of the HS equation develop singularities with steep gradients while preserving continuity of the solution itself. In order to obtain uniqueness, one is required to augment the equation itself by a measure that represents the associated energy, and the breakdown of the solution is associated with a complicated interplay where the measure becomes singular. The main result in this article is the construction of a Lipschitz metric that compares two solutions of the HS equation with the respective initial data. The Lipschitz metric is based on the use of the Wasserstein metric.     

Synthesis and characterization of polystyrene chains on the surface of silica nanoparticles: comparison of SANS, SAXS, and DLS results

An extensive characterization of well-defined polystyrene (PS)-grafted silica nanoparticles is reported. Bare SiO₂ particles (diameter 50 nm) were functionalized with a suitable initiator for the surface-initiated anionic polymerization of styrene. Both grafted and free PS chains were characterized and compared by size-exclusion chromatography (SEC). PS-grafted particles were characterized by transmission electron microscopy (TEM), thermogravimetric analysis (TGA), small-angle x-ray scattering (SAXS), small-angle neutron scattering (SANS), and dynamic light scattering (DLS). The thickness of the grafted PS chains was obtained by SANS and DLS and scaled with $M_{\mathrm {w}}^{0.6}$ displaying similar behavior with free PS chains in the same solvent used, tetrahydrofuran (THF). Grafting densities obtained from SANS data and TGA were found to be small, and the thickness of the grafted PS chains determined by SANS was found to be similar to $2R_{\mathrm {g}}$ of free PS chains in THF. Both results are consistent with a “coil-like” conformation of the grafted PS chains.     

Fluorescently Labeled Substrates for Monitoring α1,3‐Fucosyltransferase IX Activity

Fucosylation is often the final process in glycan biosynthesis. The resulting glycans are involved in a variety of biological processes, such as cell adhesion, inflammation, or tumor metastasis. Fucosyltransferases catalyze the transfer of fucose residues from the activated donor molecule GDP‐β‐L ‐fucose to various acceptor molecules. However, detailed information about the reaction processes is still lacking for most fucosyltransferases. In this work we have monitored α1,3‐fucosyltransferase activity. For both donor and acceptor substrates, the introduction of a fluorescent ATTO dye was the last step in the synthesis. The subsequent conversion of these substrates into fluorescently labeled products by α1,3‐fucosyltransferases was examined by high‐performance thin‐layer chromatography coupled with mass spectrometry as well as dual‐color fluorescence cross‐correlation spectroscopy, which revealed that both fluorescently labeled donor GDP‐β‐L ‐fucose‐ATTO 550 and acceptor N‐acetyllactosamine‐ATTO 647N were accepted by recombinant human fucosyltransferase IX and Helicobacter pylori α1,3‐fucosyltransferase, respectively. Analysis by fluorescence cross‐correlation spectroscopy allowed a quick and versatile estimation of the progress of the enzymatic reaction and therefore this method can be used as an alternative method for investigating fucosyltransferase reactions.     

NMR spectroscopy of intermetallic compounds: an experimental and theoretical approach to local atomic arrangements in binary gallides

The results of the investigation of MGa(2) with M = Ca, Sr, Ba and of MGa(4) with M = Na, Ca, Sr, Ba by a combined application of NMR spectroscopy and quantum mechanical calculations are comprehensively evaluated. The electric-field gradient (EFG) was identified as the most reliable measure to study intermetallic compounds, since it is accessible with high precision by quantum mechanical calculations and, for nuclear spin I>1/2, by NMR spectroscopy. The EFG values obtained by NMR spectroscopy and quantum mechanical calculations agree very well for both series of investigated compounds. A deconvolution of the calculated EFGs into their contributions reveals its sensitivity to the local environment of the atoms. The EFGs of the investigated di- and tetragallides are dominated by the population of the p(x)-, p(y)-, and p(z)-like states of the Ga atoms. A general combined approach for the investigation of disordered intermetallic compounds by application of diffraction methods, NMR spectroscopy, and quantum mechanical calculations is suggested. This scheme can also be applied to other classes of crystalline disordered inorganic materials.     

Colchicin

Colchicin was extracted from grinded seeds of meadow saffron and purified by flash chromatography and preparative HPLC. All analytical spectra were recorded and are reproduced either in the main part or in the supporting information. The NMR‐ and mass‐spectra have been interpreted and compared with theoretical calculations of the ¹³C chemical shifts. The project is a follow up of the recent book “Classics in Spectroscopy” by S. Berger und D. Sicker (Wiley‐VCH 2009).     

Measurement of the absolute branching fraction of D0-->K-pi+

We measure the absolute branching fraction for D(0)-->K(-)pi(+) using partial reconstruction of B(0)-->D(*+)Xl(-)nu(l) decays, in which only the charged lepton and the pion from the decay D(*+)-->D(0)pi(+) are used. Based on a data sample of 230 x 10(6) BB pairs collected at the Upsilon(4S) resonance with the BABAR detector at the PEP-II asymmetric-energy B factory at SLAC, we obtain B(D(0)-->K(-)pi(+)) = (4.007+/-0.037+/-0.072)%, where the first uncertainty is statistical and the second is systematic.