Switchable Solubility of Azobenzene-Based Bolaamphiphiles

The ability to design amphiphiles with predictable solubility properties is of everlasting interest in supramolecular chemistry. Relevant structural parameters include the hydrophobic–hydrophilic balance and structural flexibility. In this work, we investigate the water solubility of azobenzene-based triglycerol bolaamphiphiles (TGBAs). In particular, we analyzed the structural effects of backbone hydrophobicity, flexibility, and cis/trans isomerization on the water solubility of a subset of five TGBAs. This leads to the first example of a non-ionic bolaamphiphile whose water solubility can be changed by irradiation with light. The underlying kinetics were monitored using liquid chromatography and a closer analysis of the underlying aggregation processes provides a mechanistic understanding of the light-driven dissolution process. We anticipate that the results obtained will help to engineer bolaamphiphiles with predictable solution properties in the future.     

Simulation of round jets with nozzle-dependent inflow conditions using the k−ε turbulence model

In view of the “round jet initial condition anomaly”, discussed in literature, we investigate the effect of inflow conditions resulting from the use of different nozzle geometries to form the jet. RANS simulations in the framework of OpenFOAM using the k − ε turbulence model are performed. As the standard model coefficient C_ε1 = 1.44 is known to overpredict spreading rates for round jets, a value of C_ε1 = 1.6 was recommended for this case already in the 1970's. While this works well for jets issuing from long pipes, it does not give satisfactory results for other nozzle geometries. To overcome this deficiency while keeping the k − ε model, we suggest modified coefficients C_ε1 based on profiles of mean flow and turbulence at the nozzle exit. We determine optimal values of C_ε1 for three different nozzle geometries, and test them at various Reynolds numbers. Good agreement with experimental data is obtained. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Two-cluster bifurcations in systems of globally pulse-coupled oscillators

For a system of globally pulse-coupled phase-oscillators, we derive conditions for stability of the completely synchronous state and all stationary two-cluster states and explain how the different states are naturally connected via bifurcations. The coupling is modeled using the phase-response-curve (PRC), which measures the sensitivity of each oscillator’s phase to perturbations. For large systems with a PRC, which is zero at the spiking threshold, we are able to find the parameter regions where multiple stable two-cluster states coexist and illustrate this by an example. In addition, we explain how a locally unstable one-cluster state may form an attractor together with its homoclinic connections. This leads to the phenomenon of intermittent, asymptotic synchronization with abating beats away from the perfect synchrony.     

Realizing a laser-driven electron source applicable for radiobiological tumor irradiation

Laser-accelerated electron pulses have been used to irradiate human tumors grown on mice’s ears during radiobiological experiments. These experiments have been carried out with the JETI laser system at the Institute of Optics and Quantum Electronics in Jena, Germany. To treat a total of more than 50 mice, a stable and reliable operation of the laser-electron accelerator with a dose rate exceeding 1 Gy/min was necessary. To achieve this, a sufficient number of electrons at energies in excess of 5 MeV had to be generated. The irradiation time for a single mouse was a few minutes. Furthermore, the particle pulses’ parameters needed to remain achievable for a time period of several weeks. Due to the online detection of the radiation dose, the unavoidable shot-to-shot fluctuations, currently still typical for laser-based particle accelerators, could be compensated. The results demonstrate that particle pulses generated with laser-based accelerators have the potential to be a future alternative for conventional particle accelerators used for the irradiation of tumors.     

LC–MS analysis of low molecular weight organic acids derived from root exudation

A sensitive method for quantification of citric, fumaric, malic, malonic, oxalic, trans aconitic, and succinic acid in soil- and root-related samples is presented. The method is based on a novel, fast, and simple esterification procedure and subsequent analysis via liquid chromatography–mass spectrometry. Derivatization comprises in situ generation of HCl, which catalyzes the Fischer esterification with benzyl alcohol. As a key advance, the esterification with the aromate allows reversed-phase separation and improves electrospray ionization efficiency. The method provided procedural detection limits of 1 nM for citric, 47 nM for fumaric, 10 nM for malic, 10 nM for malonic, 16 nM for oxalic, 15 nM for succinic, and 2 nM for aconitic acid utilizing 500 μL of liquid sample. The working range was 3 nM to 10 μM for citric acid, 158 nM to 10 μM for fumaric acid, 34 nM to 10 μM for malic acid, 33 nM to 10 μM for malonic acid, 53 nM to 10 μM for oxalic acid, 48 nM to 10 μM for succinic acid, and 6 nM to 10 μM for aconitic acid. Quantification of the analytes in soil-related samples was performed via external calibration of the entire procedure utilizing ¹³C-labeled oxalic and citric acid as internal standards. The robustness of the method was tested with soil extracts and samples from hydroponic experiments. The latter concerned the regulation of phosphorus solubilization via plant root exudation of citric, malic, and oxalic acid.     

Use of average value of Langmuir probe characteristic for characterization of pulsed discharges

Based on numerical calculations a new method has been developed, which enables plasma analysis from the average value of the Langmuir probe current measured in pulsed discharge. The application of this method for characterization of a planar reactor used for plasma enhanced chemical vapor deposition of TiN and (TiAl)N hard coatings is described as an example. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Unimolecular reactions of the resonance-stabilized cyclopentadienyl radicals and their role in the polycyclic aromatic hydrocarbon formation

Resonance-stabilized cyclopentadienyl radicals are important intermediate species in the combustion of transportation fuels. It not only serves as precursors for polycyclic aromatic hydrocarbon (PAH) formation, but also involves in the formation of fundamental PAH precursors such as propargyl and acetylene. In this work, the unimolecular reactions of the cyclopentadienyl radicals are theoretically studied based on high-level quantum chemistry and RRKM/master equation calculations. Stationary points on the potential energy surface (PES) are calculated at the CCSD(T)/CBS//M06–2X/6–311++(d,p) level of theory. The branching ratios of unimolecular reactions of the cyclopentadienyl radicals are analyzed for a broad temperature range from 500 to 2500 K and pressures from 0.01 to 100 atm. It is found that the isomerization reaction of the cyclopentadienyl radical via 1,2-hydrogen transfer dominates at low temperatures and high pressures, while the well-skipping decomposition reaction which forms propargyl and acetylene is important at high temperatures and low pressures. Both the decomposition reaction of the cyclopentadienyl radicals and its reverse reaction show pronounced pressure dependence, and their reaction rate constants are compared against available low-pressure experimental measurements and theoretical studies. The temperature- and pressure-dependent rate coefficients for important reactions involved on the C₅H₅ PES are calculated and updated in a chemical kinetic model. Impacts of the unimolecular reactions of the cyclopentadienyl radicals on the PAH formation are explored by the numerical modeling of a low-pressure cyclopentene counterflow diffusion flame.