Originalarbeiten 133m Xe zur Markierung von Gasphasen bei technischen Tracerexperimenten

Bei technischen Tracerexperimenten bereitet die Markierung von Gasphasen Schwierigkeiten, wenn man auf Außenwandmessungen angewiesen ist, da die Auswahl an geeigneten Radionukliden bzw. radioaktiv markierten Verbindungen dann sehr beschrānkt ist. Eine gute Ergänzung des Radionuklidangebotes für den genannten Zweck bietet ^133mXe, Halbwertszeit 2,3 d, E_γ = 0,23 MeV (16%). ^133mXe erhält man mit guten Ausbeuten bei einer Reaktoraktivierung von natürlichem Xenon. Die Sälligungsaktivität fär ^133mXe beträgt bei einem Fluß von 5,0 μ 10¹³ n/cm²s 48,5 mCi/cm³ Xenon (unter Normalbedingungen). An Veweilzeitmessungen von Gasphasen in technischen Anlagen werden die Einsatzmöglichkeiten des ^133mXe dargestellt.     

Boundedness and Stability for Higher Order Difference Equations*

Sufficient conditions are given under which the higher order difference equation x _n+1= f(x _n,x _n-1,...,x_n-k ), n=0,1,2,... generates an order preserving discrete dynamical system with respect to the discrete exponential ordering. It is shown that under the above monotonicity assumption the boundedness of all solutions as well as the local and global stability of an equilibrium hold if and only if they hold for the much simpler first order equation x _n+1=h(x _n ), where h(x)=f(x,x,…,x). As an application, a second order nonlinear difference equation from macroeconomics and a discrete analogue of a model of haematopoiesis are discussed.     

Ultrafast transverse thermoelectric response in c‐axis inclined epitaxial La0.5Sr0.5CoO3 thin films

Ultrafast transverse thermoelectric voltage response has been observed in c‐axis inclined epitaxial La_0.5Sr_0.5CoO₃thin films. Voltage signals with the rise time of 7 ns have been detected under the irradiation of pulse laser with duration of 28 ns. A concept, named response rate ratio, has been proposed to evaluate the intrinsic response rate, and this ratio in La_0.5Sr_0.5CoO₃is smaller than that in other reported materials. The low resistivity is thought to be responsible for the ultrafast response, as low resistivity induces small optical penetration depth, and response time has a monotonous increasing relationship with this depth.

     

Impact of molecular tilt angle on the absorption spectra of pentacene:perfluoropentacene blends

We investigate the relation between the optical properties and the average molecular tilt angle for blends of pentacene and perfluoropentacene, which can be considered as a prototypical donor–acceptor complex. Combining near‐edge X‐ray absorption fine‐structure spectroscopy and optical spectroscopy we study thin films of these compounds prepared at three different substrate temperatures T_sub. For T_sub =180 K we observe a larger average tilt angle than for blends prepared at higher substrate temperatures. This orientational change has significant impact on the uniaxial anisotropic optical properties of the mixed films which we measure post growth as well as in real‐time during growth. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Implementation of REDIM reduced chemistry to model an axisymmetric laminar diffusion methane–air flame

The goal of this work is to analyze the use of automatically reduced chemistry by the Reaction–Diffusion Manifold (REDIM) method in simulating axisymmetric laminar coflow diffusion flames. Detailed chemical kinetic models are usually computationally prohibitive for simulating complex reacting flows, and therefore reduced models are required. Automatic reduction model approaches usually exploit the natural multi-scale structure of combustion systems. The novel REDIM approach applies the concept of invariant manifolds to treat also the influence of the transport processes on the reduced model, which overcomes a fundamental problem of model reduction in neglecting the coupling of molecular transport with thermochemical processes. We have considered a previously well studied atmospheric pressure nitrogen-diluted methane–air flame as a test case to validate the methodology presented here. First, one-dimensional and two-dimensional REDIMs were computed and tabulated in lookup tables. Then, the full set of governing equations are projected on the REDIM and implemented in the object-oriented C++ Gascoigne code with a new add-on library to deal with the REDIM tables. The projected set of governing equations have been discretized by the Finite Element Method (FEM) and solved by a GMRES iteration preconditioned by a geometric multigrid method. Local grid refinement, adaptive mesh and parallelization are applied to ensure efficiency and precision. The numerical results obtained using the REDIM approach have shown very good agreement with detailed numerical simulations and experimental data.     

Effect of addition of a non-equidiffusional reactant to an equidiffusional diffusion flame

A Burke–Schumann (flame-sheet) formulation is developed for diffusion flames between a fuel and oxidiser with Lewis numbers of unity, subject to addition to the fuel and/or oxidiser stream of a different reactant for which the Lewis number differs from unity. This formulation is applied to laminar counterflow diffusion-flame experiments, reported here, in which hydrogen was added to either methane–nitrogen mixtures or oxygen–nitrogen mixtures at normal atmospheric pressure, with both feed streams at normal room temperature. Experimental conditions were adjusted to fix selected values of the stoichiometric mixture fraction and the adiabatic flame temperature, and the strain rate was increased gradually, maintaining the momentum balance of the two streams, until extinction occurred. At the selected sets of values, the strain rate at extinction was measured as a function of the hydrogen concentration in the fuel or oxidiser stream. The ratio of the fraction of the oxidiser flux that consumes hydrogen to the fraction that consumes fuel was calculated from the new Burke–Schumann formulation, and it was found that, within experimental uncertainty, the ratio of the extinction strain rate with hydrogen addition to that without was the same at any given value of this oxygen flux ratio, irrespective of whether the hydrogen was added on the fuel or oxidiser side. This experimental result was also in close agreement with computational predictions employing detailed chemistry. These results imply that differences in detailed hydrogen concentration profiles within the reaction zone have little or no influence on the chemical kinetics of extinction when the stoichiometric mixture fraction, the adiabatic flame temperature, and the proportion of oxygen that consumes the added fuel are fixed. This same correspondence may be expected to apply for other fuels and additives.     

Solid state 19F NMR parameters of fluorine-labeled amino acids. Part I: aromatic substituents

Structural parameters of peptides and proteins in biomembranes can be directly measured by solid state NMR of selectively labeled amino acids. The 19F nucleus is a promising label to overcome the low sensitivity of 2H, 13C or 15N, and to serve as a background-free reporter group in biological compounds. To make the advantages of solid state 19F NMR fully available for structural studies of polypeptides, we have systematically measured the chemical shift anisotropies and relaxation properties of the most relevant aromatic and aliphatic 19F-labeled amino acids. In this first part of two consecutive contributions, six different 19F-substituents on representative aromatic side chains were characterized as polycrystalline powders by static and MAS experiments. The data are also compared with results on the same amino acids incorporated in synthetic peptides. The spectra show a wide variety of lineshapes, from which the principal values of the CSA tensors were extracted. In addition, temperature-dependent T(1) and T(2) relaxation times were determined by 19F NMR in the solid state, and isotropic chemical shifts and scalar couplings were obtained in solution.     

Directed Evolution of a Bacterial Laccase (CueO) for Enzymatic Biofuel Cells

Escherichia coli's copper efflux oxidase (CueO) has rarely been employed in the cathodic compartment of enzymatic biofuel cells (EBFCs) due to its low redox potential (0.36 V vs. Ag/AgCl, pH 5.5) towards O₂ reduction. Herein, directed evolution of CueO towards a more positive onset potential was performed in an electrochemical screening system. An improved CueO variant (D439T/L502K) was obtained with a significantly increased onset potential (0.54 V), comparable to that of high‐redox‐potential fungal laccases. Upon coupling with an anodic compartment, the EBFC exhibited an open‐circuit voltage (V_oc) of 0.56 V. Directed enzyme evolution by tailoring enzymes to application conditions in EBFCs has been validated and might, in combination with molecular understanding, enable future breakthroughs in EBFC performance     

Ethynylphosphonamidates for the Rapid and Cysteine‐Selective Generation of Efficacious Antibody–Drug Conjugates

Requirements for novel bioconjugation reactions for the synthesis of antibody–drug conjugates (ADCs) are exceptionally high, since conjugation selectivity as well as the stability and hydrophobicity of linkers and payloads drastically influence the performance and safety profile of the final product. We report Cys‐selective ethynylphosphonamidates as new reagents for the rapid generation of efficacious ADCs from native non‐engineered monoclonal antibodies through a simple one‐pot reduction and alkylation. Ethynylphosphonamidates can be easily substituted with hydrophilic residues, giving rise to electrophilic labeling reagents with tunable solubility properties. We demonstrate that ethynylphosphonamidate‐linked ADCs have excellent properties for next‐generation antibody therapeutics in terms of serum stability and in vivo antitumor activity.