I. Allgemeine analytische Methoden, Apparate und Reagentien

Ohne Zusammenfassung     

Investigation of 28Si levels with the (α, γ) and (p, γ) reactions

Particle energies have been measured for resonances in the ²⁷Al(p, γ)²⁸Si and ²⁴Mg(α, γ)²⁸Si reactions with an accuracy of 0.5 × 10^?4 and 1 × 10^?4, respectively. The E_p = 991.88 ± 0.04 keV²⁷Al(p, γ)²⁸Si resonance served as calibration point. From these data the Q-value of the reaction ²⁷Al(p, α)²⁴Mg has been determined as 1600.14 ± 0.21 keV. Excitation energies of ²⁸Si levels have been measured with the ²⁷Al(p, γ)²⁸Si reaction; the reaction energy is Q = 11584.5 ± 0.4 keV.Of 33 resonances observed in the ²⁴Mg(α, γ)²⁸Si reaction (E_α = 1.5–3.8 MeV), energies, strengths and γ-ray decay have been measured; five of these resonances had not been reported previously. The γ-ray angular distribution measurements at three resonances yield the resonance J^π values and the mixing ratios of the strongest transitions involved in the decay. The 10.38 MeV level has J^π = 3⁺, T = 1. The arguments on which T-assignments can be based are critically reviewed. These arguments are used to assign T = 1 character to ¹⁹ states of ²⁸Si.     

On transient behavior of non-premixed counter-flow diffusion flames within the REDIM based model reduction concept

In the present work non-stationary behavior of the counter-flow diffusion flame is examined in the context of the recently developed approach of model reduction called REaction–DIffusion Manifolds (REDIM) method. It is a natural extension of the ILDM approach which takes into account both the chemical reaction and the diffusion processes. It has been developed to treat both premixed and non-premixed regimes of combustion. In this work we investigate the ability of the concept to describe transient processes of extinction and re-ignition. A very simple flame configuration and transport model are considered in this current study for the sake of transparency because the main focus is on the transient and non-stationary behavior of flames. H₂/O₂/N₂ combustion system is considered in a non-premixed counter-flow diffusion 1D flame configuration. This study shows how the REDIM concept performs in the transient regimes; it interprets the effect of local extinction and reigniting phenomena using detailed and reduced models. It shows how the unstable/transient behavior of a detailed system can be successfully accounted with the help of the REDIM based reduced model.     

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.     

The extension of the ILDM concept to reaction–diffusion manifolds

In the present work, the method of simplifying chemical kinetics based on Intrinsic Low-Dimensional Manifolds (ILDMs) is modified to deal with the coupling of reaction and diffusion processes. Several problems of the ILDM method are overcome by a relaxation to an invariant system manifold (Reaction–Diffusion Manifold – REDIM). This relaxation process is governed by a multidimensional parabolic partial differential equation system, where, as an initial solution, an extended ILDM is used. Furthermore, a method for the solution and tabulation of the manifold is proposed in terms of generalized coordinates, with a subsequent procedure for the integration of the reduced system on the found manifold. This modification of the ILDM significantly improves the performance of the concept and allows us to extend its area of applicability. Illustrative comparative calculations of detailed and reduced models of flat laminar flames verify the approach.     

N-triflyl-propiolamides: Preparation and transamidation reactions

N-Trifluoromethylsulfonyl-propiolamides have been prepared by two methods: a) N-triflation of secondary acetylenic carboxanilides, prepared in two steps from terminal alkynes, with triflic anhydride (Tf₂O) and b) from terminal alkynes and an aryl or alkyl isocyanate followed by Tf₂O in a consecutive one-pot reaction. The title compounds are bench-stable and insensitive to water and alcohols but amenable to transamidation reactions with a wide range of amine nucleophiles. Conversely, they are excellent reagents for the propynoylation of ammonia, primary and secondary amines, anilines, and hydrazines.     

Some Aspects of Time-Reversal in Chemical Kinetics

Chemical kinetics govern the dynamics of chemical systems leading towards chemical equilibrium. There are several general properties of the dynamics of chemical reactions such as the existence of disparate time scales and the fact that most time scales are dissipative. This causes a transient relaxation to lower dimensional attracting manifolds in composition space. In this work, we discuss this behavior and investigate how a time reversal effects this behavior. For this, both macroscopic chemical systems as well as microscopic chemical systems (elementary reactions) are considered.     

Crystal structure of diheterolevulosan II: α-d-Fructofuranose-β-d-fructopyranose 1,2′:2,1′ dianhydride and molecular mechanics calculations on diheterolevulosan II and IV with chair and boat conformations of the central 1,4-dioxane ring

C₁₂H₂₀O₁₀,M _r=324.28, orthorhombic,P2₁2₁2₁,a=9.4476(8),b=10.2247(8),c=13.5827(11) Å,V=1312.07(18) ų,Z=4,D _x=1.642 g cm^?3, MoKα radiation (λ=0.71073 Å)μ=1.4 cm^?1,F(000)=688,T=295 K, finalR=0.041 for 1089 reflections withI≥2.5σa(I). The molecule consists of aβ-d-fructopyranose and a α-d-fructofuranose ring which are linked by a 1,4-dioxane ring. The pyranose ring and the dioxane ring both have a chair conformation, and the furanose ring has an envelope conformation. All six hydroxyl groups act as donors in intermolecular hydrogen bonding. Each molecule is hydrogen-bonded to eight neighbor molecules by fourteen hydrogen bonds, forming a three-dimensional framework. The hydrogen bonds of varying geometry give rise to five sharp hydroxyl stretch vibrations in the infrared spectrum. In diheterolevulosan IV the central dioxane ring is a boat. Molecular mechanics calculations on diheterolevulosan II and IV having different boat and chair conformations of the dioxane ring show that the lowest energy conformations correspond to the conformations observed in the crystal structure. For comparison the calculations also have been applied to 1,4-dioxane having boat and chair conformations.     

Recovering Invisible Signals by Two‐Field NMR Spectroscopy

Nuclear magnetic resonance (NMR) studies have benefited tremendously from the steady increase in the strength of magnetic fields. Spectacular improvements in both sensitivity and resolution have enabled the investigation of molecular systems of rising complexity. At very high fields, this progress may be jeopardized by line broadening, which is due to chemical exchange or relaxation by chemical shift anisotropy. In this work, we introduce a two‐field NMR spectrometer designed for both excitation and observation of nuclear spins in two distinct magnetic fields in a single experiment. NMR spectra of several small molecules as well as a protein were obtained, with two dimensions acquired at vastly different magnetic fields. Resonances of exchanging groups that are broadened beyond recognition at high field can be sharpened to narrow peaks in the low‐field dimension. Two‐field NMR spectroscopy enables the measurement of chemical shifts at optimal fields and the study of molecular systems that suffer from internal dynamics, and opens new avenues for NMR spectroscopy at very high magnetic fields.