Insights into the oxidation of propylene oxide through the analysis of experiments and kinetic modeling

Cyclic ethers are important intermediates in the oxidation of hydrocarbons and biofuels. Studying the oxidation and pyrolysis of cyclic ethers will help in improving our understanding of this functional group and provide consistency to the base mechanism where they play an important role. In this aspect, propylene oxide has been investigated in this study by obtaining ignition delay time measurements in the rapid compression machine and shock tube. The experiments were performed in a range of pressures varying from 10 to 40 bar at different equivalence ratios (0.5–2.0) and dilution percentages. Additionally, speciation measurements in the shock tube at pyrolysis conditions have been performed at a pressure of 40 bar to explore the isomerization pathways. A detailed kinetic mechanism was developed to describe both the oxidation and pyrolysis chemistry of propylene oxide. The mechanism is not only able to predict the data obtained from this study but also reproduces the data from the literature in a consistent trend. For a better understanding of the oxidation and pyrolysis chemistry of propylene oxide, the kinetic analyses were performed using the developed mechanism to comprehend the important reaction pathways and sensitive reactions. At the investigated regime, the consumption of propylene oxide through its isomerization channels is the critical pathway that controls the reactivity of the fuel.     

Preparation,catalytical activity and crystal structure of a heptanuclear zinc acetate cluster

Reaction of [Zn₄(µ₄-O)(O₂CCH₃)₆] with one equivalent of 4-tertiary-butylpyridine leads to a nearly quantitative formation of the heptanuclear cluster [Zn₇O₂(O₂CCH₃)₁₀(^tbupy)₂] (1). Here, we present the crystal structure of 1 and first results of the examination of its catalytic activity in transesterification reactions and polymerization of lactide compared to the activity of [Zn₄(µ₄-O)(O₂CCH₃)₆] in the presence of 4-tertiary-butylpyridine.     

Regioselective Oxidative Ring Opening of Cyclopropyl Silyl Ethers: A Quantum Chemical Study

In contrast to the structurally and configurationally stable alkyl‐ or aryl‐substituted cyclopropyl radical cations, cyclopropyl silyl ethers undergo spontaneous ring opening upon oxidation whereby the endocyclic C? C(O‐TMS) bond is cleaved with remarkable selectivity. DFT calculations on 1‐trimethylsilyloxybicyclo[4.1.0]heptane show that this selectivity arises from the topology of the potential surface of the corresponding radical cation which is initially generated in a very steep region of the potential surface from where the steepest descent leads to cleavage of the endocyclic rather than the lateral C? C(OTMS) bond. Cleavage of the lateral bond leads to interesting conformational changes which are explored in detail.     

Size‐Tunable Micron‐Bubbles Based on Fluorous–Fluorous Interactions of Perfluorinated Dendritic Polyglycerols

This paper describes the behavior of various generations of polyglycerol dendrimers that contain a perfluorinated shell. The aggregation in organic solvents is based on supramolecular fluorous–fluorous interactions, which can be described by means of ¹⁹F NMR spectroscopy. In order to study the interaction and aggregation phenomena of dendrimers with perfluorinated shell and perfluoro‐tagged guest molecules we investigated [G3.5]‐dendrimer with a perfluorinated shell in the presence of perfluoro‐tagged disperse red. Noteworthy, the interaction intensities varied in an unexpected manner depending on the equivalents of perfluoro‐tagged guest molecules added to the dendrimers in solution which then formed supramolecular complexes based on fluorous–fluorous interactions. We found that these complexes aggregated around residual air in the solvent to form stable micron‐sized bubbles. Their sizes correlated with the interaction intensities measured for certain dendrimer–guest molecule ratios. Degassing of the solutions led to a quasi phase separation between organic and fluorous phase, whereby the dendrimers formed the fluorous phases. Regassing the sample with air afforded bubbles of the initial size again.     

Graphene as a reversible spin manipulator of molecular magnets

One of the primary objectives in molecular nanospintronics is to manipulate the spin states of organic molecules with a d-electron center, by suitable external means. In this Letter, we demonstrate by first principles density functional calculations, as well as second order perturbation theory, that a strain induced change of the spin state, from S=1→S=2, takes place for an iron porphyrin (FeP) molecule deposited at a divacancy site in a graphene lattice. The process is reversible in the sense that the application of tensile or compressive strains in the graphene lattice can stabilize FeP in different spin states, each with a unique saturation moment and easy axis orientation. The effect is brought about by a change in Fe-N bond length in FeP, which influences the molecular level diagram as well as the interaction between the C atoms of the graphene layer and the molecular orbitals of FeP.     

Surface termination of BaTiO3 (001) single crystals: A combined electron spectroscopic and theoretical study

The surface termination of oxide surfaces is of crucial importance for the growth of a second material like metals or other oxides. In this study we have investigated the surface of a BaTiO₃ (001) single crystal during sample preparation by various electron spectroscopic methods. It is shown by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and metastable induced electron spectroscopy (MIES) that during sputtering a Ba rich overlayer is formed, in which the Ba²⁺ ions are under coordinated. Below this layer, an oxygen deficient BaTiO₃ layer is found. During annealing, we observe the reformation of the crystalline structure. UP and MIE spectra provide clear evidence of a BaO terminated surface. X-ray photoelectron diffraction studies support this result, comparing recorded polar angle scans with calculated intensity modulations using multiple scattering cluster models.     

Smoothed performance guarantees for local search

We study popular local search and greedy algorithms for standard machine scheduling problems. The performance guarantee of these algorithms is well understood, but the worst-case lower bounds seem somewhat contrived and it is questionable whether they arise in practical applications. To find out how robust these bounds are, we study the algorithms in the framework of smoothed analysis, in which instances are subject to some degree of random noise. While the lower bounds for all scheduling variants with restricted machines are rather robust, we find out that the bounds are fragile for unrestricted machines. In particular, we show that the smoothed performance guarantee of the jump and the lex-jump algorithm are (in contrast to the worst case) independent of the number of machines. They are  \(\Theta (\phi )\) and  \(\Theta (\log \phi )\) , respectively, where  \(1/\phi \) is a parameter measuring the magnitude of the perturbation. The latter immediately implies that also the smoothed price of anarchy is  \(\Theta (\log \phi )\) for routing games on parallel links. Additionally, we show that for unrestricted machines also the greedy list scheduling algorithm has an approximation guarantee of   \(\Theta (\log \phi )\) .     

On the benefits of ODT-based stochastic turbulence modeling

We summarize the group's progress in applying, analyzing, and improving ODT and ODT-based stochastic turbulence models like ODTLES. Compared to DNS these models span a wider range of scales while compared to RANS/LES (i) the molecular effects are retained and (ii) no assumption of scale separation is made. In this regard ODTLES has more properties of DNS than of standard LES. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

An accelerated simulation method of medium density wood fiber boards

An accelerated micro-scale simulation method for the prediction of the stiffness of medium density fiber boards is proposed with the aim to increase the speed of the coupled micro-macro simulation and to study the influence of fiber orientation on material properties. The stiffness is interpolated between loads in a n-dimensional simplex figure, which is constructed in a macroscopic strain, temperature, moisture, time and other load. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Error-Controlled Model Order Reduction of Second Order Systems with Adaptive Choice of Shifts and Order

This contribution summarizes a novel approach to error-controlled model order reduction of second order systems, i. e. a new way to find a reduced order model of specified approximation quality. To this end, starting from a particular state space realization of the model, one performs multiple reduction steps and increments the reduced model until (computationally affordable) rigorous global error bounds fall below the prescribed limit. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)