On the interaction of Mg with the (111) and (110) surfaces of ceria

The catalytic activity of cerium dioxide can be modified by deposition of alkaline earth oxide layers or nanoparticles or by substitutional doping of metal cations at the Ce site in ceria. In order to understand the effect of Mg oxide deposition and doping, a combination of experiment and first principles simulations is a powerful tool. In this paper, we examine the interaction of Mg with the ceria (111) surface using both angle resolved X-ray (ARXPS) and resonant (RPES) photoelectron spectroscopy measurements and density functional theory (DFT) corrected for on-site Coulomb interactions (DFT + U). With DFT + U, we also examine the interaction of Mg with the ceria (110) surface. The experiments show that upon deposition of Mg, Ce ions are reduced to Ce(3+), while Mg is oxidised. When Mg is incorporated into ceria, no reduced Ce(3+) ions are found and oxygen vacancies are present. The DFT + U simulations show that each Mg that is introduced leads to formation of two reduced Ce(3+) ions. When Mg is incorporated at a Ce site in the (111) surface, one oxygen vacancy is formed for each Mg to compensate the different valencies, so that all Ce ions are oxidised. The behaviour of Mg upon interaction with the (110) surface is the same as with the (111) surface. The combined results provide a basis for deeper insights into the catalytic behaviour of ceria-based mixed oxide catalysts.     

Sc(OTf)3-catalyzed diastereoselective Friedel-Crafts reactions of arenes and hetarenes with 3-phenylglycidates

Five different para-substituted 3-phenylglycidates (3-phenyloxirane-2-carboxylates) were prepared and subjected to reactions with arenes and hetarenes under Lewis acid catalysis. Sc(OTf)(3) was found to effectively (5 mol%) promote a Friedel-Crafts reaction in nitromethane as the solvent. The reaction was shown to proceed stereoconvergently, which makes the intermediacy of a benzylic cation likely. The diastereoselectivities varied depending on the choice of the nucleophile and 3-arylglycidate. Best results were obtained with tert-butyl 3-anisylglycidate, which delivered the respective products with high syn-preference in diastereomeric ratios (d.r.) between 82 : 18 and >95 : 5. The observed selectivity can be explained by a model, according to which the intermediate benzylic cations adopt a preferred conformation, which allows for diastereoface-differentiation by the adjacent stereogenic center.     

Lifting and separation procedures for the cut polytope

The max-cut problem and the associated cut polytope on complete graphs have been extensively studied over the last 25 years. However, in comparison, only little research has been conducted for the cut polytope on arbitrary graphs, in particular separation algorithms have received only little attention. In this study we describe new separation and lifting procedures for the cut polytope on general graphs. These procedures exploit algorithmic and structural results known for the cut polytope on complete graphs to generate valid, and sometimes facet defining, inequalities for the cut polytope on arbitrary graphs in a cutting plane framework. We report computational results on a set of well-established benchmark problems.     

Convergence Analysis of Spatially Adaptive Rothe Methods

This paper is concerned with the convergence analysis of the horizontal method of lines for evolution equations of the parabolic type. Following a semidiscretization in time by \(S\) -stage one-step methods, the resulting elliptic stage equations per time step are solved with adaptive space discretization schemes. We investigate how the tolerances in each time step must be tuned in order to preserve the asymptotic temporal convergence order of the time stepping also in the presence of spatial discretization errors. In particular, we discuss the case of linearly implicit time integrators and adaptive wavelet discretizations in space. Using concepts from regularity theory for partial differential equations and from nonlinear approximation theory, we determine an upper bound for the degrees of freedom for the overall scheme that are needed to adaptively approximate the solution up to a prescribed tolerance.     

Derived Equivalence Classification of the Cluster-Tilted Algebras of Dynkin Type E

We obtain a complete derived equivalence classification of the cluster-tilted algebras of Dynkin type E. There are 67, 416, 1574 algebras in types E ₆, E ₇ and E ₈ which turn out to fall into 6, 14, 15 derived equivalence classes, respectively. This classification can be achieved computationally and we outline an algorithm which has been implemented to carry out this task. We also make the classification explicit by giving standard forms for each derived equivalence class as well as complete lists of the algebras contained in each class; as these lists are quite long they are provided as supplementary material to this paper. From a structural point of view the remarkable outcome of our classification is that two cluster-tilted algebras of Dynkin type E are derived equivalent if and only if their Cartan matrices represent equivalent bilinear forms over the integers which in turn happens if and only if the two algebras are connected by a sequence of “good” mutations. This is reminiscent of the derived equivalence classification of cluster-tilted algebras of Dynkin type A, but quite different from the situation in Dynkin type D where a far-reaching classification has been obtained using similar methods as in the present paper but some very subtle questions are still open.     

Consideration of slice profiles in inversion recovery Look–Locker relaxation parameter mapping

Purpose

To include the flip angle distribution caused by the slice profile into the model used for describing the relaxation curves observed in inversion recovery Look–Locker FLASH T₁ mapping for a more accurate determination of the relaxation parameters.

Materials and methods

For each inversion time, the flip angle dependent signal of the mono-exponential relaxation model is integrated across the slice profile. The resulting Consideration of Slice Profiles (CSP) relaxation curves are compared to the mono-exponential signal model in numerical simulations as well as in phantom and in-vivo experiments.

Results

All measured relaxation curves showed systematic deviations from a mono-exponential curve increasing with flip angle and T₁ but decreasing with repetition time. Additionally, the accuracy of T₁ was found to be largely dependent on the temporal coverage of the relaxation curve. All these systematic errors were largely reduced by the CSP model.

Conclusion

The proposed CSP model represents a useful extension of the conventionally used mono-exponential relaxation model. Despite inherent model inaccuracies, the mono-exponential model was found to be sufficient for many T₁ mapping situations. However, if only a poor temporal coverage of the relaxation process is achievable or a very precise modeling of the relaxation course is needed as in model-based techniques, the mono-exponential model leads to systematic errors and the CSP model should be used instead.     

Development of medium pressure laser ionization,MPLI. Description of the MPLI ion source

A novel pulsed valve/ion source combination capable of time-resolved sampling from atmospheric pressure has been developed for use with laser ionization time of flight mass spectrometry. The source allows ionization extremely close to the nozzle of the pulsed valve, enabling ultra-sensitive detection of a number of compounds, e.g., NO, at mixing ratios <1 pptV. Furthermore, at analyte mixing ratios in the ppbV range, the temporal resolution of the system is in the sub-second regime, allowing time-resolved monitoring of highly dynamic and complex mixtures, e.g., human breath or reacting chemical mixtures in atmospheric smog chamber experiments. Rotational temperatures of approximately 50 K have been observed for analytes seeded in the supersonic jet expansion at a distance of 1 mm downstream of the nozzle orifice. The refinement of the original ion source has drastically reduced the impact of reflected laser light and the resultant electron impact signals previously observed. The general applicability of this technique is demonstrated here by coupling the source to commercially available as well as home-built time-of-flight mass spectrometers. Finally, we discuss the MPLI technique in view of the very recently introduced atmospheric pressure laser ionization (APLI) as well as the traditional jet-REMPI approach.     

Optical system design and experimental evaluation of a coherent Doppler wind Lidar system for the predictive control of wind turbine

The control of wind turbine blade pitch systems by Lidar assisted wind speed prediction has been proposed to increase the electric power generation and reduce the mechanical fatigue load on wind turbines. However, the sticking point of such Lidar systems is the price. Hence, our objective is to develop a more cost efficient Lidar system to support the pitch control of horizontal axis wind turbines and therefore to reduce the material requirement, lower the operation and maintenance costs and decrease the cost of wind energy in the long term. Compared to the state of the art Lidar systems, a laser with a shorter coherence length and a corresponding fiber delay line is introduced for reducing the costs. In this paper we present the experimental evaluation of different sending and receiving optics designs for such a system from a free space laboratory setup.     

Dark field nanoparticle tracking analysis for size characterization of plasmonic and non-plasmonic particles

Journal of Nanoparticle Research - Co3O4 nanocubes with perfect shape were synthesized by a simple hydrothermal route in which Co3O4 was directly prepared in the one-pot process with aging...     

Access to Intrinsically Glucoside‐Based Microspheres with Boron Affinity

Intrinsically glucoside‐based microspheres are prepared in olive oil via a water in oil inverse suspension polymerization. The microspheres are characterized by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) microscopy, and X‐ray photoelectron spectroscopy (XPS), evidencing the intrinsic glucose character of the spheres. A novel boronic acid fluorescent molecule was subsequently conjugated to the microspheres in an aqueous environment, exhibiting the spatial and uniform distribution of glucoside as well as the affinity of the microspheres to bind with boron, evidenced via fluorescence spectroscopy measurements.