Direct conversion of hydroxy aromatic compounds to heteroarylamines via a one-pot smiles rearrangement procedure

8-Hydroxyquinoline ( 9 ) was converted to 8 -aminequinoline ( 10 ) in a one-pot procedure involving alleviation with 2-bromo-2-methylpropionamide ( 2 ) followed by Smiles rearrangement and hydrolysis, in 41% yield. The scope and limitations of this new procedure were explored with additional hydroxyquinolines.     

Detection limits of matrix-assisted laser desorption/ionisation mass spectrometry coupled to chromatography--a new application of solvent-free sample preparation

The detection limits of matrix-assisted laser desorption/ionisation mass spectrometry (MALDI-MS) by semi-online coupling with chromatography were investigated using various mixtures of polyethylene oxides (PEOs) with different end groups. In contrast to the common 'dried-droplet' sample preparation technique, which results in an inhomogeneous sample-to-matrix ratio within the MALDI spot, the used coupling technique offers a very high reproducibility combined with surpassing sensitivity of a few femtograms over a broad range of sample-to-matrix ratios. These results are in correlation with the results of the recently established solvent-free MALDI-TOFMS method utilising the grinding approach and are also of assistance towards the more theoretical aspect of MALDI that suggests that there is no necessity for an analyte incorporation into a matrix crystal for excellent matrix-assistance.     

Structural refinement of the high-pressure phase of aluminum trihydroxide: in-situ high-pressure angle dispersive synchrotron X-ray diffraction and theoretical studies

In-situ high-pressure synchrotron angle-dispersive X-ray diffraction for gibbsite (aluminum trihydroxide) was performed at room temperature up to 20 GPa. A pressure-induced phase transition was observed at 2.6 GPa. The new high-pressure phase can be recovered at ambient pressure. Rietveld refinement shows that the new phase of Al(OH)(3) has an orthorhombic structure, spacegroup Pbca, and the lattice parameters at ambient condition are a = 868.57(5) pm, b = 505.21(4) pm, c = 949.54(6) pm, V = 416.67(6) x 10(6) pm(3) with Z = 8. The compressibility of gibbsite and the high-pressure polymorph was analyzed, and their bulk moduli were estimated as 49.8 +/- 1.8 and 81.0 +/- 5.2 GPa, respectively. First-principles calculations of the high-pressure phase were performed to determine the hydrogen positions and to confirm the structural stability of the new phase.     

A periodicity lemma in linear diophantine analysis

Let g = (g₁,…,g_r) ≥ 0 and h = (h₁,…,h_r) ≥ 0, g_?, h_? ∈ $\text{J}$, be two vectors of nonnegative integers and let λ ? $\text{J}$, λ ≥ 0, λ ≡ 0 mod d, where d denotes g.c.d. (g₁,…,g_r). Define

$\text{Δ(λ)=Δ(λg,h):=}\text{min}\text{∑}\text{?=1}\text{r}\text{x}{}_{\mathrm{?}}\text{h}{}_{\mathrm{?}}\text{:x}{}_{\mathrm{?}}\text{?0,x}{}_{\mathrm{?}}\text{∈J,}\text{∑}\text{?=1}\text{?}\text{x}{}_{\mathrm{?}}\text{g}{}_{\mathrm{?}}\text{=λ}$

It is shown in this paper that Λ(λ) is periodic in λ with constant jump. If i? {1,…,r} is such that

$\text{det}\text{g}{}_{\mathrm{i}}\text{h}{}_{\mathrm{i}}\text{g}{}_{\mathrm{?}}\text{h}{}_{\mathrm{?}}\text{? (?1,…r)}$

then

$\text{Δ(λ)+g}{}_{\mathrm{i}}\text{Δ(λ)+h}{}_{\mathrm{i}}$

holds true for all sufficiently large λ, λ ≡ 0 mod d.     

Case studies on the application of high-resolution electron channelling contrast imaging – investigation of defects and defect arrangements in metallic materials

In 1967, Coates discovered the electron channelling contrast of backscattered electrons (BSEs) in scanning electron microscopy, and by this the possibility to investigate arrangements of lattice defects in deformed microstructures of materials. Since that time, a straightforward development of the scanning electron microscopes as well as of the electron channelling contrast technique took place. Nowadays, the performance of scanning electron microscopes is high enough that the resolution of electron channelling contrast imaging (ECCI) micrographs is comparable with conventional bright field transmission electron microscopy (TEM) micrographs. In the first part of the present paper, a historical review on the development of the ECCI technique starting from its discovery more than 45 years ago up to the combination with other advanced methods of scanning electron microscopy like electron backscatter diffraction or high-resolution selected area channelling patterning in the last few years is given. Major important investigations using this technique for the visualization of individual lattice defects like stacking faults (SFs) and dislocations or dislocation arrangements are chronologically summarized. The second part demonstrates that nowadays, ECCI micrographs taken in high-resolution scanning electron microscopes can be called high-resolution ECCI (HR-ECCI). It is shown that the resolution of individual SFs and dislocations in the HR-ECCI micrographs is comparable to that of conventional TEM (about 15 nm defect image width). Furthermore, the paper is demonstrating that HR-ECCI micrographs can be obtained for various types of materials after different mechanical loadings and different grain sizes ranging from large grain size of 500 μm (cast steel) down to less than 2 μm (γ-TiAl).     

2-Cyclopropyliden-1,3-cycloalkandione als Zwischenstufen einer nukleophilen Substitution am Dreiring

Reaction of morpholinobicycloalkyl-dimedone4 C with various CH-acids3 leads to a substitution of theexo-dimedone unit as a consequence of a strong preference of theexo-leaving group in a bicyclic compound of type4 and5, respectively. Dimedone (3 C) as a nucleophile, however, makes theexo substitution unproductive in4 C and allows the displacement of the morpholino moiety leading to12 C. Thus compounds12 C–12 F could be obtained directly from the N,O-acetal1 and the CH-acids3 C–3 F by a twofold substitution, the isolation of the monoalkylated compounds4 not being necessary. Formation of12 C–12 F involves aMichael addition of3 C–3 F to the unstable 2-Cyclopropylidene-1,3-cycloalkanedione intermediates7 C–7 F. Cyclopentanedione3 F as a CH-acid and1 gave the enamine17 F besides12 F. The Hexahydroazepino-N,O-acetal19 in this special case was superior leading exclusively to12 F.

     

Bimetallic Cluster Provides a Higher Activity Electrocatalyst for Methanol Oxidation

The cluster complex Pt₂Ru₄(CO)₁₈ was used as a precursor to prepare a 60 wt% 1:2 Pt:Ru nanoparticles on carbon (PtRu/C) for use as an electrocatalyst for methanol oxidation. This bimetallic carbonyl cluster complex was found to provide smaller, more uniform bimetallic nanoparticle that exhibited higher electrocatalytic activity than a 60 wt% 1:1 Pt:Ru commercial catalyst from E-Tek. Using bimetallic cluster precursors simplifies the synthetic procedures by reducing the need for high temperature reduction and assures a more intimate mixing of the two different metals. Transmission electron microscopy (TEM) images of the catalyst obtained from the cluster precursor showed bimetallic nanoparticles having a narrow size range of 2–3 nm that were dispersed uniformly over the surface of the support. Images of the commercial catalyst showed particles 3–4 nm in diameter that tended to agglomerate near the edges of the carbon support particles. Cyclic voltammograms of methanol oxidation from the two catalysts showed significantly higher activity for the cluster-derived catalyst. The onset potential for methanol oxidation for the cluster-derived catalyst was approximately 170 mV lower than that of the commercial catalyst at 100 A/g Pt, and approximately 250 mV lower at 400 A/g Pt. ^* This report is dedicated to Prof. Günter Schmid on the occasion of his 70th birthday.     

Complete efficiency and interdependencies between objective functions in vector optimization

Summary Vector optimization problems in linear spaces with respect to general domination sets are investigated including corollaries to Pareto-optimality and weak efficiency. The results contain equivalences between vector optimization problems, interdependencies between objective functions and domination sets, statements about the influence of perturbed objective functions on the decision maker's preferences and thus on the domination set, comparisons of efficiency with respect to polyhedral cones with Pareto-optimality, changes in the objective functions which restrict, extend or do not alter the set of Pareto-optima, possibilities for the use of domination sets immediately in the decision space. Conditions for complete efficiency are given.

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Zusammenfassung Untersucht werden Vektoroptimierungsprobleme in linearen Räumen bezüglich allgemeiner Dominanzmengen einschließlich Folgerungen für Pareto-Optimalität und schwache Effizienz. Die Ergebnisse enthalten Äquivalenzen zwischen Vektoroptimierungsproblemen, Wechselwirkungen zwischen Zielfunktionen und Dominanzmengen, Aussagen über den Einfluß gestörter Zielfunktionen auf die Präferenzen des Entscheidungsträgers und somit auf die Dominanzmenge, Vergleiche von Effizienz bezüglich polyedrischer Kegel mit Pareto-Optimalität, Änderungen in den Zielfunktionen, die die Menge der Pareto-Optima einschränken, erweitern oder nicht beeinflussen, Möglichkeiten für die Nutzung von Dominanzmengen unmittelbar im Entscheidungsraum. Bedingungen für vollständige Effizienz werden gegeben.

     

Fuzzy sets and Boolean-valued universes

A connection between fuzzy sets and Boolean-valued universes is made by developing a formal axiomatic system for fuzzy sets among whose models are suitably interpreted Boolean-valued universes. The formal system is an independent first-order axiomatization of fuzzy set theory which parallels the Zermelo-Fraenkel development of classical set theory.