Vinylic MIDA Boronates: New Building Blocks for the Synthesis of Aza‐Heterocycles

A two‐step synthesis of structurally diverse pyrrole‐containing bicyclic systems is reported. ortho‐Nitro‐haloarenes coupled with vinylic N‐methyliminodiacetic acid (MIDA) boronates generate ortho‐vinyl‐nitroarenes, which undergo a “metal‐free” nitrene insertion, resulting in a new pyrrole ring. This novel synthetic approach has a wide substrate tolerance and it is applicable in the preparation of more complex “drug‐like” molecules. Interestingly, an ortho‐nitro‐allylarene derivative furnished a cyclic β‐aminophosphonate motif.     

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Spray thermometry using thermographic phosphors

In this study a novel technique for 2D spray temperature measurement is presented. For this purpose the thermographic phosphor (TP) Mg₄GeO_5.5F:Mn was dispersed in n-dodecane and atomised using a conventional semi solid-cone nozzle. The thermographic phosphor was excited electronically by a frequency tripled Nd:YAG laser (355 nm). An ICCD-camera in combination with an image doubler detected the subsequently emitted phosphorescence at both peak emission wavelengths located at 633 nm and 659 nm, respectively. Utilising suitable calibration measurements, the local spray temperature was determined by evaluating the intensity ratio of both emission wavelengths. To the knowledge of the authors this is the first approach of spray temperature measurement exploiting the temperature dependent intensity ratio of thermographic phosphors. PACS 07.20.Dt; 32.50.+d     

Fabrication of material-independent morphology gradients for high-throughput applications

Gradient surfaces allow rapid, high-throughput investigations and systematic studies in many disparate fields, including biology, tribology and adhesion. We describe a novel method for the fabrication of material-independent morphology gradients, involving a two-step process of particle erosion followed by a chemical polishing procedure that preferentially removes features with a small radius of curvature as a function of time. Gradients are fabricated on aluminium surfaces, but they may be readily transferred to other materials via a replication technique, which allows for the production of identical roughness gradient samples with any chosen surface chemistry. The gradients have been characterized by means of scanning electron microscopy and optical profilometry. Standard roughness parameters (Ra, Rq, Rz, Sm and Sk) were calculated from optical profilometry data. The roughness has also been assessed over different wavelength windows by means of a fast Fourier transformation approach.     

Enantioselective hydrogenation of diaryl-substituted α,β-unsaturated nitriles

α,β-Unsaturated nitriles can be hydrogenated with enantioselectivities up to 88% ee using chiral ruthenium-diphenylphosphino bisaryl and bisheteroaryl complexes such as ruthenium(II)-BINAP and ruthenium(II)-BINP. Mechanistic investigations indicate that conversion is accelerated by electron-rich ligands and that an additional coordinative group needs be present in order to promote conversion. The chiral products are useful building blocks for the synthesis of histamine H₂ agonists of the arpromidine type.     

Problems, Models and Complexity. Part II: Application to the DLSP

In Part I of this study, we suggest to identify an operations research (OR) problem with the equivalence class of models describing the problem and enhance the standard computer-science theory of computational complexity to be applicable to this situation of an often model-based OR context. The Discrete Lot-sizing and Scheduling Problem (DLSP) is analysed here in detail to demonstrate the difficulties which can arise if these aspects are neglected and to illustrate the new theoretical concept. In addition, a new minimal model is introduced for the DLSP which makes this problem eventually amenable to a rigorous analysis of its computational complexity.