Degenerate Critical States for Polydisperse Polymer Solutions

If, in a spinodal point, the rank of the stability matrix is less than the order of this matrix minus one, then Gibbs′ determinant criterion for the critical state loses its importance since it is fulfilled automatically by the spinodal condition. In this paper a generalized critical state criterion is established for such degenerate cases in polydisperse polymer solutions.     

Oligosaccharide Synthesis via Electrophile-Induced Activation of Glycosyl-N-Allylcarbamates 1

Abstract

Glycosyl-N-allyl carbamates, obtained by reaction of anomerically unprotected saccharides with allyl isocyanate, can be activated by an electrophile-induced cyclisation and reacted with glycosyl acceptors to form the corresponding oligosaccharides By this method the mucin core 2 trisaccharide² has successfully been synthesized. Due to the mild glycosylation conditions even 1-O-acetyl protected glycosyl acceptors can be used. This was demonstrated in the synthesis of a 1,6-linked glucosyl trisaccharide whereby a reptitious glycosylation strategy could be applied.

     

Adjoint‐based airfoil optimization with discretization error control

In this article, we develop a new airfoil shape optimization algorithm based on higher‐order adaptive DG methods with control of the discretization error. Each flow solution in the optimization loop is computed on a sequence of goal‐oriented h‐refined or hp‐refined meshes until the error estimation of the discretization error in a flow‐related target quantity (including the drag and lift coefficients) is below a prescribed tolerance. Discrete adjoint solutions are computed and employed for the multi‐target error estimation and adaptive mesh refinement. Furthermore, discrete adjoint solutions are employed for evaluating the gradients of the objective function used in the CGs optimization algorithm. Furthermore, an extension of the adjoint‐based gradient evaluation to the case of target lift flow computations is employed. The proposed algorithm is demonstrated on an inviscid transonic flow around the RAE2822, where the shape is optimized to minimize the drag at a given constant lift and airfoil thickness. The effect of the accuracy of the underlying flow solutions on the quality of the optimized airfoil shapes is investigated. Copyright © 2014 John Wiley & Sons, Ltd.     

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).     

High-performance liquid-chromatographic tandem-mass spectrometric methods for atropinesterase-mediated enantioselective and chiral determination of R- and S-hyoscyamine in plasma

S-hyoscyamine (S-hyo) is a toxic tropane alkaloid from plants of the solanacea family, which is extracted for pharmaceutical purposes thereby undergoing racemization (atropine). Merely the S-hyo enantiomer acts as an antagonist of muscarinic receptors (MR). Nevertheless, racemic atropine is clinically administered in e.g. ophthalmology and for symptomatic therapy of acute poisoning with organophosphorus compounds (OPCs, e.g. pesticides, nerve agents). However, very limited data are available of comparative pharmacokinetics of S- and R-enantiomers in humans or other species. Therefore, we developed an enantioselective LC-ESI-MS/MS assay making use of rabbit serum containing atropinesterase (AtrE, EC 3.1.1.10) which is suitable for stereospecific hydrolysis of S-hyo into tropine and tropic acid while R-hyo is unaffected. For sample preparation plasma was incubated with human serum (not containing AtrE, procedure A) and with rabbit serum (procedure B). Afterwards, hyoscyamines were quantified by a validated previously published non-chiral LC-ESI-MS/MS method. Following procedure A the concentration of total hyo and following procedure B remaining R-hyo were determined. S-hyo was calculated by the difference between these concentrations. This assay design allowed reproducible, precise (RSD 2-9%), accurate (93-101%) and selective determination of total and individual hyoscyamines. Potential therapeutics for OPC poisoning (carbamates, oximes) and thiono-pesticides did not interfere with the assay whereas some oxon-pesticides inhibited S-hyo hydrolysis. A control experiment was designed allowing to be aware of such interferences thus avoiding the use of false results. To validate this assay, results were compared to those from a novel isocratic chiral LC-ESI-MS/MS method. Separation of S-hyo (t(R) 31.1 ± 0.2 min) and R-hyo (t(R) 33.4 ± 0.2 min) was achieved on α-glycoprotein (AGP) chiral stationary phase at 40°C (selectivity factor α 1.07). Ammoniumformate (0.01 M, pH 8.0) with 3.75% (v/v) acetonitrile served as mobile phase (300 μL min(-1)). Hyoscyamines were detected in the positive multiple reaction monitor mode. The enantioselective assay was applied to the analysis of atropine degradation in diluted rabbit serum in vitro as well as to human in vivo plasma samples from a pesticide-poisoned patient treated with atropine.     

Qualitative investigations of the photocatalytic dye destruction by TiO<Subscript>2</Subscript>-coated polyester fabrics

The preparation of TiO₂-coated polyester fabrics for purposes of photocatalytic water purification requires coating agents with crystalline TiO₂ particles preferably in the anatase modification. The resulting coatings should exhibit a high water resistance and high photocatalytic activity according to reaction with structurally different dyestuffs. For this, the synthesis of anatase sols by hydrolysis of tetraisopropyltitanate in acidic medium under reflux was optimized. By precoating or addition of polymeric epoxysilanes a good adhesion on the polyester support could be realized. The photocatalytic activity was tested with different dyestuffs as: Methylene blue, Rhodamine B and the azo dyes AcidOrange 7 and C.I. Reactive red 158. The rate of photodestruction depends strongly on the type of used dye and its structure. Surprisingly, no differences in photodegradation were found in case of investigations with Rhodamine B, if the photoreaction is performed under exposure with UV or with visible light. A possible explanation of the similar behavior of photoreaction under different light sources could be a photodestruction by electron transfer from Rhodamine B to TiO₂. Therefore, Rhodamine B seems to be generally not suitable for the evaluation of the photoactivity of TiO₂ under irradiation with visible light.