Comparative enantioseparations with native beta-cyclodextrin,randomly acetylated beta-cyclodextrin and heptakis-(2,3-di-O-acetyl)-beta-cyclodextrin in capillary electrophoresis

Comparative enantioseparations were performed with three neutral cyclodextrins (CDs) in capillary electrophoresis (CE). In particular, native beta-CD was compared with single component heptakis(2,3-di-O-acetyl)-beta-CD (HDA-beta-CD) and randomly acetylated beta-CD (Ac-beta-CD) with the emphasis on the enantiomer migration order. The opposite affinity of the enantiomers of several chiral analytes was observed towards native beta-CD and its acetylated derivatives. The enantiomer affinity pattern of some chiral analytes was also opposite towards the two acetylated derivatives of beta-CD. In the case of the chiral drug clenbuterol (CL) an attempt was made to evaluate the possible structural reasons of the affinity reversal using one- and two-dimensional as well as transverse rotating frame nuclear Overhauser effect spectroscopy (ROESY). Significant differences were observed between the structure of the CL complexes with beta-CD and HDA-beta-CD.     

Synthesis of intrinsically flame‐retardant copolyamides and their employment in PA6‐fibers

Flame‐retarded polyamide 6.6 (FR‐PA6.6) was prepared by the cocondensation of hexamethylene diammonium adipate (AH‐salt) with the corresponding salts of hexamethylene diamine and two different organophosphorus compounds, namely, 3‐hydroxyphenylphosphinylpropanoic acid (3‐HPP, 1) and 9,10‐dihydro‐10‐[2,3‐di (hydroxycarbonylpropyl]‐10‐phosphaphenanthrene‐10‐oxide (DDP, 2). The incorporation of the phosphorus comonomers and the thermal and physical properties of the resulting copolyamides have been studied. The phosphorus‐modified FR‐PA6.6 possesses high relative viscosities of 2.0 to 2.4, good thermal stability, and was used for the production of polyamide blends by merging FR‐PA6.6 with commercial PA6. This offered access to flame‐retarded PA6 multifilaments, which possess tensile strengths up to 0.7 GPa and elastic moduli up to 6.2 GPa. Knitted fabrics of FR‐PA6 exhibit high limiting oxygen index (LOI) values between 36 and 38 and executed burning tests demonstrate that the incorporation of phosphorus‐based comonomers improve flame retardancy significantly. The approach presented here offers a straightforward access to effective flame retardancy in nylon 6.     

Protein deformation of lipid hybrid bilayer membranes studied by sum frequency generation vibrational spectroscopy

Structural deformations of lipid hybrid bilayer membranes induced by signal peptideless (SPL) proteins have been studied for the first time using the inherently surface specific nonlinear optical technique of sum frequency generation vibrational spectroscopy. Specifically, deformations of 1,2-distearoylphosphatidylglycerol(DSPG) membranes induced by interaction with FGF-1, a SPL protein which is released asa function of cellular stress through a nonclassical pathway, have been investigated. FGF-1 was found to induce lipid alkyl chain deformations in previously highly ordered DSPG membranes at the extremely low concentration of 1 nM at 60 degrees C. The deformation process was shown to exhibit a degree of reversibility upon removal of the protein by rinsing with buffer solution.     

Reflections on spontaneous asymmetric synthesis by amplifying autocatalysis

Spontaneous generation of chirality was observed in the course of studying the mechanism of asymmetric autocatalysis by NMR in ZnR2 alkylation of pyrimidin-5-aldehydes. A systematic study was carried out in order to discover its origins. Even in clean fresh non-glass reaction vessels spontaneous ee was clearly observed, and was not dependent on any single reaction parameter. For comparison it was demonstrated that enantiomerically pure Zn alkoxide catalyst could control the configuration of the reaction product even when present at below micromolar concentrations. The high propensity of the Soai reaction system to produce an enantiomerically enriched product without initial bias is suggested to result from stochastic effects. These are especially important in autocatalysis because all the final products can be derived by breeding from a small number of initial events. The statistical excess of one enantiomer in that set is sufficient to generate a measurable ee in the product. The process is aided by the requirement for dimerisation before the product is an active catalyst. An enumeration that rationalises these observations is provided.     

A field deployable method for a rapid screening analysis of inorganic arsenic in seaweed

Inorganic arsenic (iAs) in 13 store-bought edible seaweed samples and 34 dried kelp (Laminaria digitata) samples was determined by a newly developed, field-deployable method (FDM) with the aid of a field test kit for arsenic in water. Results from the FDM were compared to results from speciation analysis achieved by using high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). The FDM consisted of a simple extraction method using diluted HNO₃ to quantitatively extract iAs without decomposing the organoarsenicals to iAs followed by the selective volatilisation of iAs as arsine (AsH₃) and subsequent chemo-trapping on a filter paper soaked in mercury bromide (HgBr₂) solution. Method optimization with a sub-set of samples showed 80–94% iAs recovery with the FDM with no matrix effect from organo-arsenic species in the form of dimethylarsinic acid (DMA) on the iAs concentration. The method displayed good reproducibility with an average error of ±19% and validation by HPLC-ICP-MS showed that the results from the FDM were comparable (slope = 1.03, R² = 0.70) to those from speciation analysis with no bias. The FDM can be conducted within an hour and the observed limit of quantification was around 0.05 mg kg^?1 (dry weight). This method is well suited for on-site monitoring of iAs in seaweed before it is harvested and can thus be recommended for use as a screening method for iAs in seaweed.

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Graphical abstract Screening seaweed for their inorganic arsenic concentration within one hour without bias has been made possible in the field by using a field deployable arsenic kit. Its accuracy and precision was compared to HPLC-ICPMS.

     

Investigation of sediment transport at the interface of a porous and a free flow domain

Sediment transport involves fluid flow in two different regions. In the free flow domain, the flow is governed by the viscous Newtonian fluid; sediment only occurs as suspended particles. In the porous domain however, the flow is governed by the pore geometry of the porous skeleton consisting of sedimented grains. In nature, the interface between these two domains is not a no-slip boundary for the free flow. In this study, we quantify how sediment transport is affected by the interaction of the two different flows. We do this by comparing fluid flow in no-slip bounded flow channels to fluid flow in channels containing both a free and a porous domain. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Application of the Finite Pointset Method (FPM) to the kinetic BGK model

The BGK model of rarefied gas dynamics [1] is solved numerically by using the Finite Pointset Method (FPM) [2], which is a particle method developed at the ITWM Kaiserslautern. For the implementation a semilagrangian scheme [3] is used. Numerical results are shown on the example of a Shock tube problem for different Knudsen numbers. The solutions are compared to the solutions of exact Euler in the case of small Knudsen numbers and to DSMC solutions for higher Knudsen numbers. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

On the asymptotic behavior of the Laurent coefficients of a class of Dirichlet series

Matsuoka showed an asymptotic formula for the coefficients of the Laurent expansion of ζ (s) at s = 1. In the present paper we extend this result to a large class of Dirichlet series which was first studied by Chandrasekharan and Narasimhan. Our proofs are based on a saddle point argument and use the fact that the Dirichlet series under consideration admit a functional equation. The second author was supported by the FWF project S381O.