Solid‐phase extraction of plant thionins employing aluminum silicate based extraction columns

Thionins belong to a family of cysteine‐rich, low‐molecular‐weight (～5 KDa) biologically active proteins in the plant kingdom. They display a broad cellular toxicity against a wide range of organisms and eukaryotic cell lines. Thionins protect plants against different pathogens, including bacteria and fungi. A highly selective solid‐phase extraction method for plant thionins is reported deploying aluminum silicate (3:2 mullite) powder as a sorbent in extraction columns. Mullite was shown to considerably improve selectivity compared to a previously described zirconium silicate embedded poly(styrene‐co‐divinylbenzene) monolithic polymer. Due to the presence of aluminum(III), mullite offers electrostatic interactions for the selective isolation of cysteine‐rich proteins. In comparison to zirconium(IV) silicate, aluminum(III) silicate showed reduced interactions towards proteins which resulted into superior washings of unspecific compounds while still retaining cysteine‐rich thionins. In the presented study, European mistletoe, wheat and barley samples were subjected to solid‐phase extraction analysis for isolation of viscotoxins, purothionins and hordothionins, respectively. Matrix‐assisted laser desorption/ionization time of flight mass spectroscopy was used for determining the selectivity of the sorbent toward thionins. The selectively retained thionins were quantified by colorimetric detection using the bicinchoninic acid assay. For peptide mass‐fingerprint analysis tryptic digests of eluates were examined.     

Mesomorphism of complexed 2,6-disubstituted pyridine ligands: crystal and molecular structure of two bent-core pyridines

Bent-core, polycatenar pyridines are reported, synthesized via a Siegrist coupling of di- and tri-alkoxybenzylidene fragments with 2,6-dimethylpyridine. None of these pyridines was liquid crystalline. Isomeric materials based on a 3,5-disubstituted pyridine core were mesomorphic in hydrogen-bonded complexes, whereas these new materials were not. However, the new pyridines did form mesomorphic metal complexes with silver salts. Some insight into this behaviour is gleaned from single crystal structure determinations of the model systems, 3,5-bis(3',4'-dimethoxystyryl)pyridine and 2,6-bis(3',4'-dimethoxystyryl)pyridine.     

Pairs selection and outranking: An application to the S&P 100 index

Pairs trading is a popular quantitative speculation strategy. This article proposes a general and flexible framework for pairs selection. The method uses multiple return forecasts based on bivariate information sets and multi-criteria decision techniques. Our approach can be seen as a sort of forecast combination but the output of the method is a ranking. It helps to detect potentially under- and overvalued stocks. A first application with S&P 100 index stocks provides promising results in terms of excess return and directional forecasting.     

Online coupling of thin layer chromatography with matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry: synthesis and application of a new material for the identification of carbohydrates by thin layer chromatography/matrix free material enhanced laser desorption/ionization mass spectrometry

This article describes the online hyphenation of thin layer chromatography with matrix free material enhanced laser desorption/ionization mass spectrometry (mf‐MELDI‐MS), the preparation of new material for MELDI and application of this newly synthesized material using TLC/MELDI‐MS for the analysis of carbohydrate reference standards and plant extracts. Samples included within these analyses are standard solutions of glucose, sucrose, raffinose and a plant extract of Quercus robur, which is used for its anti‐inflammatory, anti‐viral and anthelminitc properties in phytomedicine. A new material for mf‐MELDI‐MS is prepared by immobilizing bradykinin – a peptide, on silica gel coupled to 4‐(3‐triethoxysilylpropylureido)azobenzene. This modification enables the absorption of laser energy sufficient for desorption and ionization of low molecular weight molecules like carbohydrates and amino acids. The newly synthesized material delivered excellent results in respect to signal‐to‐noise (S/N) ratio (S/N ratio: >9/1) and sensitivity (limit of detection (LOD): lower to ng/µL). Hyphenation of TLC to MELDI‐MS employing the novel developed material simultaneously as chromatographic and mass spectrometric sorbent was shown for the first time for the analysis of low molecular weight molecules like mono‐ and oligosaccharides. Copyright © 2010 John Wiley & Sons, Ltd.     

Comparative analysis of naphthodianthrone and phloroglucine derivatives in St. John's Wort extracts by near infrared spectroscopy, high-performance liquid chromatography and capillary electrophoresis

A near infrared spectroscopic (NIRS) method is established for quantitative determination of naphthodianthrones and phloroglucine derivatives in St. John's Wort extracts. The validated NIRS method is compared with optimised liquid chromatography (LC) and capillary electrophoresis (CE), applying UV as a detection tool. Optimisation of stationary and mobile phase conditions in reversed-phase liquid chromatography (RP-LC) allow separating the derivatives of interest with high peak symmetry and robustness. Elution takes 15 and 25 min on non-porous or porous silica C18 with different porosities, respectively. Capillary electrophoresis (CE) is used for cross-validation of RP-LC. CE enables baseline separation of hypericine and pseudohypericine in less than 2 min, but is ten times less sensitive. The validated RP-LC is chosen as a reference method for calibration of the NIRS-system. Analysis of 80 St. John's Wort extracts (320 NIR spectra) and the subsequent chemometric calculations of the best regression model show that NIRS is suitable for analysis of hypericine, pseudohypericine and hyperforine. RP-LC or CE must be employed for the other remaining lower concentrated naphthodianthrone and phloroglucine derivatives. Hypericine and hyperforine are analysed via NIRS with a standard error of estimation (SEE) of 0.52 and 0.50 μg mL⁻¹ and standard error of prediction (SEP) of 0.64 and 0.71 μg mL⁻¹ within few seconds. The current study demonstrates the suitability of NIRS as an alternative to LC and CE for St. John's Wort producing phytopharmaceutical industry. The short analysis time of few seconds’ assures high sample throughput in routine analysis.     

Three-stage switching of surface wetting using phosphate-bearing polymer brushes

Surface initiated polymer brushes containing phosphate side groups have been used to reversibly switch wettability and hydration between three different states.     

First-Year Undergraduate Laboratory Experiments with Zeolites

The synthesis of Zeolite A or Linde Type A zeolite is described as an undergraduate laboratory geared for the first-year student in general chemistry. The procedure describes the synthesis, isolation, and various qualitative and quantitative characterization methods related to the materials water-softening ability.