Production of a calibrant certified reference material for determination of the estrogenic mycotoxin zearalenone

Several previous interlaboratory studies in the field of mycotoxin analysis have revealed considerable problems, apparent as high between-laboratory standard deviations, or rather non-comparable and non-traceable results. A major reason is lack of proper calibrants for external calibration. Public awareness of substances that mimic or interfere with the activity of natural hormones (endocrine disrupters) has led to increased interest in mycotoxins with estrogenic potential, e.g. zearalenone (ZON). During a large-scale standard measurement and testing (SMT) project of the European Commission (EC) dealing with the preparation and certification of reference materials for determination of the mycotoxin ZON in maize, a ZON calibrant in acetonitrile was prepared and intensively checked for purity, homogeneity, and stability. Preparation of the material, study of its homogeneity and stability, and characterisation of the calibrant on the basis of its preparation, with discussion of the results obtained, are described in this paper. The certified value of 9.95 µg mL^–1 for ZON in acetonitrile and its corresponding expanded uncertainty of ±0.30 µg mL^–1 were calculated in compliance with the Guide to the Expression of Uncertainty in Measurement (GUM).     

MEPS as a rapid sample preparation method to handle unstable compounds in a complex matrix: determination of AZD3409 in plasma samples utilizing MEPS-LC-MS-MS

The aim of the present investigation is to develop a simple, fast, and sensitive method for the determination of a new candidate drug, AZD3409, in rat, dog, and human plasma samples. AZD3409 is stable in aqueous solutions at low pH (< 4) but not in whole blood or in plasma. In rat plasma at 25 degrees C, more than 90% of the compound is degraded within 40 min. When 20 mg of NaF and 50 microL of protease inhibitor cocktail are added to 1.0 mL of rat blood, AZD3409 is stable for up to about 90 min. Due to the instability of AZD3409, microextraction in packed syringe (MEPS) is used as an online and fast sample-preparation method, followed by liquid chromatography-tandem mass spectrometry (LC-MS-MS) for the quantitation of this compound in plasma samples. In MEPS, the sampling sorbent is 1 mg of polystyrene polymer packed in a 250-microL syringe. When the plasma sample (50-250 microL) is withdrawn through the syringe by an autosampler, the analyte is adsorbed to the solid phase. The analyte is then eluted with an organic solvent such as methanol or the LC mobile phase (20-50 microL) directly into the instrument's injector. MEPS is rapid and easy to use. The lower limit of quantitation for AZD3409 is established to be 0.024 microM. The accuracy of the quality-control samples ranged from 89% to 102%, and the precision (C.V.%) had a value of 11-16% for the plasma samples. The calibration curve in plasma is obtained in the concentration range 0.022-9.0 microM. The coefficients of determination (R2) for plasma samples were > or = 0.998 for all runs. The present method is used for the analysis of rat and dog plasma samples.     

Effect of polymer architecture on the adsorption properties of a nonionic polymer

The adsorption of a linear- and bottle-brush poly(ethylene oxide (PEO))-based polymer, having comparable molecular weights, was studied by means of quartz crystal microbalance with dissipation monitoring ability (QCM-D) and AFM colloidal probe force measurements. The energy dissipation change monitored by QCM-D and the range of the steric forces obtained from force measurements demonstrated that linear PEO forms a more extended adsorption layer than the bottle-brush polymer, despite that the adsorbed mass is higher for the latter. Competitive adsorption studies revealed that linear PEO is readily displaced from the interface by the bottle-brush polymer. This was attributed to the higher surface affinity of the latter, which is governed by the number of contact points between the polymers and the interface, and the smaller loss of conformational entropy.     

Determination of binding affinity of enantiomers to albumin by liquid chromatography

The principles of the determination of the binding affinity constants of small molecules to albumin by liquid chromatography, using albumin as a mobile phase additive, are outlined. Chromatographic conditions for determinations of constants are presented and applied to enantiomers of tryptophan and omeprazole. The influence of albumin on the retaining properties of LiChrosorb RP-8, Phenyl Hypersil and LiChrosorb Diol was studied.     

Electron and energy transfer in donor-acceptor systems with conjugated molecular bridges

Electron and energy transfer reactions in covalently connected donor-bridge-acceptor assemblies are strongly dependent, not only on the donor-acceptor distance, but also on the electronic structure of the bridge. In this article we describe some well characterised systems where the bridges are pi-conjugated chromophores, and where, specifically, the interplay between bridge length and energy plays an important role for the donor-acceptor electronic coupling. For any application that relies on the transport of electrons, for example molecule based solar cells or molecular scale electronics, it will be imperative to predict the electron transfer capabilities of different molecular structures. The potential difficulties with making such predictions and the lack of suitable models are also discussed.     

Bipartite 2‐Factorizations of Complete Multipartite Graphs

It is shown that if K is any regular complete multipartite graph of even degree, and F is any bipartite 2‐factor of K, then there exists a factorization of K into F; except that there is no factorization of K_{6, 6} into F when F is the union of two disjoint 6‐cycles.     

Femtosecond coherent anti-Stokes Raman-scattering polarization beat spectroscopy of I2-Xe complex in solid krypton

Time-resolved coherent anti-Stokes Raman-scattering (CARS) measurements are carried out to study the interaction between xenon atom and iodine molecule in a solid krypton matrix. Interference between the CARS polarizations of the "free" and complexed iodine molecules is observed, while the quantum beats of the complex are not detected due to low concentration. Vibrational analysis based on the polarization beats yields accurate molecular constants for the I2-Xe complex. The harmonic frequency of the I2-Xe complex is found to be redshifted by 0.90 cm-1 when compared to the free I2, whereas the anharmonicity is approximately the same. The dephasing rate of the complex is found to be somewhat higher than that of the free iodine molecule in solid Kr, showing that the complexation affects dephasing, although not dramatically. Molecular dynamics simulations are carried out to find the conformation of the complex, and wave packet simulations are used to reproduce the CARS signal to confirm the assignments of the observed beatings as quantum and polarization beats. The results show that the polarization beats are a useful tool for investigating weak interactions in condensed phase.