Packing spheres tightly: influence of mechanical stability on close-packed sphere structures

Many experiments and simulations of packings of monodisperse hard spheres report a dominance of the face-centered cubic structure in the hexagonally close-packed limit, even though it has no significant energetic or entropic gain over other close-packed configurations. Combining simulations and experiments, we demonstrate that a simple mechanical instability which occurs during the packing process may play an important role in selecting the face-centered cubic structure over other close-packed alternatives. Our argument is supported by detailed quantitative analyses of key configurations in sphere packings and highlights the importance of the packing dynamics. The proposed mechanism is elementary and should therefore play a role in a wide range of sphere systems.     

Guiding Molecularly Imprinted Polymer Design by Pharmacophore Modeling

Molecularly imprinted polymers (MIP) combine the selectivity of immunoaffinity chromatography with the robustness of common solid-phase extraction in what is referred to as molecularly imprinted solid-phase extraction (MISPE). This contribution shows how MIP design may be guided by pharmacophore modeling for the example of citrinin, which is an emerging mycotoxin from cereals. The obtained pharmacophore model allowed searching public databases for a set of citrinin-mimicking molecular surrogates. Imprinted and non-imprinted polymers were subsequently obtained through bulk and core-shell polymerization in the presence of these surrogates. Evaluation of their binding ability for citrinin and structurally related ochratoxin A revealed a promising MIP derived from rhodizonic acid. A protocol for MISPE of citrinin from cereals was subsequently developed and compared to immunoaffinity chromatography with respect to clean-up efficiency and recovery.     

Structure and dynamics of water in nonionic reverse micelles: A combined time-resolved infrared and small angle x-ray scattering study

We study the structure and reorientation dynamics of nanometer-sized water droplets inside nonionic reverse micelles (water/Igepal-CO-520/cyclohexane) with time-resolved mid-infrared pump-probe spectroscopy and small angle x-ray scattering. In the time-resolved experiments, we probe the vibrational and orientational dynamics of the O-D bonds of dilute HDO:H(2)O mixtures in Igepal reverse micelles as a function of temperature and micelle size. We find that even small micelles contain a large fraction of water that reorients at the same rate as water in the bulk, which indicates that the polyethylene oxide chains of the surfactant do not penetrate into the water volume. We also observe that the confinement affects the reorientation dynamics of only the first hydration layer. From the temperature dependent surface-water dynamics, we estimate an activation enthalpy for reorientation of 45 ± 9 kJ mol(-1) (11?±?2 kcal mol(-1)), which is close to the activation energy of the reorientation of water molecules in ice.     

A ferrocene-based reagent for the conjugation and quantification of reactive metabolites

In the present study, a method for the analysis of reactive metabolites via liquid chromatography (LC) with inductively coupled plasma–mass spectrometry (MS) was developed. A ferrocenyl-modified glutathione (GSH) reagent, consisting of GSH and succinimidyl-3-ferrocenylpropionate, was synthesized. Derivatization of the tripeptide was performed at the N-terminus, leaving the nucleophilic thiol group vacant for the attack of electrophilic compounds. The potential of ferrocenylpropionate (FP)-GSH as a trapping agent for reactive metabolites was investigated using an electrochemical flow-through cell for metabolism simulation coupled online to a LC system with electrospray ionization mass spectrometric detection. The pharmaceuticals amodiaquine, an antimalarial agent, and clozapine, an antipsychotic compound, served as model substances. By proving the successful adduct formation between the reactive metabolite and ferrocene-labeled GSH, it could be shown that FP-GSH is an effective trapping agent which eases routine reversed-phase LC analyses. In contrast to GSH, which is usually used for the conjugation of reactive metabolites and where the resulting adducts often show no or only very little retention, FP-GSH facilitates the detection of the corresponding metabolite adducts due to higher retention times.     

Parameter Inequalities for Orthogonal Arrays with Mixed Levels

An important question in the construction of orthogonal arrays is what the minimal size of an array is when all other parameters are fixed. In this paper, we will provide a generalization of an inequality developed by Bierbrauer for symmetric orthogonal arrays. We will utilize his algebraic approach to provide an analogous inequality for orthogonal arrays having mixed levels and show that the bound obtained in this fashion is often sharper than Raos bounds. We will also provide a new proof of Raos inequalities for arbitrary orthogonal arrays with mixed levels based on the same method.     

Sequencing and scheduling for filling lines in dairy production

We consider an integrated sequencing and scheduling problem arising at filling lines in dairy industry. Even when a processing sequence is decided, still a scheduling problem has to be solved for the sequence. This incorporates typical side constraints as they occur also in other sequencing problems in practice. Previously, we proposed a framework for general sequencing and scheduling problems: A genetic algorithm is utilized for the sequencing, incorporating a problem specific algorithm for the fixed-sequence scheduling. In this paper, we investigate how this approach performs for filling lines. Based on insights into structural properties of the problem, we propose different scheduling algorithms. In cooperation with Sachsenmilch GmbH, the algorithm was implemented for their bottleneck filling line, and evaluated in an extensive computational study. For the real data from production, our algorithm computes almost optimal solutions. However, as a surprising result, our simple greedy algorithms outperform the more elaborate ones in many aspects, showing interesting directions for future research.