Development of reference materials for microbiological analysis

The reliability of reference materials (RMs) depends on properties such as fitness, robustness, commutability, stability and homogeneity. The development of RMs for microbiological analysis is especially challenged through questions around the stabilisation and recovery of viable cells, the dispersion of precise numbers of cells, matrix effects and, when using molecular techniques, the presence of nucleic acids (e.g. DNA) of dead and live target organisms. However, RMs are indispensable tools for quality control in microbiological analysis. The Institute for Reference Materials and Measurements (IRMM), as part of the European Commission, concentrates its efforts on the development of RMs to support the development, implementation and monitoring of EU legislation. A special focus is given to highly precise RMs for presence/absence and enumeration tests in microbiological food and water analysis. Another group of new RMs certified by the IRMM comprise DNA-based materials to control the identity of micro-organisms in qualitative assays. All of these activities serve to improve quality control in microbiological analysis. Presented at ‘BERM-10’, April 2006, Charleston, SC, USA.     

Facilitating access to the most easily ionized molecule: an improved synthesis of the key intermediate, W2(hpp)4Cl2, and related compounds

A far superior synthesis is reported for W(2)(hpp)(4)Cl(2), a key intermediate in the synthesis of the most easily ionized closed-shell molecule W(2)(hpp)(4) (hpp = the anion of the bicyclic guanidine compound 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine). At 200 degrees C, the one-pot reaction of the air-stable and commercially available compounds W(CO)(6) and Hhpp in o-dichlorobenzene produces W(2)(hpp)(4)Cl(2) in multigram quantities with isolated yields of over 90%. At lower temperatures, the reaction can lead to other compounds such as W(Hhpp)(2)(CO)(4) or W(2)(mu-CO)(2)(mu-hpp)(2)(eta(2)-hpp)(2), which are isolable in good purity depending upon the specific conditions employed. These compounds provide insight into the reaction pathway to W(2)(hpp)(4)Cl(2) and W(2)(hpp)(4). Two additional derivatives, W(2)(hpp)(4)X(2) where X is PF(6)(-) or the anion tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (TFPB), have also been synthesized and structurally characterized. A comparison of the electrode potentials of W(2)(mu-CO)(2)(mu-hpp)(2)(eta(2)-hpp)(2) and the di-p-anisylformamidinate analogue shows that oxidation of the hpp compound is significantly displaced (1.12 V) and shows that the bicyclic guanidinate ligand is considerably better than the formamidinate anion at stabilizing high oxidation states. A differential pulse voltammogram of W(2)(hpp)(4)(TFPB)(2) in THF shows two reduction processes with an E(1/2) of -0.97 V for the first and -1.81 V (vs Ag/AgCl) for the second. DFT calculations on the W(2)(hpp)(4)(2+) units in W(2)(hpp)(4)X(2) compounds show that the metal-metal bonding orbitals are destabilized by the axial ligands, which accounts for significant variations in the W-W distances. The low-energy gas-phase ionizations of W(2)(hpp)(4) are also reported and discussed.     

Influence of particle-particle interactions and particles rotational motion in traveling wave dielectrophoresis

Traveling wave dielectrophoresis provides an interesting method for the controlled movement of microsized particles in suspended mixtures, and as such is a promising tool in microfluidic technology. In this case, the electrostatic force acting on the particles has two components: one due to the spatially varying magnitude of the electric field and the other due to the spatially varying phase. The actual movement of the particle is determined by the combined effect of these two forces and corresponding torques, the viscous drag exerted by the fluid on the particle, and the electrostatic and hydrodynamic particle-particle interactions. This paper presents the first numerical simulations of the motion of particles subjected to all previous forces and torques. Our technique is based on a finite-element scheme in which the particles are moved using a direct simulation scheme respecting the fundamental equations of motion for both the fluid and the solid particles. The fluid-particle motion is resolved by the method of distributed Lagrange multipliers and the electrostatic forces are computed using the point-dipole approximation. Our simulations show that the particle behavior strongly depends on the mismatch of the dielectric properties between the particles and the fluid, and that the particle-particle interaction force as well as particles rotation speeds play crucial roles in the various regimes.     

Vibronic coupling in organic semiconductors: the case of fused polycyclic benzene-thiophene structures

The nature of vibronic coupling in fused polycyclic benzene-thiophene structures has been studied using an approach that combines high-resolution gas-phase photoelectron spectroscopy measurements with first-principles quantum-mechanical calculations. The results indicate that in general the electron-vibrational coupling is stronger than the hole-vibrational coupling. In acenedithiophenes, the main contributions to the hole-vibrational coupling arise from medium- and high-frequency vibrations. In thienobisbenzothiophenes, however, the interaction of holes with low-frequency vibrations becomes significant and is larger than the corresponding electron-vibrational interaction. This finding is in striking contrast with the characteristic pattern in oligoacenes and acenedithiophenes in which the low-frequency vibrations contribute substantially only to the electron-vibrational coupling. The impact of isomerism has been studied as well.     

Determination of pharmaceuticals, iodinated contrast media and musk fragrances in sludge by LC/tandem MS and GC/MS

Analytical methods have been developed that allow for the determination of antiphlogistics, lipid regulators, the antiepileptic carbamazepine, cytostatic agents, the psychiatric drug diazepam and iodinated contrast media (ICM) as well as two major polycyclic musk fragrances HHCB (galaxolide) and AHTN (tonalide) in activated and digested sludge. The procedures consist of ultrasonic solvent extraction (USE) using methanol/acetone or pressurized liquid extraction (PLE) using 100% methanol. Clean-up was performed with C18ec material and silica gel followed by LC tandem MS (electrospray or atmospheric pressure chemical ionization) detection for pharmaceuticals and iodinated contrast media as well as GC/MS in the SIM mode for musk fragrances. Absolute recoveries from spiked activated sludge in general ranged from 88+/-4 to 119+/-20% for ICM and were 78+/-15 and 87+/-10% for the AHTN and HHCB, respectively. For the pharmaceuticals, absolute recoveries in activated sludge ranged between 43 and 78%. Subsequently, compensation of losses was carried out by using surrogate standards (acidic pharmaceuticals: fenoprop, neutral pharmaceuticals: dihydro-carbamazepine, musk fragrances: AHTN-D3). With one exception the recoveries were also adequate in digested sludge ranging from 43% to 120%.     

Multi-dimensional,mechanical stimulation of cartilage implants

In biomedical engineering, it is a common practice to replace injured cartilage by implants, which are seeded with human cartilage cells. Before implanting, the implants are cultivated and usually stimulated electrically or mechanically in a bioreactor to initiate cell multiplication and oriented cell growth. A new experimental set-up is developed leading to the possibility of stimulating such implants in a multi-dimensional, physiologically consistent way. In cooperation with the University Medical Centre Aachen, a human knee simulator is developed. Cell-seeded implants are placed in a recreated human environment and stimulated with several load cycles of reproduced walking. After the cultivation period, the implanted material is removed and biologically and mechanically evaluated. The quality of the implanted material as well as the influence of the body-conformable load on the material is studied. To understand the correlation between tissue remodelling and mechanical load history, the load and movement scenario is also numerically investigated. For this reason, the experiment is transferred to a geometrically realistic FE model of a human knee. As a first approach, an elastic material model is used. The aim is to have a predictive FE model with an optimal trade-off between accuracy and efficiency using an appropriate material formulation. The results will be compared to experimental data. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Abstract Hardy-Sobolev spaces and interpolation

The purpose of this work is to describe an abstract theory of Hardy-Sobolev spaces on doubling Riemannian manifolds via an atomic decomposition. We study the real interpolation of these spaces with Sobolev spaces and finally give applications to Riesz inequalities.     

The Si-Si effect on ionization of beta-disilanyl sulfides and selenides

The ionization energies of conformationally constrained, newly synthesized beta-disilanyl sulfides and selenides were determined by photoelectron spectroscopy. These ionization energies reflect substantial (0.53-0.75 eV) orbital destabilizations. The basis for these destabilizations was investigated by theoretical calculations, which reveal geometry-dependent interaction between sulfur or selenium lone pair orbitals and sigma-orbitals, especially Si-Si sigma-orbitals. These results presage facile redox chemistry for these compounds and significantly extend the concept of sigma-stabilization of electron-deficient centers.