Manifestation of biquadratic coupling in the smectic C* phase soft mode dielectric response

The soft mode dielectric response of three ferroelectric chiral smectic C* substances is studied in the vicinity of the smectic C*-smectic A* phase transition. For some substances the soft mode dielectric strength exhibits a pronounced anomaly in the C* phase just below the phase transition. We show how this anomaly can be systematically correlated with a corresponding anomaly in the experimentally determined ratio of spontaneous polarization over tilt. By comparing the experimental results with the theoretical predictions of an extended Landau model, we demonstrate how the crossover behaviour of the system can be interpreted as being the consequence of the presence of a biquadratic coupling between tilt and polarization in the Landau free-energy of the system.     

Cationic poly(methacryl oxyethyl trimethylammonium) and its poly(ethylene glycol)‐grafted analogue as capillary coating materials in electrophoresis

Cationic polyelectrolytes were synthesized and used as semipermanent coating materials for capillaries in electrophoresis. The polyelectrolytes used were a homopolymer of poly(methacryl oxyethyl trimethylammonium chloride) (PMOTAC) and its poly(ethylene glycol) (PEG)‐grafted analogue. Two PMOTAC polyelectrolytes, with molar masses of 85,000 and 300,000 g/mol, and PEG‐grafted PMOTAC with a molar mass of 280,000 g/mol were synthesized and then characterized by size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) spectroscopy. Attachment of the polyelectrolytes to the wall of the fused silica capillary for electrophoresis caused the electroosmotic flow (EOF) to reverse. The polyelectrolyte coatings were tested over the pH range 2–11 at different buffer ionic strengths, and the most stable and strongest anodic EOFs were obtained at acidic pH values with low ionic strength buffers. Between runs the capillary is merely rinsed for 2 or 3 min with the background electrolyte solution. With the PMOTAC coatings at pH values ≤5, the RSDs of the EOFs were less than 2.9% after 60 injections. The effects of the molar mass of the polycation and of PEGylation of PMOTAC on the interactions between the polycations and basic proteins were studied at acidic pH values. The differences in the effective electrophoretic mobilities, resolution values, and plate numbers of the proteins with the different coatings were due to the EOF, as demonstrated through calculations of reduced mobilities, relative resolution values, and relative plate numbers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2655–2663, 2007     

The structure of defect Ru4Si3

The nature of the defect structure of Ru₄Si₃ has been studied with electron diffraction and electron microscopy methods. Lattice image pictures, interpreted with histogram analysis, reveal that planar defects of chemical twinning type are common in the crystals.     

Chemical fourling on the unit cell level as a structure-building operation in the solid state

Chemical fourling on the unit-cell level is introduced as a structure-building operation in the solid state. A chemical fourling structure is achieved when two twin planes are perpendicular to each other. Each fourling unit has infinite extension in only one direction and can be related to a well-known structure type or packing of atoms. The structures of the tetragonal tungsten bronzes M_xWO₃ and Pd(NH₃)₄Cl · H₂O are presented as examples of chemical fourlings of cubic close packing. The structures of SeO₂, Mn₂Hg₅, and Zr₂F₇O are shown to be a sequence of chemical fourlings of primitive cubic packing. Chemical fourling units of hexagonal close packing are found in the structures of tetragonal Ti₃Sb, α-V₃S and Sb₆O₇(SO₄)₂. The structures of CuAl₂, SeTl, NbTe₄, Ti₃Sb, and MnU₆ all have the same chemical fourling unit. Cr₂₃C₆ is described as a bounded chemical fourling of cubic close packing.     

In vitro high throughput screening of compounds for favorable metabolic properties in drug discovery

Drug metabolism can have profound effects on the pharmacological and toxicological profile of therapeutic agents. In the pharmaceutical industry, many in vitro techniques are in place or under development to screen and optimize compounds for favorable metabolic properties in the drug discovery phase. These in vitro technologies are meant to address important issues such as: (1) is the compound a potent inhibitor of drug metabolising enzymes (DMEs)? (2) does the compound induce the expression of DMEs? (3) how labile is the compound to metabolic degradation? (4) which specific enzyme(s) is responsible for the compound's biotransformation? and (5) to which metabolites is the compound metabolized? Answers to these questions provide a basis for judging whether a compound is likely to have acceptable pharmacokinetic properties in vivo. To address these issues on the increasing number of compounds inundating the drug discovery programs, high throughput assays are essential. A combination of biochemical advances in the understanding of the function and regulation of DMEs (in particular, cytochromes P450, CYPs) and automated analytical technologies are revolutionizing drug metabolism research. Automated LC-MS based metabolic stability, fluorescence, radiometric and LC-MS based CYP inhibition assays are now in routine use. Automatible models for studying CYP induction based on enzyme activity, quantitative RT-PCR and reporter gene systems are being developed. We will review the utility and limitations of these HTS approaches and highlight on-going developments and emerging technologies to answer metabolism questions at the different stages of the drug discovery process.     

Dissociative recombination cross section and branching ratios of protonated dimethyl disulfide and N-methylacetamide

Dimethyl disulfide (DMDS) and N-methylacetamide are two first choice model systems that represent the disulfide bridge bonding and the peptide bonding in proteins. These molecules are therefore suitable for investigation of the mechanisms involved when proteins fragment under electron capture dissociation (ECD). The dissociative recombination cross sections for both protonated DMDS and protonated N-methylacetamide were determined at electron energies ranging from 0.001 to 0.3 eV. Also, the branching ratios at 0 eV center-of-mass collision energy were determined. The present results give support for the indirect mechanism of ECD, where free hydrogen atoms produced in the initial fragmentation step induce further decomposition. We suggest that both indirect and direct dissociations play a role in ECD.