Monochromatic surface waves on impermeable boundaries in two-component poroelastic media

The dispersion relation for surface waves on an impermeable boundary of a fully saturated poroelastic medium is investigated numerically over the whole range of applicable frequencies. To this aim a linear simplified model of a two-component poroelastic medium is used. Similarly to the classical Biot’s model, it is a continuum mechanical model but it is much simpler due to the lack of coupling of stresses. However, results for bulk waves following for these two models agree very well indeed which motivates the application of the simplified model in the analysis of surface waves. In the whole range of frequencies there exist two modes of surface waves corresponding to the classical Rayleigh and Stoneley waves. The numerical results for velocities and attenuations of these waves are shown for different values of the bulk permeability coefficient in different ranges of frequencies. In particular, we expose the low and high frequency limits, and demonstrate the existence of the Stoneley wave in the whole range of frequencies as well as the leaky character of the Rayleigh wave.     

Thermodynamics of carbon monoxide adsorption on polycrystalline titania studied by static adsorption microcalorimetry

The adsorption of CO on polycrystalline TiO2 was investigated by static adsorption microcalorimetry. The initial differential heat of adsorption (qdiff,0) of CO on polycrystalline titania is 40 kJ/mol, and the standard adsorption entropy (Deltas0) is -104 J mol(-1) K(-1). These results are consistent with those derived from temperature-programmed desorption and FTIR results in the literature. The good reproducibility of the isotherms and the stable qdiff indicate that the lattice oxygen and hydroxyl groups on titania surface are basically not reactive to adsorbed CO.     

Development of adamantan-1-yl-methoxy-functionalized 1-deoxynojirimycin derivatives as selective inhibitors of glucosylceramide metabolism in man

In this article, we present a straightforward synthesis of adamantan-1-yl-methoxy-functionalized 1-deoxynojirimycin derivatives. The used synthetic routes are flexible and can be used to create a wide variety of lipophilic mono- and difunctionalized 1-deoxynojirimycin derivatives. The compounds reported here are lipophilic iminosugar based on lead compound 4, a potent inhibitor of the three enzymes involved in the metabolism of the glycosphingolipid glucosylceramide. Iminosugar-based inhibitors of glucosylceramide synthase, one of these three enzymes, have attracted increasing interest over the past decade due to the crucial role of this enzyme in glycosphingolipid biosynthesis. Combined with the fact that an increasing number of pathological processes are being linked to excessive glycosphingolipid levels, glucosylceramide synthase becomes a very attractive therapeutic and research target. Our results presented here demonstrate that relocating the lipophilic moiety from the nitrogen atom to other positions on the 1-deoxynojirimycin ring system does not lead to a more potent or selective inhibitor of glucosylceramide synthase. The beta-aza-C-glycoside analogue (17) retained the best inhibitory potency for glucosylceramide synthase and is a more potent inhibitor than the therapeutic agent N-butyl-1-deoxynojirimycin (3), marketed as treatment for Gaucher disease under the commercial name Zavesca.     

The influence of fluoroquinolone drugs on the bacterial growth of S. epidermidis utilizing the unique potential of vibrational spectroscopy

Increasing resistance of many antibiotics has made the design of new drugs necessary. To assist a target-oriented search for new structures and for the elucidation of the mode of action of existing drugs, powerful analytical techniques are required. In this work, vibrational spectroscopy is used to shed more light on the as-yet elusive interaction of gyrase inhibitors of the fluoroquinolone type with their biological target inside the Gram-positive bacterium Staphylococcus epidermidis by investigating whole-cell changes that occur as a result of the presence of the drug moxifloxacin. IR absorption and Raman spectra with excitation off resonance (lambda exc = 532 nm) and in resonance with the biological targets DNA and the aromatic amino acids of gyrase (lambda exc = 244 nm) were recorded for unperturbed bacteria and bacteria in varying drug concentrations (0.08, 0.16, 0.27, and 0.62 microg moxifloxacin/mL bacterial culture). The spectral changes caused by the action of the drug were analyzed with the help of statistical methods, such as hierarchical cluster analysis (HCA), principal component analysis (PCA), and Fisher's linear discriminant analysis (LDA) combined with variable selection. The wavenumbers mostly affected by the action of the drug could be assigned to protein and DNA moieties, supporting the proposed mechanisms of a tertiary complex of the fluoroquinolone, the enzyme gyrase, and DNA.     

On extremal hypergraphs for Hamiltonian cycles

We study sufficient conditions for Hamiltonian cycles in hypergraphs, and obtain both Turán- and Dirac-type results. While the Turán-type result gives an exact threshold for the appearance of a Hamiltonian cycle in a hypergraph depending only on the extremal number of a certain path, the Dirac-type result yields a sufficient condition relying solely on the minimum vertex degree.     

Surface characterization of polymer‐stabilized colloidal metal catalysts

A new method for measuring hydrogen chemisorption on polymer‐stabilized metal colloids, in conjunction with variable coverage infrared spectroscopy of adsorbed CO, is applied to analyse the surface of Pt/polyvinylpyrrolidone colloids. The results correlate well with the measured activity of Pt/PVP as a hydrogenation catalyst.     

Revealing structure formation in PCPDTBT by optical spectroscopy

The low‐bandgap polymer poly{[4,4‐bis(2‐ethylhexyl)‐cyclopenta‐(2,1‐b;3,4‐b′)dithiophen]‐2,6‐diyl‐alt‐(2,1,3‐benzo‐thiadiazole)?4,7‐diyl} (PCPDTBT) is widely used for organic solar cell applications. Here, we present a comprehensive study of the optical properties as a function of temperature for PCPDTBT in solution and in thin films with two distinct morphologies. Using absorption and photoluminescence spectroscopy as well as Franck‐Condon analyses, we show that PCPDTBT in solution undergoes a phase transformation at 300 K from a disordered to a truly aggregated state on cooling. The saturation value of aggregates in solution is reached in PCPDTBT thin films at any temperature. In addition, we demonstrate that the photophysical properties of the aggregates in films are similar to those in solution and that a low percentage of thermally activated excimer states is present in the films at temperatures above 200 K. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1416–1430     

WAVELENGTH DEPENDENCE FOR AMT CROSSLINKING OF pBR322 DNA

Abstract The wavelength dependence for 4'aminomethyl-4,5',8-trimethylpsoralen crosslinking of a linearized plasmid DNA (pBR322) by narrow band UV-A light (298–382 nm) has been determined. Maximal levels of crosslinking occurred with light in the 322–346 nm range. Crosslinks were shown to be photoreversible by shorter wavelength photons (298 and 310 nm). The correlation between the wavelength dependence for crosslink formation and the optimal wavelength for most psoralen action spectra further supports the notion that crosslinks are the major lesion responsible for the effectiveness of psoralen plus ultraviolet A therapies.     

Understanding the Sequence Preference of Recurrent RNA Building Blocks using Quantum Chemistry: The Intrastrand RNA Dinucleotide Platform

Folded RNA molecules are shaped by an astonishing variety of highly conserved noncanonical molecular interactions and backbone topologies. The dinucleotide platform is a widespread recurrent RNA modular building submotif formed by the side-by-side pairing of bases from two consecutive nucleotides within a single strand, with highly specific sequence preferences. This unique arrangement of bases is cemented by an intricate network of noncanonical hydrogen bonds and facilitated by a distinctive backbone topology. The present study investigates the gas-phase intrinsic stabilities of the three most common RNA dinucleotide platforms - 5'-GpU-3', ApA, and UpC - via state-of-the-art quantum-chemical (QM) techniques. The mean stability of base-base interactions decreases with sequence in the order GpU > ApA > UpC. Bader's atoms-in-molecules analysis reveals that the N2(G)…O4(U) hydrogen bond of the GpU platform is stronger than the corresponding hydrogen bonds in the other two platforms. The mixed-pucker sugar-phosphate backbone conformation found in most GpU platforms, in which the 5'-ribose sugar (G) is in the C2'-endo form and the 3'-sugar (U) in the C3'-endo form, is intrinsically more stable than the standard A-RNA backbone arrangement, partially as a result of a favorable O2'…O2P intra-platform interaction. Our results thus validate the hypothesis of Lu et al. (Lu Xiang-Jun, et al. Nucleic Acids Res. 2010, 38, 4868-4876), that the superior stability of GpU platforms is partially mediated by the strong O2'…O2P hydrogen bond. In contrast, ApA and especially UpC platform-compatible backbone conformations are rather diverse and do not display any characteristic structural features. The average stabilities of ApA and UpC derived backbone conformers are also lower than those of GpU platforms. Thus, the observed structural and evolutionary patterns of the dinucleotide platforms can be accounted for, to a large extent, by their intrinsic properties as described by modern QM calculations. In contrast, we show that the dinucleotide platform is not properly described in the course of atomistic explicit-solvent simulations. Our work also gives methodological insights into QM calculations of experimental RNA backbone geometries. Such calculations are inherently complicated by rather large data and refinement uncertainties in the available RNA experimental structures, which often preclude reliable energy computations.