Large Deviations from a Stationary Measure for a Class of Dissipative PDEs with Random Kicks

We study a class of dissipative PDEs perturbed by a bounded random kick force. It is assumed that the random force is nondegenerate, so that the Markov process obtained by the restriction of solutions to integer times has a unique stationary measure. The main result of the paper is a large deviations principle for occupation measures of the Markov process in question. The proof is based on Kifer's large‐deviation criterion, a coupling argument for Markov processes, and an abstract result on large‐time asymptotic for generalized Markov semigroups.© 2015 Wiley Periodicals, Inc.     

Nafion-graphene composite film modified glassy carbon electrode for voltammetric determination of p-aminophenol

A Nafion-graphene (Nafion-GR) nanocomposite film modified glassy carbon electrode was fabricated by a simple drop-casting method, and used in the electrochemical detection of p-aminophenol (4-AP). Owing to the large surface area, good conductivity of GR and good affinity of Nafion, the sensor exhibited excellent electrocatalytic activity for the oxidation of 4-AP. The electrochemical behaviors of 4-AP on Nafion/GR film modified glassy carbon electrodes were investigated by cyclic voltammetry and differential pulse voltammetry. A calibration curve is constructed in the same matrix, urine, as the unknown samples to be analyzed. The Nafion-GR film modified electrode was linearly dependent on the 4-AP concentration and the linear analytical curve was obtained in the ranges of 0.5–200 μM with differential pulse voltammetry (DPV) and the detection limit was 0.051 μM. The Nafion-graphene nanocomposite modified electrode exhibited good reusability than pure graphene modified GCE. This procedure can be used for the determination of p-aminophenol in the presence of its degradation products and paracetamol. Finally, the proposed method was successfully used to determine p-aminophenol in local tap water samples in urine samples and pharmaceutical preparations.     

Novel anhydrous proton conducting copolymers of 1‐vinyl‐1,2,4‐triazole and diisopropyl‐p‐vinylbenzyl phosphonate

Phosphonic acid functional polymers are currently of interest because of their high proton conductivity in humidified and anhydrous systems. In addition, heterocyclic compounds are used in anhydrous proton conducting polymer membranes. In that study, a new copolymer based on 1‐vinyl‐1,2,4‐triazole (VTri) and diisopropyl‐p‐vinylbenzyl phosphonate (VBP) was synthesized, and their thermal, chemical, and proton conducting properties were investigated. The copolymers were synthesized by free radical copolymerization of the corresponding monomers at several monomer feed ratios to obtain P(VTri‐co‐VBP) copolymers. The copolymer samples were then hydrolyzed to produce poly(vinyl triazole‐co‐vinyl phosphonic acid) copolymers. The composition of the copolymers was determined by elemental analysis. The copolymerization and hydrolysis reactions were verified by Fourier transform infrared spectroscopy and ion exchange capacity measurements. Thermogravimetry analysis indicates that the copolymers are thermally stable up to 300°C. In order to increase the proton conductivity, the copolymers were doped with H₃PO₄ at several stoichometric ratios. The proton conductivity increases with triazole and phosphoric acid content. In the absence of humidity, the copolymer electrolyte, P(VTri‐co‐VBPA)1:0.5 X = 2, showed a proton conductivity of 0.005 S/cm at 150°C. Copyright © 2013 John Wiley & Sons, Ltd.     

X-ray structural analysis and antitumor activity of new salicylic acid derivatives

Tetrakis-, tris-, bis-, and mono salicylic acid derivatives 1–4 were synthesized by reaction of methyl 2-hydroxy benzoate (methyl salicylate) with 2,2-bis (hydroxymethyl) propane-1,3-diol (pentaerythritol) in the presence of sodium. Yields of different salicyloyloxy derivatives were changed by varying the molar ratios of reactants. For compounds 2 and 3, X-ray structure analysis was performed, as well as molecular energy minimization, to define their conformation in terms of their energy minima. Comparison of crystal and energy minimized structures for these two compounds (2 and 3) revealed that the intramolecular hydrogen bonds play an important role, stabilizing conformation of the most part of the molecule. The antioxidant activity and cytotoxicity of the synthesized derivatives were evaluated in a series of in vitro tests, as well as 17β-hydroxysteroid dehydrogenase type 2 inhibition potency. Tetrakis salicyloyloxy derivative 1 expressed the highest antioxidant potency, tris salicyloyloxy derivative 2 was the best inhibitor of 17βHSD2 enzyme, while bis salicyloyloxy derivative 3 showed strong cytotoxicity against prostate and breast cancer cells with no cytotoxicity against healthy cells.     

Chemometrics approach for the prediction of structure–activity relationship for membrane transporter bilitranslocase

Membrane transport proteins are essential for cellular uptake of numerous salts, nutrients and drugs. Bilitranslocase is a transporter, specific for water-soluble organic anions, and is the only known carrier of nucleotides and nucleotide-like compounds. Experimental data of bilitranslocase ligand specificity for 120 compounds were used to construct classification models using counter-propagation artificial neural networks (CP-ANNs) and support vector machines (SVMs). A subset of active compounds with experimentally determined transport rates was used to build predictive QSAR models for estimation of transport rates of unknown compounds. Several modelling methods and techniques were applied, i.e. CP-ANN, genetic algorithm, self-organizing mapping and multiple linear regression method. The best predictions were achieved using CP-ANN coupled with a genetic algorithm, with the external validation parameter Q_V² of 0.96. The applicability domains of the models were defined to determine the chemical space in which reliable predictions can be obtained. The models were applied for the estimation of bilitranslocase transport activity for two sets of pharmaceutically interesting compounds, antioxidants and antiprions. We found that the relative planarity and a high potential for hydrogen bond formation are the common structural features of anticipated substrates of bilitranslocase. These features may serve as guidelines in the design of new pharmaceuticals transported by bilitranslocase.     

Spectroscopy and X-ray studies of {{6,6′-dimethoxy-2,2′-[ethane-1,2-diyl-bis-(nitrilomethylidyne)]diphenolato}(aqua)-dioxouranium(VI)} dehydrate

The C₁₈H₂₀N₂O₇U · 2H₂O (I) complex has been prepared and characterized by single crystal X-ray diffraction properties (CIF file CCDC no. 913243). The title compound crystallizes in the orthorhombic system, space group Pbca with a = 19.542(5), b = 9.916(5), c = 21.940(5) Å, V = 4252(3) ų and Z = 8. In complex I, the U atom has a distorted pentagonal-bipyramidal geometry with a tetradentate Schiff base ligand and water molecule in the equatorial plane and oxo atoms in the axial positions. The crystal packing occurs intra-inter molecular hydrogen bonds.     

Strong ionic interactions in noncovalent complexes between poly(ethylene imine), a cationic electrolyte,and Cibacron Blue,a nucleotide mimic – implications for oligonucleotide vectors

Cationic polymers can bind DNA to form polyplexes, which are noncovalent complexes used for gene delivery into the targeted cells. For more insight on such biologically relevant systems, the noncovalent complexes between the cationic polymer poly(ethylene imine) (PEI) and the nucleotide mimicking dye Cibacron Blue F3G‐A (CB) were investigated using mass spectrometry methods. Two PEIs of low molecular weight were utilized (M_n ≈ 423 and 600 Da). The different types of CB anions produced by Na⁺/H⁺ exchanges on the three sulfonic acid groups of CB and their dehydrated counterparts were responsible for complex formation with PEI. The CB anions underwent noncovalent complex formation with protonated, but not with sodiated PEI. A higher proportion of cyclic oligomers were detected in PEI423 than PEI600, but both architectures formed association products with CB. Tandem mass spectrometry studies revealed a significantly stronger noncovalent interaction between PEI and dehydrated CB than between PEI and intact CB. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis and thermal behavior of new ambazone complexes with some transitional cations

Ambazone is a pharmaceutical compound that possesses antiseptic activity and tested as well for anti-tumor properties. Metal complexes of Zn(II), Fe(III), and Cu(II) containing ambazone as ligand were synthesized using a molar ratio salt:ligand of 1:1, heating the mixture up to 50 °C for 6 h. Coordination compounds were characterized by thin-layer chromatography, FT-IR spectroscopy, elemental analysis, and thermal behavior. The non-isothermal experiments were carried out in order to investigate the thermal degradation process of these complexes and were performed in a dynamic air atmosphere at a heating rate β = 10 °C min^?1 from ambient temperature, up to 500 °C. It was revealed that decomposition process is a multistadial one.     

The Origin of the Selectivity and Activity of Ruthenium‐Cluster Catalysts for Fuel‐Cell Feed‐Gas Purification: A Gas‐Phase Approach

Gas‐phase ruthenium clusters Ru_n⁺ (n=2–6) are employed as model systems to discover the origin of the outstanding performance of supported sub‐nanometer ruthenium particles in the catalytic CO methanation reaction with relevance to the hydrogen feed‐gas purification for advanced fuel‐cell applications. Using ion‐trap mass spectrometry in conjunction with first‐principles density functional theory calculations three fundamental properties of these clusters are identified which determine the selectivity and catalytic activity: high reactivity toward CO in contrast to inertness in the reaction with CO₂; promotion of cooperatively enhanced H₂ coadsorption and dissociation on pre‐formed ruthenium carbonyl clusters, that is, no CO poisoning occurs; and the presence of Ru‐atom sites with a low number of metal–metal bonds, which are particularly active for H₂ coadsorption and activation. Furthermore, comprehensive theoretical investigations provide mechanistic insight into the CO methanation reaction and discover a reaction route involving the formation of a formyl‐type intermediate.