Photocatalytic titania based surfaces: Environmental benefits

The use of photocatalytic titania nanoparticles in the development of self-cleaning and de-polluting paints and microbiological surfaces is demonstrated. In the former case surface erosion and sensitised photooxidation is shown to be controlled by the use of catalytic grades of anatase nanoparticles. For environmental applications in the development of coatings and cementitious materials for destroying atmospheric pollutants such as nitrogen oxides (NOX) stable substrates are also illustrated with photocatalytic nanoparticles. Here porosity of the coatings through calcium carbonate doping is shown to be crucial in the control of the effective destruction of atmospheric NOX gases. Good environmental stability of the coatings is also crucial for long-term durability and this aspect is examined for a variety of material substrates. For the development of microbiological substrates for the destruction of harmful bacteria/fungi effective nanoparticle anatase titania is shown to be important with hydrated high surface area particles giving the greatest activity. Data from commercial pilot studies is used to signify the important practicalities of this type of new technology.     

Rate of Convergence in Trotter’s Approximation Theorem

We give a quantitative estimate of the convergence in Trotter’s approximation theorem on the convergence of iterates of linear operators to an assigned semigroup. An application is given concerning the classical Bernstein operator on the d-dimensional simplex.      

Calibration-quality adiabatic potential energy surfaces for H3(+) and its isotopologues

Calibration-quality ab initio adiabatic potential energy surfaces (PES) have been determined for all isotopologues of the molecular ion H(3)(+). The underlying Born-Oppenheimer electronic structure computations used optimized explicitly correlated shifted Gaussian functions. The surfaces include diagonal Born-Oppenheimer corrections computed from the accurate electronic wave functions. A fit to the 41,655 ab initio points is presented which gives a standard deviation better than 0.1 cm(-1) when restricted to the points up to 6000 cm(-1) above the first dissociation asymptote. Nuclear motion calculations utilizing this PES, called GLH3P, and an exact kinetic energy operator given in orthogonal internal coordinates are presented. The ro-vibrational transition frequencies for H(3)(+), H(2)D(+), and HD(2)(+) are compared with high resolution measurements. The most sophisticated and complete procedure employed to compute ro-vibrational energy levels, which makes explicit allowance for the inclusion of non-adiabatic effects, reproduces all the known ro-vibrational levels of the H(3)(+) isotopologues considered to better than 0.2 cm(-1). This represents a significant (order-of-magnitude) improvement compared to previous studies of transitions in the visible. Careful treatment of linear geometries is important for high frequency transitions and leads to new assignments for some of the previously observed lines. Prospects for further investigations of non-adiabatic effects in the H(3)(+) isotopologues are discussed. In short, the paper presents (a) an extremely accurate global potential energy surface of H(3)(+) resulting from high accuracy ab initio computations and global fit, (b) very accurate nuclear motion calculations of all available experimental line data up to 16,000 cm(-1), and (c) results suggest that we can predict accurately the lines of H(3)(+) towards dissociation and thus facilitate their experimental observation.     

Atropisomers of hindered triarylisocyanurates: structure, conformation, stereodynamics, and absolute configuration

The syn and anti diastereoisomers of some 1,3,5-triarylisocyanurate derivatives were isolated and their configuration assigned by NOE experiments and by X-ray diffraction. The kinetics of the syn/anti interconversion were determined, and the experimental activation energies matched satisfactorily the values predicted by DFT computations. Low-temperature NMR spectra were employed to determine the rotation barrier of N-bonded unhindered aryl substituents: these barriers, too, are satisfactorily reproduced by DFT computations. In the case of racemic diastereoisomers, the two expected enantiomers (atropisomers) were isolated by enantioselective HPLC and the absolute configuration established by DFT simulation of the electronic and vibrational circular dichroism spectra.     

Xylanase and β-Xylosidase Production by <Emphasis Type="BoldItalic">Aspergillus ochraceus</Emphasis>: New Perspectives for the Application of Wheat Straw Autohydrolysis Liquor

The xylanase biosynthesis is induced by its substrate—xylan. The high xylan content in some wastes such as wheat residues (wheat bran and wheat straw) makes them accessible and cheap sources of inducers to be mainly applied in great volumes of fermentation, such as those of industrial bioreactors. Thus, in this work, the main proposal was incorporated in the nutrient medium wheat straw particles decomposed to soluble compounds (liquor) through treatment of lignocellulosic materials in autohydrolysis process, as a strategy to increase and undervalue xylanase production by Aspergillus ochraceus. The wheat straw autohydrolysis liquor produced in several conditions was used as a sole carbon source or with wheat bran. The best conditions for xylanase and β-xylosidase production were observed when A. ochraceus was cultivated with 1% wheat bran added of 10% wheat straw liquor (produced after 15 min of hydrothermal treatment) as carbon source. This substrate was more favorable when compared with xylan, wheat bran, and wheat straw autohydrolysis liquor used separately. The application of this substrate mixture in a stirred tank bioreactor indicated the possibility of scaling up the process to commercial production.     

Update on selective oxidation using gold

This critical review aims to update the recent development in the selective oxidation of organic compounds by gold catalysis, highlighting the progress in the last three years. Following the impressive developments in the last decades, several protocols for catalytic oxidation are today available, which are based on the extraordinary properties of gold in terms of catalytic activity, selectivity, reusability and resistance to poisons. Beside many other applications, gold can be recommended for green processes dedicated to fine chemicals, pharmaceuticals and the food industry owing to its recognized bio-compatibility. The collected literature is focused on experiments concerning the oxidation of different chemical groups and could be of interest, in the wide area of organic chemistry, for improving previous processes or for exploring new catalytic pathways (174 references).     

Cell fluidics: producing cellular streams on micropatterned synthetic surfaces

Patterning cell-adhesive molecules on material surfaces provides a powerful tool for controlling and guiding cell locomotion and migration. Here we report fast, reliable, easy to implement methods to fabricate large patterns of proteins on synthetic substrates to control the direction and speed of cells. Two common materials exhibiting very different protein adsorption capacities, namely, polystyrene and Teflon, were functionalized with micrometric stripes of laminin. The protein was noncovalently immobilized onto the surface by following either lithographically controlled wetting (LCW) or micromolding in capillaries (MIMIC). These techniques proved to be sufficiently mild so as not to interfere with the protein adhesion capability. Cells adhered onto the functionalized stripes and remained viable for more than 20 h. During this time frame, cells migrated along the lanes and the dynamics of motion was strongly affected by the substrate surface chemistry and culturing conditions. In particular, enhanced mismatches of cell adhesive properties obtained by the juxtaposition of bare and laminin-functionalized Teflon caused cells to move slowly and their movement to be highly confined. The patterning procedure was also effective at guiding migration on conventional cell culture dishes that were functionalized with laminin patterns, even in the presence of serum proteins, although to a lesser extent compared to that for Teflon. This work demonstrates the possibility of creating well-defined, long-range cellular streams on synthetic substrates by pursuing straightforward functionalizing techniques that can be implemented for a broad class of materials under conventional, long-time cell-culturing conditions. The procedure effectively confines cells to migrate along predefined patterns and can be implemented in different biomedical and biotechnological applications.     

Preparation and Thermal Characterization of PTFE/PES Nanocomposites

Summary: PTFE/PES composites were prepared by precipitation of Radel A® into a PTFE latex containing nanoparticles with average diameters of 48 nm and spherical shape. Several samples were prepared by varying the relative ratio between the Radel A® and PTFE content. The combination of SEM and AFM analysis indicates that the precipitation of Radel A in the presence of PTFE leads mainly, if not exclusively, to a bimodal mixture of the two homoparticles. The fractionated crystallization behaviour of these samples is revealing of the PTFE dispersion degree within the Radel A® matrix. When the PTFE amount is lower than 2%, a perfect PTFE nanoparticle dispersion is obtained. When the amount of PTFE is comprised between 5 and 30%, larger PTFE clusters are obtained that, after melting, coalesce and crystallize at higher temperatures depending on the crystallization propensity of their individual heterogeneous nuclei. Finally, in case of samples 40%, only one crystallization exotherm is observed at 310 °C indicating the formation of very large clusters that after melting coalesce into wide domains.     

Empirical properties of group preference aggregation methods employed in AHP: Theory and evidence

We study various methods of aggregating individual judgments and individual priorities in group decision making with the AHP. The focus is on the empirical properties of the various methods, mainly on the extent to which the various aggregation methods represent an accurate approximation of the priority vector of interest. We identify five main classes of aggregation procedures which provide identical or very similar empirical expressions for the vectors of interest. We also propose a method to decompose in the AHP response matrix distortions due to random errors and perturbations caused by cognitive biases predicted by the mathematical psychology literature. We test the decomposition with experimental data and find that perturbations in group decision making caused by cognitive distortions are more important than those caused by random errors. We propose methods to correct the systematic distortions.     

Shape memory and phase transitions for auxetic materials

We present a mathematical model describing the auxetic‐austenitic phase transition phenomenon by a second order shape memory phase transition. The typical properties of auxetic materials, as the negative Poisson ratio ν, are described by a function of the phase ?, called order parameter, which relates the phase transition with a change of the internal order structure of the material. In our model, the auxetic phase is represented by an order parameter ? = 1, which provides a negative Poisson's ratio, while the austenitic phase will be denoted by ? = 0. Copyright © 2013 John Wiley & Sons, Ltd.