The Effect of Water on the Activity and Selectivity for γ-Alumina Supported Cobalt Fischer–Tropsch Catalysts with Different Pore Sizes

The effect of water on the activity and selectivity for a series of γ-Al₂O₃ supported cobalt Fischer–Tropsch catalysts has been studied in an isothermal fixed-bed reactor at T = 483 K, P = 20 bar, and H₂/CO = 2.1. The catalysts were produced applying incipient wetness impregnation and consisted of 20 wt.% cobalt and 0.5 wt.% rhenium deposited on γ-Al₂O₃ supports with different pore characteristics. For the narrow-pore catalysts, addition of water corresponding to an inlet partial pressure ratio of P_H2O/P_H2 = 0.4 reduced the reaction rates. In contrast, for a catalyst with larger pores the same water pressure increased the reaction rates. For all catalysts, water amounts equal to P_H2O/P_H2 = 0.7 at the reactor inlet suppressed the reaction rates and led to permanent deactivation. The addition of water increased the C₅₊ selectivity and decreased the CH₄ selectivity for all catalysts. The pore characteristics seem to determine the effect of water on the rates.     

Form finding methodology for force-modelled anticlastic shells in glass fibre textile reinforced cement composites

The reinforcement of a specifically developed fine grained cement matrix with glass fibre textiles in high fibre volume fractions creates a fire safe composite that has-besides its usual compressive strength-an important tensile capacity and omits the need for any steel reinforcement. Strongly curved shells made of textile reinforced cement composites (TRC) can cover medium (up to 15 m) span spaces with three times smaller shell thicknesses than conventional steel-reinforced concrete shells. This paper presents a methodology to generate force-modelled anticlastic shell shapes that exploit both the tensile and compressive load carrying capacities of TRC. The force-modelling is based on the dynamic relaxation form finding method developed for gravity (in this case self-weight) loaded systems. The potential of the presented methodology to develop structurally sound anticlastic shell shapes is illustrated by four case studies.     

Chiral switching by spontaneous conformational change in adsorbed organic molecules

Self-assembly of adsorbed organic molecules is a promising route towards functional surface nano-architectures, and our understanding of associated dynamic processes has been significantly advanced by several scanning tunnelling microscopy (STM) investigations. Intramolecular degrees of freedom are widely accepted to influence ordering of complex adsorbates, but although molecular conformation has been identified and even manipulated by STM, the detailed dynamics of spontaneous conformational change in adsorbed molecules has hitherto not been addressed. Molecular surface structures often show important stereochemical effects as, aside from truly chiral molecules, a large class of so-called prochiral molecules become chiral once confined on a surface with an associated loss of symmetry. Here, we investigate a model system in which adsorbed molecules surprisingly switch between enantiomeric forms as they undergo thermally induced conformational changes. The associated kinetic parameters are quantified from time-resolved STM data whereas mechanistic insight is obtained from theoretical modelling. The chiral switching is demonstrated to enable an efficient channel towards formation of extended homochiral surface domains. Our results imply that appropriate prochiral molecules may be induced (for example, by seeding) to assume only one enantiomeric form in surface assemblies, which is of relevance for chiral amplification and asymmetric heterogenous catalysis.     

SAXS/DSC/WAXD study of TiO2 nanoparticles and the effect of γ-radiation on nanopolymer electrolyte

Nanostructured polymer electrolytes are very attractive materials for components of batteries and opto-electronic devices. (PEO)₈ZnCl₂ polymer electrolytes and nanocomposites were prepared using Poly(ethylene oxide) (PEO) γ-irradiated with a selected dose of 529 kGy and with an addition of 10% of TiO₂ nanograins. The influence of the added nanosize TiO₂ grains on the polymer electrolytes and the effect of the γ-radiation from a Co-60 source were studied by small-angle X-ray scattering (SAXS) simultaneously recorded with differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) at the synchrotron ELETTRA. Infrared (IR) and impedance spectroscopy (IS) were also performed [1]. It was shown by previously performed IS that the room temperature conductivity of the nanocomposite polymer electrolyte increased more than two times above 65 °C, relative to pure composites of PEO and salts. We observed all changes between 20 °C and 100 °C for treated and as prepared polymer electrolyte in the SAXS, DSC and WAXD spectra and especially during the phase transition to the super-ionic phase at 65 °C [2] and [3]. The SAXS/DSC measurements yielded insight into the temperature-dependent changes of the grains of the electrolyte as well as into the differences due to different heating and cooling rates. The crystal structure and the melting and crystallization temperatures of the nanosize grains were revealed by the simultaneous WAXD measurements.     

Low-level occupational 14C contamination--results from a pilot study

This paper presents a pilot study in which specific activities of 14C in hair and urine from 11 radiation workers handling 14C-containing substances have been measured using accelerator mass spectrometry. Varying degrees of contamination were revealed: up to 63% excess in hair and 400% excess in urine. Although the 14C excess reported in this study would result in low effective doses, it would be of interest to monitor the situation at other workplaces with potentially higher risks of contamination. Simultaneous measurements of 14C in hair and urine with additional random measurements of 14C in faeces and exhaled air could provide a means of improving dose estimates for workers handling different types of 14C-containing substances.     

A pumping lemma for random permitting context languages

Random context grammars belong to the class of context-free grammars with regulated rewriting. Their productions depend on context that may be randomly distributed in a sentential form. Context is classified as either permitting or forbidding, where permitting context enables the application of a production and forbidding context inhibits it. For random context languages of finite index a generalization of the well-known pumping lemma for context-free languages has been proven. We drop the finite index restriction and concentrate on non-erasing grammars that use permitting context only. We prove a pumping lemma for their languages that generalizes and refines the existing one, and show that these grammars are strictly weaker than the non-erasing random context grammars.     

The role of electrical current mode in calcium carbonate deposition on conductive carbon nanofiber–epoxy coating

Calcium carbonate is one of the most common scaling minerals. In this paper we have used different electrical current modes (direct current [DC], pulsed DC, and alternating current [AC]) to control the amount, morphology, and distribution of calcium carbonate deposit on electroconductive epoxy/carbon nanofiber (CNF) coating. The effect of different current modes on surface scaling was visualized using scanning electron microscopy. It has been shown that both AC and DC anodic polarization limited scale deposition on epoxy/CNF coated surfaces, although the mechanisms of scale inhibition during AC and DC polarization were different. DC polarization of the coating at +2 V resulted in the smallest scale buildup without leading to coating degradation, while DC polarization at potentials as high as +5 V caused the coating to degrade. Interestingly, application of pulsed DC with high pulse frequency (50 Hz) inhibited the degradation. The type of current applied affected also the morphology of the precipitate at the cathode. The results presented in this work show, for the first time, how different modes of electrical current applied to electroconductive composite coatings can be used to control the morphology and distribution of calcium carbonate scale, and how the organic coating degradation at high polarization potentials can be avoided.     

Alternating Current Electrophoretic Deposition of Antibacterial Bioactive Glass-Chitosan Composite Coatings

Alternating current (AC) electrophoretic deposition (EPD) was used to produce multifunctional composite coatings combining bioactive glass (BG) particles and chitosan. BG particles of two different sizes were used, i.e., 2 μm and 20–80 nm in average diameter. The parameter optimization and characterization of the coatings was conducted by visual inspection and by adhesion strength tests. The optimized coatings were investigated in terms of their hydroxyapatite (HA) forming ability in simulated body fluid (SBF) for up to 21 days. Fourier transform infrared (FTIR) spectroscopy results showed the successful HA formation on the coatings after 21 days. The first investigations were conducted on planar stainless steel sheets. In addition, scaffolds made from a TiAl4V6 alloy were considered to show the feasibility of coating of three dimensional structures by EPD. Because both BG and chitosan are antibacterial materials, the antibacterial properties of the as-produced coatings were investigated using E. coli bacteria cells. It was shown that the BG particle size has a strong influence on the antibacterial properties of the coatings.     

Lithological and pedological influences on the magnetic susceptibility of soil: their consideration in magnetic pollution mapping

Magnetic susceptibility measurements are widely used to map and monitor the heavy metal pollution of soils. However, the magnetic properties of soils are influenced significantly by the bedrock lithology and soil-forming processes. Therefore, a main challenge in the data interpretation is to filter out the anthropogenic pollution signal. In this study we address this problem by analysing susceptibility values, heavy metal concentrations, as well as pedological parameters in a large soil data set from the eastern segment of Austria, covering a wide range of different lithologies and soil types. The statistic assessment demonstrates an influence of lithology and soil type on the magnetic susceptibility signal. Therefore anomalies are defined in sub sets of different soil types separately. Three different methods were applied to detect susceptibility anomalies: the median absolute deviation method, the boxplot method, and the population modelling method. These methods evaluate topsoil data only and can therefore also be applied to field measurements of magnetic susceptibility. The results were compared to the conventional method of calculating the difference of topsoil and subsoil susceptibility. All three approaches identify the main anomalies in the study area and are successful in circumventing the problem of erroneous anomaly definition due to pedological processes. However, knowledge of the lithological background is still necessary for a meaningful interpretation and can only be substituted by a large amount of data. The tested methods lead to thresholds of different height and therefore act as filters of different strength for the definition of anomalies.     

Salmonella biofilms: An overview on occurrence,structure, regulation and eradication

The ability of Salmonella to form complex surface-associated communities, called biofilms, contributes to its resistance and persistence in both host and non-host environments and is especially important in food processing environments. In this review, the different types of abiotic (plastic, glass, cement, rubber, and stainless steel) and biotic surfaces (plant surfaces, epithelial cells, and gallstones) on which Salmonella biofilms have been described are discussed, as well as a number of commonly used laboratory setups to study Salmonella biofilm formation (rdar morphotype, pellicle formation, and biofilms on polystyrene pegs). Furthermore, the structural components important during Salmonella biofilm formation are described (curli and other fimbriae, BapA, flagella, cellulose, colanic acid, anionic O-antigen capsule and fatty acids), with special attention to the structural variations of biofilms grown on different surfaces and under different conditions. Indeed, biofilm formation is strongly influenced by different environmental signals, via a complex regulatory network. An extensive overview is given on the current understanding of this genetic network and the interactions between its different components (CsgD, RpoS, Crl, OmpR, IHF, H-NS, CpxR, MlrA, c-di-GMP, BarA/SirA, Csr, PhoPQ, RstA, Rcs, metabolic processes and quorum sensing). To further illustrate that biofilm formation is a mechanism of Salmonella to adapt to different environments, the resistance of Salmonella biofilms against different stress factors including desiccation stress, disinfectants (e.g. hypochlorite, glutaraldehyde, cationic tensides and triclosan) and antibiotics (e.g. ciprofloxacin) is described. Finally, a number of Salmonella biofilm inhibitors, identified through bottom-up- and top-down-approaches, are discussed, such as surfactin, glucose, halogenated furanones, 4(5)-aryl 2-aminoimidazoles, furocoumarins and salicylates. Also the potential of combination therapy (e.g. combinations of triclosan and quaternary ammonium salts or halogenated furanones and antibiotics/disinfectants) and nano- and micro-emulsions to inhibit Salmonella biofilm formation is discussed. Insight into the pathogen's complex biofilm process will eventually lead to further unraveling of its intricacies and more efficient strategies to combat Salmonella biofilms.