Diffusion within ultrathin, dense nanoporous silica films

In this work the origin of permselectivity in dense silica films which possess a pore structure with pore sizes commensurate with the molecular size of the diffusing gas species is investigated. Much of the recently reported work in this field has involved the development of composite membrane films, and while it is generally assumed that the transport process of the gas species within the selective layer of these films is activated in nature, there are anomalies with this simplified picture. In this paper a new model is developed which, for the first time, explains the permselective behavior of the thin selective coatings ubiquitous to membrane separation processes. The model involves the existence of two primary transport domains within the solid film, one of which rapidly conducts the permeating gas (under non-Fickian conditions), while the second domain involves a slow diffusion mode characterized by normal Fickian transport. To validate the model, molecular dynamics simulations are conducted for diffusion of a number of simple gases (He, N(2), and CO(2)) within silica glasses over a range of solid densities. The silica media employed in these studies are based on a novel approach developed in this work for the construction of three-dimensionally periodic atomistic structures of silica of arbitrary density in which network bond connectivity is ensured. The results obtained from this work are in qualitative agreement with experimental observations and confirm the existence of dual mode transport which is central to the interpretation of the permselectivity in composite membranes systems.     

Rapid identification, by use of the LTQ Orbitrap hybrid FT mass spectrometer, of antifungal compounds produced by lactic acid bacteria

Fungal contamination of food causes health and economic concerns. Several species of lactic acid bacteria (LAB) have antifungal activity which may inhibit food spoilage fungi. LAB have GRAS (generally recognised as safe) status, allowing them to be safely integrated into food systems as natural food preservatives. A method is described herein that enables rapid screening of LAB cultures for 25 known antifungal compounds associated with LAB. This is the first chromatographic method developed which enables the rapid identification of a wide range of antifungal compounds by a single method with a short analysis time (23 min). Chromatographic separation was achieved on a Phenomenex Gemini C18 100A column (150 mm?×?2.0 mm; 5 μm) by use of a mobile-phase gradient prepared from (A) water containing acetic acid (0.1%) and (B) acetonitrile containing acetic acid (0.1%), at a flow rate of 0.3 µL min^?1. The gradient involved a progressive ramp from 10–95% acetonitrile over 13 min. The LC was coupled to a hybrid LTQ Orbitrap XL fourier-transform mass spectrometer (FTMS) operated in negative ionisation mode. High mass accuracy data (<3 ppm) obtained by use of high resolution (30,000 K) enabled unequivocal identification of the target compounds. This method allows comprehensive profiling and comparison of different LAB strains and is also capable of the identification of additional compounds produced by these bacteria.     

Cell-like equivalences and boundaries of CAT(0) groups

In 2000, Croke and Kleiner showed that a CAT(0) group G can admit more than one boundary. This contrasted with the situation for ??-hyperbolic groups, where it was well-known that each such group admitted a unique boundary??in a very stong sense. Prior to Croke and Kleiner??s discovery, it had been observed by Geoghegan and Bestvina that a weaker sort of uniquness does hold for boundaries of torsion free CAT(0) groups; in particular, any two such boundaries always have the same shape. Hence, the boundary really does carry significant information about the group itself. In an attempt to strengthen the correspondence between group and boundary, Bestvina asked whether boundaries of CAT(0) groups are unique up to cell-like equivalence. For the types of space that arise as boundaries of CAT(0) groups, this is a notion that is weaker than topological equivalence and stronger than shape equivalence. In this paper we explore the Bestvina Cell-like Equivalence Question. We describe a straightforward strategy with the potential for providing a fully general positive answer. We apply that strategy to a number of test cases and show that it succeeds??often in unexpectedly interesting ways.     

The geometry of spheres in free abelian groups

We study word metrics on ${\mathbb{Z}^d}$ by developing tools that are fine enough to measure dependence on the generating set. We obtain counting and distribution results for the words of length n. With this, we show that counting measure on spheres always converges to cone measure on a polyhedron (strongly, in an appropriate sense). Using the limit measure, we can reduce probabilistic questions about word metrics to problems in convex geometry of Euclidean space. We give several applications to the statistics of ??size-like?? functions.     

Alginate hydrogels as biomaterials

[Image: see text] Alginate hydrogels are proving to have a wide applicability as biomaterials. They have been used as scaffolds for tissue engineering, as delivery vehicles for drugs, and as model extracellular matrices for basic biological studies. These applications require tight control of a number of material properties including mechanical stiffness, swelling, degradation, cell attachment, and binding or release of bioactive molecules. Control over these properties can be achieved by chemical or physical modifications of the polysaccharide itself or the gels formed from alginate. The utility of these modified alginate gels as biomaterials has been demonstrated in a number of in vitro and in vivo studies.Micro-CT images of bone-like constructs that result from transplantation of osteoblasts on gels that degrade over a time frame of several months leading to improved bone formation.     

Evaluation of a polymerase chain reaction-based heteroduplex assay for detecting the adulteration of processed orange juice with mandarin juice

A polymerase chain reaction (PCR)-based heteroduplex assay was evaluated for the detection of mandarin juice in processed orange juice. PCR amplification of a fragment of the chloroplast trnT-trnL intergenic spacer derived from mixtures of DNA extracted from orange and mandarin juice resulted in heteroduplex formation. The heteroduplex resulted from the co-amplification of a fragment containing an 8 base-pair indel that distinguished mixtures of orange and mandarin juice from orange juice and mandarin juice alone. The heteroduplex assay was evaluated against authentic juices obtained from different citrus species and confirmed that the marker was homogeneous within Citrus. The data obtained demonstrated maternal inheritance of chloroplast type in Citrus sp. and allowed the identification and confirmation of the maternal parentage of unknown and known citrus hybrids. Analysis of the quantitative potential of the PCR and polyacrylamide gel electrophoresis (PAGE) analysis demonstrated good repeatability with a coefficient of variation of 7.5%. Greatest sources of variance in experimental results were attributable to species and varietal differences in the levels of the PCR target. Mandarin juice contained approximately 18% (w/v) less PCR target sequence than did orange juice. The assay was tested in a blind trial using processed juices and correctly identified 20/22 samples with no false-positive results.     

The effect of severe thermal pretreatment on the redox behaviour of gold in aqueous acid solution

Severe thermal pretreatment of gold wire electrodes in an inert gas atmosphere resulted in the appearance of dramatic premonolayer oxidation responses, which in some instances commenced at 0.25 V (RHE), for the resulting active gold electrodes in aqueous acid media. Similar behaviour was reported earlier for platinum and gold activated by cathodic pretreatment in acid solution; these active noble metal surfaces are evidently more susceptible to oxidation than bulk copper. Such behaviour was attributed to the effect of surface disorder; many of the metal atoms at the interface are assumed to be in a very active, metastable state possessing quite low lattice stabilization energy. Premonolayer oxidation responses are again correlated with electrocatalytic behaviour and the existence of unusual chemisorption behaviour for molecules reacting at highly active states of metals is outlined. Electronic Publication     

Auto-inhibition of hydrogen gas evolution on gold in aqueous acid solution

It was demonstrated recently that dramatic changes in the redox behaviour of gold/aqueous solution interfaces may be observed following either cathodic or thermal electrode pretreatment. Further work on the cathodic pretreatment of gold in acid solution revealed that as the activity of the gold surface was increased, its performance as a substrate for hydrogen gas evolution under constant potential conditions deteriorated. The change in activity of the gold atoms at the interface, which was attributed to a hydrogen embrittlement process (the occurrence of the latter was subsequently checked by surface microscopy), was confirmed, as in earlier work, by the appearance of a substantial anodic peak at ca. 0.5 V (RHE) in a post-activation positive sweep. Changes in the catalytic activity of a metal surface reflect the fact that the structure (or topography), thermodynamic activity and electronic properties of a surface are dependent not only on pretreatment but also, in the case of the hydrogen evolution reaction, vary with time during the course of reaction. As will be reported shortly, similar (and often more dramatic) time-dependent behaviour was observed for hydrogen gas evolution on other metal electrodes. Electronic Publication     

Thin tantalum pentoxide films deposited by photo-induced chemical vapor deposition using an injection liquid source

We report the growth of thin tantalum pentoxide films on Si (100) by ultraviolet-assisted injection liquid source (UVILS) chemical vapor deposition (CVD) at low temperatures (200-350 °C). This new technique combines the intense radiation from an excimer lamp (5=222 nm) with a novel injection liquid source capable of delivering precisely controllable quantities of a liquid metalorganic precursor into the CVD chamber. The composition and optical properties of the oxides were determined using a variety of standard characterization methods. After optimization of the deposition parameters, the best layers were incorporated into simple MOS test structures to enable electrical characterization. Refractive index values of 2.09ǂ.07, fixed oxide charge content of <5᎒¹⁰ cm^-2, breakdown fields higher than 2 MV/cm and dielectric constant values of 18-24 were readily achievable in the as-deposited films. These properties compare favorably with those for layers prepared by conventional thermal-CVD at significantly higher temperatures of 500 °C.