Determining adsorbate configuration on alumina surfaces with 13C nuclear magnetic resonance relaxation time analysis

Relative strengths of surface interaction for individual carbon atoms in acyclic and cyclic hydrocarbons adsorbed on alumina surfaces are determined using chemically resolved 13C nuclear magnetic resonance (NMR) T1 relaxation times. The ratio of relaxation times for the adsorbed atoms T1,ads to the bulk liquid relaxation time T1,bulk provides an indication of the mobility of the atom. Hence a low T1,ads/T1,bulk ratio indicates a stronger surface interaction. The carbon atoms associated with unsaturated bonds in the molecules are seen to exhibit a larger reduction in T1 on adsorption relative to the aliphatic carbons, consistent with adsorption occurring through the carbon-carbon multiple bonds. The relaxation data are interpreted in terms of proximity of individual carbon atoms to the alumina surface and adsorption conformations are inferred. Furthermore, variations of interaction strength and molecular configuration have been explored as a function of adsorbate coverage, temperature, surface pre-treatment, and in the presence of co-adsorbates. This relaxation time analysis is appropriate for studying the behaviour of hydrocarbons adsorbed on a wide range of catalyst support and supported-metal catalyst surfaces, and offers the potential to explore such systems under realistic operating conditions when multiple chemical components are present at the surface.

Organo-mineral complexation alters carbon and nitrogen cycling in stream microbial assemblages

Inland waters are of global biogeochemical importance receiving carbon inputs of ~ 4.8 Pg C y^-1. Of this 12 % is buried, 18 % transported to the oceans, and 70 % supports aquatic secondary production. However, the mechanisms that determine the fate of organic matter (OM) in these systems are poorly defined. One important aspect is the formation of organo-mineral complexes in aquatic systems and their potential as a route for OM transport and burial vs. their use potential as organic carbon (C) and nitrogen (N) sources. Organo-mineral particles form by sorption of dissolved OM to freshly eroded mineral surfaces and may contribute to ecosystem-scale particulate OM fluxes. We tested the availability of mineral-sorbed OM as a C & N source for streamwater microbial assemblages and streambed biofilms. Organo-mineral particles were constructed in vitro by sorption of ¹³C:¹⁵N-labelled amino acids to hydrated kaolin particles, and microbial degradation of these particles compared with equivalent doses of ¹³C:¹⁵N-labelled free amino acids. Experiments were conducted in 120 ml mesocosms over 7 days using biofilms and streamwater sampled from the Oberer Seebach stream (Austria), tracing assimilation and mineralization of ¹³C and ¹⁵N labels from mineral-sorbed and dissolved amino acids.Here we present data on the effects of organo-mineral sorption upon amino acid mineralization and its C:N stoichiometry. Organo-mineral sorption had a significant effect upon microbial activity, restricting C and N mineralization by both the biofilm and streamwater treatments. Distinct differences in community response were observed, with both dissolved and mineral-stabilized amino acids playing an enhanced role in the metabolism of the streamwater microbial community. Mineral-sorption of amino acids differentially affected C & N mineralization and reduced the C:N ratio of the dissolved amino acid pool. The present study demonstrates that organo-mineral complexes restrict microbial degradation of OM and may, consequently, alter the carbon and nitrogen cycling dynamics within aquatic ecosystems.

Dynamics and structure of self-generated magnetics fields on solids following high contrast, high intensity laser irradiation

The dynamics of self-generated magnetic B-fields produced following the interaction of a high contrast, high intensity (I > 10¹⁹W cm^-2) laser beam with thin (3 μm thick) solid (Al or Au) targets is investigated experimentally and numerically. Two main sources drive the growth of B-fields on the target surfaces. B-fields are first driven by laser-generated hot electron currents that relax over ∼10-20 ps. Over longer timescales, the hydrodynamic expansion of the bulk of the target into vacuum also generates B-field induced by non-collinear gradients of density and temperature. The laser irradiation of the target front side strongly localizes the energy deposition at the target front, in contrast to the target rear side, which is heated by fast electrons over a much larger area. This induces an asymmetry in the hydrodynamic expansion between the front and rear target surfaces, and consequently the associated B-fields are found strongly asymmetric. The sole long-lasting (>30 ps) B-fields are the ones growing on the target front surface, where they remain of extremely high strength (∼8-10 MG). These B-fields have been recently put by us in practical use for focusing laser-accelerated protons [B. Albertazzi et al., Rev. Sci. Instrum. 86, 043502 (2015)]; here we analyze in detail their dynamics and structure.

Design and deployment of secure, robust, and resilient SDN Controllers

The scale of the Software-Defined Network (SDN) Controller design problem has become apparent with the expansion of SDN deployments. Initial SDN deployments were small-scale, single controller environments for research and usecase testing. Today, enterprise deployments requiring multiple controllers are gathering momentum e.g. Google’s backbone network, Microsoft’s public cloud, and NTT’s edge gateway. Third-party applications are also becoming available e.g. HP SDN App Store. The increase in components and interfaces for the evolved SDN implementation increases the security challenges of the SDN controller design. In this work, the requirements of a secure, robust, and resilient SDN controller are identified, stateof-the-art open-source SDN controllers are analyzed with respect to the security of their design, and recommendations for security improvements are provided. This contribution highlights the gap between the potential security solutions for SDN controllers and the actual security level of current controller designs.

ALMA Observations of a Gap and a Ring in the Protoplanetary Disk around TW Hya

We report the first detection of a gap and a ring in dust continuum emission from the protoplanetary disk around TW Hya, using the Atacama Large Millimeter/Submillimeter Array. The gap and ring are located at 25 and 41 AU from the central star, respectively, and are associated with the CO snowline at ~ 30AU. The gap width and depth are 15AU at the maximum and 23% at the minimum, respectively, regarding that the observations are limited to an angular resolution of ~ 15AU. In addition, we detect a decrement in CO line emission down to ~ 10AU, indicating freeze-out of gas-phase CO onto grain surfaces and possible subsequent surface reactions to form larger molecules. According to theoretical studies, the gap could be caused by gravitational interaction between the disk gas and a planet with a mass less than super-Neptune (2 Neptune mass), or result from destruction of large dust aggregates due to the sintering of CO ice.

Porous Materials with Tunable Structure and Mechanical Properties via Templated Layer-by-Layer Assembly

The deposition of stiff and strong coatings onto porous templates offers a novel strategy for fabricating macroscale materials with controlled architectures at the micro- and nanoscale. Here, layer-by-layer assembly is utilized to fabricate nanocomposite-coated foams with highly customizable properties by depositing polymer–nanoclay coatings onto open-cell foam templates. The compressive mechanical behavior of these materials evolves in a predictable manner that is qualitatively captured by scaling laws for the mechanical properties of cellular materials. The observed and predicted properties span a remarkable range of density-stiffness space, extending from regions of very soft elastomer foams to very stiff, lightweight honeycomb and lattice materials.

Enteropathogenic Escherichia coli O125:H6 triggers attaching and effacing lesions on human intestinal biopsy specimens independently of Nck and TccP/TccP2

Typical enteropathogenic Escherichia coli (EPEC) and enterohemorrhagic E. coli (EHEC) employ either Nck, TccP/TccP2, or Nck and TccP/TccP2 pathways to activate the neuronal Wiskott-Aldrich syndrome protein (N-WASP) and to trigger actin polymerization in cultured cells. This phenotype is used as a marker for the pathogenic potential of EPEC and EHEC strains. In this paper we report that EPEC O125:H6, which represents a large category of strains, lacks the ability to utilize either Nck or TccP/TccP2 and hence triggers actin polymerization in vitro only inefficiently. However, we show that infection of human intestinal biopsies with EPEC O125:H6 results in formation of typical attaching and effacing lesions. Expression of TccP in EPEC O125:H6, which harbors an EHEC O157-like Tir, resulted in efficient actin polymerization in vitro and enhanced colonization of human intestinal in vitro organ cultures with detectable N-WASP and electron-dense material at the site of bacterial adhesion. These results show the existence of a natural category of EPEC that colonizes the gut mucosa using Nck- and TccP-independent mechanisms. Importantly, the results highlight yet again the fact that conclusions made on the basis of in vitro cell culture models cannot be extrapolated wholesale to infection of mucosal surfaces and that the ability to induce actin polymerization on cultured cells should not be used as a definitive marker for EPEC and EHEC virulence.

Sedimentology, structure and age estimate of five continental slope submarine landslides, eastern Australia

Sedimentological and accelerator mass spectrometry (AMS) 14C data provide estimates of the structure and age of five submarine landslides (∼0.4–3 km3) present on eastern Australia's continental slope between Noosa Heads and Yamba. Dating of the post-slide conformably deposited sediment indicates sediment accumulation rates between 0.017 m ka–1 and 0.2 m ka–1, which is consistent with previous estimates reported for this area. Boundary surfaces were identified in five continental slope cores at depths of 0.8 to 2.2 m below the present-day seafloor. Boundary surfaces present as a sharp colour-change across the surface, discernible but small increases in sediment stiffness, a slight increase in sediment bulk density of 0.1 g cm–3, and distinct gaps in AMS 14C ages of at least 25 ka. Boundary surfaces are interpreted to represent a slide plane detachment surface but are not necessarily the only ones or even the major ones. Sub-bottom profiler records indicate that: (1) the youngest identifiable sediment reflectors upslope from three submarine landslides terminate on and are truncated by slide rupture surfaces; (2) there is no obvious evidence for a post-slide sediment layer draped over, or burying, slide ruptures or exposed slide detachment surfaces; and (3) the boundary surfaces identified within the cores are unlikely to be near-surface slide surfaces within an overall larger en masse dislocation. These findings suggest that these submarine landslides are geologically recent (<25 ka), and that the boundary surfaces are either: (a) an erosional features that developed after the landslide, in which case the boundary surface age provides a minimum age for the landslide; or (b) detachment surfaces from which slabs of near-surface sediment were removed during landsliding, in which case the age of the sediment above the boundary surface indicates the approximate age of landsliding. While an earthquake-triggering mechanism is favoured for the initiation of submarine landslides on the eastern Australian margin, further evidence is required to confirm this interpretation.

Settlement Duration and Materiality:Formal Chronological Models for the Development of Barnhouse, a Grooved Ware Settlement in Orkney

Radiocarbon dating and Bayesian chronological modelling, undertaken as part of the investigation by the Times of Their Lives project into the development of Late Neolithic settlement and pottery in Orkney, has provided precise new dating for the Grooved Ware settlement of Barnhouse, excavated in 1985–91. Previous understandings of the site and its pottery are presented. A Bayesian model based on 70 measurements on 62 samples (of which 50 samples are thought to date accurately the deposits from which they were recovered) suggests that the settlement probably began in the later 32nd century cal bc (with Houses 2, 9, 3 and perhaps 5a), possibly as a planned foundation. Structure 8 – a large, monumental structure that differs in character from the houses – was probably built just after the turn of the millennium. Varied house durations and replacements are estimated. House 2 went out of use before the end of the settlement, and Structure 8 was probably the last element to be abandoned, probably during the earlier 29th century cal bc. The Grooved Ware pottery from the site is characterised by small, medium-sized, and large vessels with incised and impressed decoration, including a distinctive, false-relief, wavy-line cordon motif. A considerable degree of consistency is apparent in many aspects of ceramic design and manufacture over the use-life of the settlement, the principal change being the appearance, from c. 3025–2975 cal bc, of large coarse ware vessels with uneven surfaces and thick applied cordons, and of the use of applied dimpled circular pellets. The circumstances of new foundation of settlement in the western part of Mainland are discussed, as well as the maintenance and character of the site. The pottery from the site is among the earliest Grooved Ware so far dated. Its wider connections are noted, as well as the significant implications for our understanding of the timing and circumstances of the emergence of Grooved Ware, and the role of material culture in social strategies.

Parametric optimisation of manufacturing tolerances at the aircraft surface

Up until now, aircraft surface smoothness requirements have been aerodynamically driven with tighter manufacturing tolerance to minimize drag, that is, the tighter the tolerance, the higher is the assembly cost in the process of manufacture. In the current status of commercial transport aircraft operation, it can be seen that the unit cost contributes to the aircraft direct operating cost considerably more than the contribution made by the cost of block fuel consumed for the mission profile. The need for a customer-driven design strategy to reduce direct operating cost by reducing aircraft cost through manufacturing tolerance relaxation at the wetted surface without unduly penalizing parasite drag is investigated. To investigate this, a preliminary study has been conducted at 11 key manufacturing features on the surface assembly of an isolated nacelle. In spite of differences in parts design and manufacture, the investigated areas associated with the assembly of nacelles are typical of generic patterns in the assembly of other components of aircraft. The study is to be followed up by similar studies extended to lifting surfaces and fuselage

Geophysical imaging of stimulated microbial biomineralization

Understanding how microorganisms influence the physical and chemical properties of the subsurface is hindered by our inability to observe microbial dynamics in real time and with high spatial resolution. Here, we investigate the use of noninvasive geophysical methods to monitor biomineralization at the laboratory scale during stimulated sulfate reduction under dynamic flow conditions. Alterations in sediment characteristics resulting from microbe-mediated sulfide mineral precipitation were concomitant with changes in complex resistivity and acoustic wave propagation signatures. The sequestration of zinc and iron in insoluble sulfides led to alterations in the ability of the pore fluid to conduct electrical charge and of the saturated sediments to dissipate acoustic energy. These changes resulted directly from the nucleation, growth, and development of nanoparticulate precipitates along grain surfaces and within the pore space. Scanning and transmission electron microscopy (SEM and TEM) confirmed the sulfides to be associated with cell surfaces, with precipitates ranging from aggregates of individual 3-5 nm nanocrystals to larger assemblages of up to 10-20 m in diameter. Anomalies in the geophysical data reflected the distribution of mineral precipitates and biomass over space and time, with temporal variations in the signals corresponding to changes in the aggregation state of the nanocrystalline sulfides. These results suggest the potential for using geophysical techniques to image certain subsurface biogeochemical processes, such as those accompanying the bioremediation of metal-contaminated aquifers.

Acylation of sulfonamines using silica grafted 1-butyl-3-(3-triethoxysilylpropyl)-4,5-dihydroimidazolium ionic liquids as catalysts

Heterogeneous immobilized ionic liquid catalysts were prepared via grafting of 1,3-dimethyl-3-(3-triethoxysilylpropyl)-imidazolium tetrafluoroborate or bist{(trifluoromethyl)sulfonyl} imide ([NTf2](-)) on silica supports with different surfaces and pore size. In addition to the adsorption-desorption isotherms of nitrogen at -196C, the catalysts were characterized by TG-DTA, XPS, DRIFTS, DR-UV-vis, NMR, and XRD techniques. The catalytic behavior was checked in the acylation of three different sulfonamines: benzenesulfonamine, p-nitrobenzene-sulfonamine, and p-methoxybenzene-sulfonamine with acetic acid, acetic anhydride and maleic anhydride. These tests confirmed the acid Lewis properties of these catalysts. (c) 2007 Elsevier B.V. All rights reserved.

A density functional theory study of the a-olefin selectivity in Fischer-Tropsch synthesis

We studied the alpha-olefin selectivity in Fischer-Tropsch (FT) synthesis using density functional theory (131717) calculations. We calculated the relevant elementary steps from C-2 to C-6 species. Our results showed that the barriers of hydrogenation and dehydrogenation reactions were constant with different chain lengths, and the chemisorption energies of alpha-olefins from DFT calculations also were very similar, except for C-2 species. A simple expression of the paraffin/olefin ratio was obtained based on a kinetic model. Combining the expression of the paraffin/olefin ratio and our calculation results, experimental findings are satisfactorily explained. We found that the physical origin of the chain length dependence of paraffin/olefin ratio is the chain length dependence of both the van der Waals interaction between adsorbed alpha-olefins and metal surfaces and the entropy difference between adsorbed and gaseous alpha-olefins, and that the greater chemisorption energy of ethylene is the main reason for the abnormal ethane/ethylene ratio. (c) 2008 Elsevier Inc. All rights reserved.

CHx hydrogenation on Co(0001): A density functional theory study

Hydrogenation is an important process in the Fischer-Tropsch synthesis. In this work, all the elementary steps of the hydrogenation from C to CH4 are studied on both flat and stepped Co(0001) using density functional theory (DFT). We found that (i) CH3 hydrogenation (CH3+H-->CH4) is the most difficult one among all the elementary reactions on both surfaces, possessing barriers of around 1.0 eV; (ii) the other elementary reactions have the barriers below 0.9 eV on the flat and stepped surfaces; (iii) CH2 is the least stable species among all the CHx(x=1-3) species on both surfaces; and (iv) surface restructuring may have little effect on the CHx(x=0-3) hydrogenation. The barriers of each elementary step on both flat and stepped surfaces are similar and energy profiles are also similar. The reason as to why CHx hydrogenation is not structure-sensitive is also discussed. (C) 2005 American Institute of Physics.

Compressed Metal Powders that Remain Superhydrophobic After Abrasion

Superhydrophobic “lotus effect” materials are typically not sufficiently robust for most real world applications because their small surface features are both easily damaged and vulnerable to fouling. Here, a method for preparing a new type of superhydrophobic (? > 162°) composite material by compression of superhydrophobic metal particles is reported. This material, which has no natural analogue, has low-surface-energy microstructures extending throughout its whole volume. Removing its outer layer by abrasion or cutting deep into it does not result in loss of superhydrophobicity because it merely exposes a fresh portion of the underlying superhydrophobic material. The high contact angle is therefore retained even after accidental damage, and vigorous abrasion can be used to restore hydrophobicity after fouling.