Effect of the carburization of MoO3-based catalysts on the activity for butane hydroisomerization

Catalysts based on molybdena (MoO3) reduced at mild temperatures are highly active and selective for the hydroisomerization of alkanes: however, further catalyst development has been hampered by the structural complexity of the material and the controversy regarding the nature of the active phase. The present work is aimed at determining the relationship between the content of carbon present in an oxycarbide phase and the activity for n-butane hydroisomerization. A series of temperature-programmed oxidation (TPO) and temporal analysis of product (TAP) data showed that the oxycarbidic carbon content is not related to the activity of the sample for the isomerization of n-butane to isobutane. The formation of a carbon-containing phase is, therefore, not crucial to obtain an active catalyst. This study also highlights the capability of the multi-pulse TAP technique to investigate structure-activity relationships over materials with readily variable atomic composition. (C) 2008 Elsevier B.V. All rights reserved.

A DFT study of the chain growth probability in Fischer-Tropsch synthesis

The chain growth probability (alpha value) is one of the most significant parameters in Fischer-Tropsch (FT) synthesis. To gain insight into the chain growth probability, we systematically studied the hydrogenation and C-C coupling reactions with different chain lengths on the stepped Co(0001) surface using density functional theory calculations. Our findings elucidate the relationship between the barriers of these elementary reactions and the chain length. Moreover, we derived a general expression of the chain growth probability and investigated the behavior of the alpha value observed experimentally. The high methane yield results from the lower chain growth rate for C-1 + C-1 coupling compared with the other coupling reactions. After C-1, the deviation of product distribution in FT synthesis from the Anderson-Schulz-Flory distribution is due to the chain length-dependent paraffin/olefin ratio. (C) 2008 Elsevier Inc. All rights reserved.

Steric effects in the selective hydrogenation of cinnamaldehyde to cinnamyl alcohol using an Ir/C catalyst

The liquid phase selective hydrogenation of cinnamaldehyde to cinnamyl alcohol has been carried out over a graphite-supported iridium catalyst. The effect of reaction parameters such as temperature, pressure, concentration of reactant, the effect of addition of product to the feed and pre-reduction of the catalyst were studied. In situ pre-reduction of the catalyst with hydrogen had a very significant enhancing effect on the conversion of cinnamaldehyde and selectivity of the catalyst to cinnamyl alcohol. Kinetic analysis of the pre-reduced catalyst showed that the reaction is zero order with respect to cinnamaldehyde and first order with respect to hydrogen. The reaction follows an Arrhenius behaviour with an activation energy of 37 kJ mol(-1). Detailed analysis of the reaction showed that hydrogenation of the C=C double bond to give hydrocinnamaldehyde predominantly occurred at low conversions of cinnamaldehyde (

Archaeological and Palaeoecological investigations of a Middle Bronze Age settlement at Ballyarnet Lake, Co. Derry

Excavations at Ballyarnet Lake, Co Derry, have identified a Middle Bronze Age settlement site at the margins of the lake. The site is characterised by a palisaded enclosure surrounding a structure containing a hearth. Finds include a large quantity of Cordoned Urn ware, lithics and a faience bead. Palaeoenvironmental studies, including pollen, plant macrofossil and beetle analyses, provide insights into the environmental background of the settlement. The site is considered in terms of the broader context of Middle Bronze Age settlement.

Use of Digital Manufacturing to Improve Management Learning in Aerospace Assembly

The primary goal of this work is to quantify any bene?ts that the use of digital manufacturing methods can offer when used upstream from production, for manufacturing process design, and tool development. Learning at this stage of product development is referred to as management learning. Animated build simulations have been used to develop build procedures and tooling for a panel assembly for the new Bombardier CRJ1000 (Canadair Regional Jet, 100 seat). When the jig format was developed, its simulated performance was compared to that of current CRJ700/900 panel builds to identify and quantify any improvements in terms of tooling cost and panel build time. When comparing like-for-like functions between existing CRJ700/900 (Canadair Regional Jet, 70/90 seat) and the
CRJ1000 tooling, it was predicted that the digitally assisted improvements had brought about a 4.9% reduction in jig cost. An evaluation of the build process for the CRJ1000 uplock panel predicted a 5.2% reduction in the assembly time. In addition to the improvement of existing tooling functions, new jig functionality was added so that both the drilling and riveting functions could be carried out in a single jig for the new RJ1000 panel.

Statistical theory of finite Fermi systems with chaotic excited eigenstates

A theory of strongly interacting Fermi systems of a few particles is developed. At high excit at ion energies (a few times the single-parti cle level spacing) these systems are characterized by an extreme degree of complexity due to strong mixing of the shell-model-based many-part icle basis st at es by the residual two- body interaction. This regime can be described as many-body quantum chaos. Practically, it occurs when the excitation energy of the system is greater than a few single-particle level spacings near the Fermi energy. Physical examples of such systems are compound nuclei, heavy open shell atoms (e.g. rare earths) and multicharged ions, molecules, clusters and quantum dots in solids. The main quantity of the theory is the strength function which describes spreading of the eigenstates over many-part icle basis states (determinants) constructed using the shell-model orbital basis. A nonlinear equation for the strength function is derived, which enables one to describe the eigenstates without diagonalization of the Hamiltonian matrix. We show how to use this approach to calculate mean orbital occupation numbers and matrix elements between chaotic eigenstates and introduce typically statistical variable s such as t emperature in an isolated microscopic Fermi system of a few particles.

Cost performance of Irish credit unions

There are 424 credit unions in Ireland with assets under their control of €14.3bn and a membership of 2.5m which equates to about 66% of the economically active population, the highest penetration level of any country. That said, the Irish movement sits at a critical development stage, well behind mature markets such as Canada and the US in terms of product provision, technological sophistication, fragmentation of trade bodies and regulatory environment. This study analyses relative cost efficiency or performance of Irish credit unions using the popular frontier approach which measures an entity’s efficiency relative to a frontier of best practice. Parametric techniques are utilised, with variation in inefficiency being attributed to credit union-specific factors. The stochastic cost frontier parameters and the credit-union specific parameters are simultaneously estimated to produce valid statistical inferences. The study finds that the majority of Irish credit unions are not operating at optimal levels. It further highlights the factors which drive efficiency variation across credit unions and they include technological sophistication, ‘sponsor donated’ resources, interest rate differentials and the levels of bad debt written off

Influence of water on the carbon dioxide absorption by 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide

The effect of the addition of water on the absorption of carbon dioxide by the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide was studied experimentally by measuring the low-pressure carbon dioxide solubility and the viscosity of the liquid solvent at temperatures from 303 to 323 K. Water is only partially miscible with the ionic liquid up to a mole fraction of 0.302 at 293 K, 0.321 at 303 K and 0.381 at 323 K. It was observed that the solubility of carbon dioxide decreases with the quantity of water from a mole fraction of 2.63 × 10-2 for the pure ionic liquid at 303.4 K to a value of 1.88 × 10-2, a reduction of 30% of the solubility, for a mole fraction of water of 0.28. The viscosity of the liquid solvent also decreases, up to 40% at 303 K, from 28.6 mPa s for the pure ionic liquid to 16.4 mPa s for a water mole fraction of 0.302.

Effect of plasticizer-polymer compatibility on the response characteristics of optical thin CO2 and O-2 sensing films

A homologous family of dialkyl phthalates has been used to investigate the effect of plasticizer/polymer compatibility on the response characteristics of transparent, plastic, thin optical gas sensing films for CO2 and oxygen. Plasticizer/polymer compatibilities were determined through the value of the difference in solubility parameter, i.e. Delta delta, for the plasticizer and polymer with a Delta delta value of zero indicating high compatibility. A strong correlation was found between plasticizer/polymer compatibility and sensitivity in phenol red/ethyl cellulose CO2-sensitive films and this relationship extended to CO2-sensitive films based on other polymers such as polystyrene and poly(methyl methacrylate). It extended also to optical O-2-sensitive films implying that the relationship is general for thin-film optical sensors. Other results from the CO2-sensitive films in different polymers indicated that the film sensitivity is largely independent of the polymer matrix regardless of its inherent gas permeability, when a sufficient quantity of compatible plasticizer is present. (C) 1998 Elsevier Science B.V.

Textural, viscoelastic and mucoadhesive properties of pharmaceutical gels composed of cellulose polymers

This study examined the mechanical/textural, viscoeiastic and mucoadhesive properties of a range of aqueous gels composed of either hydroxyethylcellulose (HEC) or sodium carboxymethylcellulose (Na CMC). The mechanical/textural properties of each formulation were determined using texture profile analysis. The viscoelastic properties of each formulation were examined over a defined frequency range (0.01-1.0 Hz) using oscillatory rheometry in conjunction with stainless steel parallel plate geometry. The mucoadhesive properties of the gels were evaluated by measuring the tensile force required to overcome the gel/mucin adhesive interaction. Both gel hardness and compressibility, properties that affect the ease of product removal from a container and spreadability, increased as a function of increasing polymer concentrations. This is attributed to the effects of HEC and Na CMC on gel viscosity. Gel adhesiveness, a property related to bioadhesion, also increased as a function of polymer concentration and is attributed to the reported adhesive nature of these polymers. Increasing frequency of oscillation increased the storage and loss moduli yet decreased bath the dynamic viscosity of each gel type and also the loss tangent of HEC (but not Na CMC) gels. Therefore, following exposure to the range of oscillatory stresses that may be expected in vivo, HEC gels will be more susceptible than Na CMC gels to alterations in these rheological properties. Consequently, it would be expected that the clinical performance of HEC gels will be modified to a greater extent than Na CMC gels. In general, HEC gels exhibited a greater elastic nature than Na CMC gels over the frequency range employed for oscillation The storage and loss moduli and dynamic viscosity of both gel types increased, yet the loss tangent of both gel types decreased as a function of increasing polymer concentration. Gel mucoadhesive strength was dependent on both the time of contact of the formulation with mucin and also on polymer concentration. In conclusion, this study has characterised a number of gels containing either HEC or Na CMC in terms of their mechanical/textural, viscoelastic and mucoadhesive properties. Due to its relevance to the clinical performance, it is suggested that the information derived from these methods may be usefully combined to provide a more rational basis for the selection of polymers and their formulation as topical drug delivery systems. (C) 1997 Elsevier Science B.V.

Dynamic grey-box modeling for online monitoring of extrusion viscosity

Melt viscosity is a key indicator of product quality in polymer extrusion processes. However, real time monitoring and control of viscosity is difficult to achieve. In this article, a novel “soft sensor” approach based on dynamic gray-box modeling is proposed. The soft sensor involves a nonlinear finite impulse response model with adaptable linear parameters for real-time prediction of the melt viscosity based on the process inputs; the model output is then used as an input of a model with a simple-fixed structure to predict the barrel pressure which can be measured online. Finally, the predicted pressure is compared to the measured value and the corresponding error is used as a feedback signal to correct the viscosity estimate. This novel feedback structure enables the online adaptability of the viscosity model in response to modeling errors and disturbances, hence producing a reliable viscosity estimate. The experimental results on different material/die/extruder confirm the effectiveness of the proposed “soft sensor” method based on dynamic gray-box modeling for real-time monitoring and control of polymer extrusion processes. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers

Exposure of mortars to cyclic chloride ingress and carbonation

The presence of chloride ions is one of the primary factors causing the degradation of reinforced concrete structures. An investigation to monitor ingress of chlorides during a 24-week wetting and drying exposure regime to simulate conditions in which multiple-mode transport mechanisms are active was conducted on a variety of binders. Penetration was evaluated using free and total chloride profiles. Acid extraction of chlorides is quantitatively reliable and practical for assessing penetration. X-ray diffraction was used to determine the presence of bound chlorides and carbonation. The ability of the cement blends to resist chloride penetration was, from best to worst, ground granulated blast-furnace slag, microsilica, pulverised-fuel ash, Portland cement. The effect of carbonation on binding capability was observed and the relative quantity of chlorides also showed a correlation with the amount of chlorides bound in the form of Friedel’s salt.

The wbbD gene of E. coli strain VW187 (O7:K1) encodes a UDP-Gal:GlcNAc{alpha}-pyrophosphate-R {beta}1,3-galactosyltransferase involved in the biosynthesis of O7-specific lipopolysaccharide

In this work, we demonstrate that the wbbD gene of the O7 lipopolysaccharide (LPS) biosynthesis cluster in Escherichia coli strain VW187 (O7:K1) encodes a galactosyltransferase involved in the synthesis of the O7-polysaccharide repeating unit. The galactosyltransferase catalyzed the transfer of Gal from UDP-Gal to the GlcNAc residue of a GlcNAc-pyrophosphate-lipid acceptor. A mutant strain with a defective wbbD gene was unable to form O7 LPS and lacked this specific galactosyltransferase activity. The normal phenotype was restored by complementing the mutant with the cloned wbbD gene. To characterize the WbbD galactosyltransferase, we used a novel acceptor substrate containing GlcNAcalpha-pyrophosphate covalently bound to a hydrophobic phenoxyundecyl moiety (GlcNAc alpha-O-PO(3)-PO(3)-(CH(2))(11)-O-phenyl). The WbbD galactosyltransferase had optimal activity at pH 7 in the presence of 2.5 mM MnCl(2). Detergents in the assay did not increase glycosyl transfer. Digestion of enzyme product by highly purified bovine testicular beta-galactosidase demonstrated a beta-linkage. Cleavage of product by pyrophosphatase and phosphatase, followed by HPLC and NMR analyses, revealed a disaccharide with the structure Gal beta1-3GlcNAc. Our results conclusively demonstrate that WbbD is a UDP-Gal: GlcNAcalpha-pyrophosphate-R beta1,3-galactosyltransferase and suggest that the novel synthetic glycolipid acceptor may be generally applicable to characterize other bacterial glycosyltransferases.

Development of a multi-media book for clinical supervision training in undergraduate nursing

There is an increased interest in higher education in the use of e-learning resources for students. This can be attributed to many factors including, the availability of advanced technology systems, a growing student population that is technology focused, financial implications and the recruitment of international students. However, the introduction of technology and e-learning into teaching has given rise to issues regarding quality and quantity of educational practice . The challenge now is for educationalists is to deliver an optimal learning experience that is effective and appropriate for students’ learning needs.

Field fluxes and speciation of arsines emanating from soils

The biogeochemical cycle of arsenic (As) has been extensively studied over the past decades because As is an environmentally ubiquitous, nonthreshold carcinogen, which is often elevated in drinking water and food. It has been known for over a century that micro-organisms can volatilize inorganic As salts to arsines (arsine AsH(3), mono-, di-, and trimethylarsines, MeAsH(2), Me(2)AsH, and TMAs, respectively), but this part of the As cycle, with the exception of geothermal environs, has been almost entirely neglected because of a lack of suited field measurement approaches. Here, a validated, robust, and low-level field-deployable method employing arsine chemotrapping was used to quantify and qualify arsines emanating from soil surfaces in the field. Up to 240 mg/ha/y arsines was released from low-level polluted paddy soils (11.3 ± 0.9 mg/kg As), primarily as TMAs, whereas arsine flux below method detection limit was measured from a highly contaminated mine spoil (1359 ± 212 mg/kg As), indicating that soil chemistry is vital in understanding this phenomenon. In microcosm studies, we could show that under reducing conditions, induced by organic matter (OM) amendment, a range of soils varied in their properties, from natural upland peats to highly impacted mine-spoils, could all volatilize arsines. Volatilization rates from 0.5 to 70 µg/kg/y were measured, and AsH(3), MeAsH(2), Me(2)AsH, and TMAs were all identified. Addition of methylated oxidated pentavalent As, namely monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA), to soil resulted in elevated yearly rates of volatilization with up to 3.5% of the total As volatilized, suggesting that the initial conversion of inorganic As to MMAA limits the rate of arsine and methylarsines production by soils. The nature of OM amendment altered volatilization quantitatively and qualitatively, and total arsines release from soil showed correlation between the quantity of As and the concentration of dissolved organic carbon (DOC) in the soil porewater. The global flux of arsines emanating from soils was estimated and placed in the context of As atmospheric inputs, with arsines contributing from 0.9 to 2.6% of the global budget.