Efficient heterogeneous asymmetric catalysis of the Mukaiyama aldol reaction by silica- and ionic liquid-supported Lewis acid copper(II) complexes of bis(oxazolines)

Lewis acid complexes based on copper(II) and an imidazolium-tagged bis(oxazoline) have been used to catalyse the asymmetric Mukaiyama aldol reaction between methyl pyruvate and 1-methoxy-1-tri-methylsilyloxypropene under homogeneous and heterogeneous conditions. Although the ees obtained in ionic liquid were similar to those found in dichloromethane, there was a significant rate enhancement in the ionic liquid with reactions typically reaching completion within 2 min compared with only 55% conversion after 60 min in dichloromethane. However, this rate enhancement was offset by lower chemoselectivity in ionic liquids due to the formation of 3-hydroxy-1,3-diphenylbutan-1-one as a by-product. Supporting the catalyst on silica or an imidazolium-modified silica using the ionic liquid or in an ionic liquid-diethyl ether system completely suppressed the formation of this by-product without reducing the enantioselectivity. Although the heterogeneous systems were characterised by a drop in catalytic activity the system could be recycled up to five times without any loss in conversion or ee.

Ionic Liquid Effect on the Reversal of Configuration for the Magnesium(II) and Copper(II) Bis(oxazoline)-Catalysed Enantioselective Diels-Alder Reaction

Ionic liquids have been used to support a range of magnesium-and copper-based bis(oxazoline) complexes for the enantioselective Diels-Alder reaction between N-acryloyloxazolidinone and cyclopentadiene. Compared with reaction performed in dichloromethane or diethyl ether, an enhancement in ee is observed with a large increase in reaction rate. In addition, for non-sterically hindered bis(oxazoline) ligands, that is, phenyl functionalised ligands, a reversal in configuration is found in the ionic liquid, 1-ethyl-3-methylimidazolium bis[(trifluoromethanesulfonyl)imide], compared with molecular solvents. Supported ionic liquid phase catalysts have also been developed using surface-modified silica which show good reactivity and enantioselectivity for the case of the magnesium-based bis(oxazoline) complexes. Poor ees and conversion were observed for the analogous copper-based systems. Some drop in ee was found on supporting the catalyst due a drop in the rate of reaction and, therefore, an increase in the contribution from the uncatalysed a chiral reaction.

Voltammetric Currents in Room Temperature Ionic Liquids Can Reflect Solutes Other Than the Electroactive Species and Are Influenced by Carbon Dioxide

The effects of such solutes such as halides and water on the physical properties of room temperature ionic liquids (RTILs) have been extensively studied, This work examines the effect of the solute carbon dioxide on the RTIL 1-ethyl-3-methylimidazolium bis(trifluoromethane-sulfonyl)imide ([C(2)mim][NTf2]) and its influence on the electrochemical characterization of the important redox couple ferrocene/ferrocenium (Fc/Fc(+)). The system was studied using cyclic voltammetry, chronoamperometry, and electron spin resonance (ESR) spectroscopy. Addition Of 100% CO2 to a solution of Fc in [C(2)mim][NTf2] resulted in a substantial increase in both the limiting oxidative current and diffusion coefficient of Fc. Arrhenius plots of Fc diffusion coefficients in the pure and CO2-saturated ionic liquid revealed a decrease in activation energy of translational diffusion from 29.0 (+/- 0.5) kJ mol(-1) to 14.7 (+/- 1.6) kJ mol(-1), suggesting a reduction in the viscosity of the ionic liquid with addition Of CO2. ESR spectroscopy was then used to calculate the rotational correlation coefficients of a probe molecule, 2,2,6,6-tetramethyl-1-piperinyloxyl (TEMPO), to add supporting evidence to this hypothesis. Arrhenius plots of rotational correlation coefficients in the pure and CO2-saturated ionic liquid resulted in a similar drop in activation energy from 28.7 (+/- 2.1) kJ mol(-1) to 18.2 (+/- 5.6) kJ mol(-1). The effect of this solute on the ionic liquid [C(2)mim][NTf2] and on the electrochemical measurements of the Fc/Fc(+) couple emphasizes the necessity of fastidious sample preparation, as it is clear that the voltammetric currents of the electroactive species under study are influenced by the presence of CO2 in solution. The voltammetric response of the electroactive species in RTILs cannot be assumed to be independent of other solutes.

Effect of Free-Fall Height in Water on Performance of Flowable Concrete

Concrete placed under water should be proportioned to flow readily into place with minimum materials separation. Unlike concrete cast for deep tremie seals, the use of concrete in repairs often necessitates some free fall of the mixture through water. Such placement conditions lead to greater risk of water erosion and segregation, and should be addressed in proportioning highly flowable underwater concrete. This paper evaluates the effect of free-fall height (FFH) of concrete through water on resulting in-place properties. Concrete was cast in blocks measuring 0.54 x 0.44 x 1 m with the initial FFH in water ranging between 0.25 and 0.60 m. In-place compressive and splitting tensile strengths, unit weight, and depth of washed-out and sedimentation materials were determined. In total, 24 highly flowable mixtures with slump flows greater than 500 mm were investigated. The evaluated mixtures were prepared with various hydraulic binders, including conventional Type 10 cement, a binary mixture with 10% of silica fume (SF), and a ternary binder incorporating 20% of fly ash (FA) and 6% of SF. The mixtures were proportioned with water-binder ratios (w/b) ranging between 0.41 and 0.47. Test results show that the increase of FFH of fresh concrete in water can greatly decrease the residual strength and significantly increase the thickness of washed out and sedimentation materials. The incorporation of 10% of SF, or 20% of FA and 6% of SF, and the reduction of the w/b from 0.47 to 0.41 can, however, lead to a significant increase in washout resistance and residual strength. A relationship between residual strength and the coupled factor of free-fall drop of concrete in water and washout resistance is established.

Chironomid-inferred Late-Glacial Summer Air Temperatures From Lough Nadourcan, Co. Donegal, Ireland.

Western Ireland, located adjacent to the North Atlantic, and with a strongly oceanic climate, is potentially sensitive to rapid and extreme climate change. We present the first high-resolution chironomid-inferred mean July temperature reconstruction for Ireland, spanning the late-glacial and early Holocene (LGIT, 15-10 ka BP). The reconstruction suggests an initial rapid warming followed by a short cool phase early in the interstadial. During the interstadial there are oscillations in the inferred temperatures which may relate to Greenland Interstadial events GI-1a-e. The temperature decrease into the stadial occurs in two stages. This two-stage drop can also be seen in other late-glacial chironomid-inferred temperature records from the British Isles. A stepped rise in temperatures into the Holocene, consistent with present-day temperatures in Donegal, is inferred. The results show strong similarities with previously published LGIT chironomid-inferred temperature reconstructions, and with the NGRIP oxygen-isotope curve, which indicates that the oscillations observed in the NGRIP record are of hemispherical significance. The results also highlight the influence of the North Atlantic on the Irish climate throughout the LGIT.

Interfacial tensions of imidazolium-based ionic liquids with water and n-alkanes

The interfacial tension of the liquid-liquid phase boundary of several 1,3-dialkyl imidazolium based ionic liquids, namely, 1,3-dimethylimidazolium bis{(trifluoromethyl)sulfonyl}imide [C(1)mim][NTf2], 1-ethyl-3-methylimidazoliurn bis{(trifluoromethyl)sulfonyl}imide [C(2)mim][NTf2], 1-butyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide [C(4)mim][NTf2], 1-hexyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide [C(6)mim][NTf2], 1-octyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide [C(8)mim][NTf2], 1-butyl-3-methylimidazolium trifluoromethylsulfonate [C(4)mim][CF3SO3], and 1-butyl-3-methylimidazolium trifluoroacetate [C(4)mim][CF3COO] with water and with the n-alkanes, n-hexane, n-octane and n-decane, has been measured using the pendant drop method as a function of temperature from 293 to 323 K. The experimental interfacial tension data were correlated using the ionic liquid parachor estimation method and a mutual solubility model. The influence of the cation and anion of ionic liquids and also of alkyl chain length of n-alkanes on interfacial tension is discussed. It has also been demonstrated that the interfacial tension data estimated by the correlation methods are in good agreement with the experimental data. (C) 2010 Elsevier B.V. All rights reserved.

A Scalable and Programmable Modular Traffic Manager Architecture

A key issue in the design of next generation Internet routers and switches will be provision of traffic manager (TM) functionality in the datapaths of their high speed switching fabrics. A new architecture that allows dynamic deployment of different TM functions is presented. By considering the processing requirements of operations such as policing and congestion, queuing, shaping and scheduling, a solution has been derived that is scalable with a consistent programmable interface. Programmability is achieved using a function computation unit which determines the action (e.g. drop, queue, remark, forward) based on the packet attribute information and a memory storage part. Results of a Xilinx Virtex-5 FPGA reference design are presented.

Evaluation of a new peat-based sorbent for metals capture

A new peat-based sorbent was evaluated for the capture of heavy metals from waste streams. The media is a pelletted blend of organic humic material targeted for the capture of soluble metals from industrial waste streams and stormwater. The metals chosen for the media evaluation were Cd, Cu, Ni, and Zn due to their occurrence and abundance in waste streams and runoff. Sorption tests included an evaluation of the rate and extent of metals capture by the media, single versus multicomponent metals uptake, pH, anion influence, leaching effects and the effect of media moisture content on uptake rate and capacity. Isotherms of the sorption results showed that the presence of multiple metals increased the total sorption capacity of the media compared to the single component metal capacity; a result of site selectivity within the media. However the capacity for an individual metal in a multicomponent metal matrix was reduced compared to its single component capacity, due to competition for sites. Evidence of ion exchange behavior was observed but did not account for all metals capture. The media also provided a buffering action to counter the pH drop typically associated with metals capture.

The AGE inhibitor pyridoxamine inhibits development of retinopathy in experimental diabetes

We examined the ability of pyridoxamine (PM), an inhibitor of formation of advanced glycation end products (AGEs) and lipoxidation end products (ALEs), to protect against diabetes-induced retinal vascular lesions. The effects of PM were compared with the antioxidants vitamin E (VE) and R-alpha-lipoic acid (LA) in streptozotocin-induced diabetic rats. Animals were given either PM (1 g/l drinking water), VE (2,000 IU/kg diet), or LA (0.05%/kg diet). After 29 weeks of diabetes, retinas were examined for pathogenic changes, alterations in extracellular matrix (ECM) gene expression, and accumulation of the immunoreactive AGE/ALE N-epsilon-(carboxymethyl)lysine (CML). Acellular capillaries were increased more than threefold, accompanied by significant upregulation of laminin immunoreactivity in the retinal microvasculature. Diabetes also increased mRNA expression for fibronectin (2-fold), collagen IV (1.6-fold), and laminin beta chain (2.6-fold) in untreated diabetic rats compared with nondiabetic rats. PM treatment protected against capillary drop-out and limited laminin protein upregulation and ECM mRNA expression and the increase in CML in the retinal vasculature. VE and LA failed to protect against retinal capillary closure and had inconsistent effects on diabetes-related upregulation of ECM mRNAs. These results indicate that the AGE/ALE inhibitor PM protected against a range of pathological changes in the diabetic retina and may be useful for treating diabetic retinopathy.

Structural and magnetic properties of sol-gel Co2xNi0.5-xZn0.5-xFe2O4 thin films

Nanocrystalline Co2xNi0.5-xZn0.5-xFe2O4 (x = 0-0.5) thin films have been synthesized with various grain sizes by a sol-gel method on polycrystalline silicon substrates. The morphology as well as magnetic and microwave absorption properties of the films calcined at 1073 K were studied using X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and vibrating sample magnetometry. All films were uniform with out microcracks . The Co content in the Co-Ni-Zn films resulted in a grain size ranging from 15 to 32 nm while it ranged from 33 to 49 nm in the corresponding powders. Saturation and remnant magnetization increased with increase in grain size, while coercivity demonstrated a drop due to multidomain behavior of crystallites for a given value of x. Saturation magnetization increased and remnant magnetization had a maximum as a function of grain size in dependent of x. In turn, coercivity increased with x independent of grain size. Complex permittivity of the Co-Ni-Zn ferrite films was measured in the frequency range 2-15 GHz. The highest hysteretic heating rate in the temperature range 315-355 K was observed in CoFe2O4. The maximum absorption band shifted from 13 to 11GHz as cobalt content increased from x = 0.1 to 0.2.

Comparison of Experimental PIV Data and CFD Simulations for Flow in a Diesel Particulate Filter Inlet Diffuser

Flow maldistribution of the exhaust gas entering a Diesel Particulate Filter (DPF) can cause uneven soot distribution during loading and excessive temperature gradients during the regeneration phase. Minimising the magnitude of this maldistribution is therefore an important consideration in the design of the inlet pipe and diffuser, particularly in situations where packaging constraints dictate bends in the inlet pipe close to the filter, or a sharp diffuser angle. This paper describes the use of Particle Image Velocimetry (PIV) to validate a Computational Fluid Dynamic (CFD) model of the flow within the inlet diffuser of a DPF so that CFD can be used with confidence as a tool to minimise this flow maldistribution. PIV is used to study the flow of gas into a DPF over a range of steady state flow conditions. The distribution of flow approaching the front face of the substrate was of particular interest to this study. Optically clear diffusing cones were designed and placed between pipe and substrate to allow PIV analysis to take place. Stereoscopic PIV was used to eliminate any error produced by the optical aberrations caused by looking through the curved wall of the inlet cone. In parallel to the experiments, numerical analysis was carried out using a CFD program with an incorporated DPF model. Boundary conditions for the CFD simulations were taken from the experimental data, allowing an experimental validation of the numerical results. The CFD model incorporated a DPF model, the cement layers seen in segmented filters and the intumescent matting that is commonly used to pack the filter into a metal casing. The mesh contained approximately 580,000 cells and used the realizable ?-e turbulence model. The CFD simulation predicted both pressure drop across the DPF and the velocity field within the cone and at the DPF face with reasonable accuracy, providing confidence in the use the CFD in future work to design new, more efficient cones.

Dimerisation of cyclooctene using Grubbs' catalysts

The dimerisation of cyclooctene (COE) to 1,9-cyclohexadecadiene, a molecule of interest to the fragrance industry, has been achieved using ruthenium catalysts in organic solvents with significantly better selectivities (47-74%) and yields (39-60%) than previously reported (34% and 30%, respectively). Grubbs' first and second generation catalysts, the Hoveyda-Grubbs' catalyst and a phosphonium alkylidene catalyst were tested in a range of organic solvents and ionic liquids (ILs), including 1:1 IL/dichloromethane mixtures and biphasic IL + pentane systems. The best results (74% selectivity, 60% yield) were obtained using Grubbs' first generation catalyst in 1,2-dichloroethane. The formation of trimer, tetramer and other higher molecular mass products were found to be favoured at low catalyst loadings (0.77 mM). Studies of metathesis reactions using 1,9-cyclohexadecadiene as substrate indicated that the monomer-dimer and monomer-trimer reactions are faster than the dimer-dimer reaction. The use of IL media allowed for the recyclability of the catalyst, although a drop in the yield of dimer generally occurred after the first run. Heterogeneized catalysts, where the IL-catalyst system was immobilised onto silica, resulted in fast reactions leading to poor yields of dimer. (C) 2011 Elsevier B.V. All rights reserved.

Geophysical and geochemical survey of a large marine pockmark on the Malin Shelf, Ireland

Marine pockmarks are a specific type of seabed geological setting resembling craters or pits and are considered seabed surface expressions of fluid flow in the subsurface. A large composite pockmark on the Malin Shelf, off the northern coast of Ireland was surveyed and ground truthed to assess its activity and investigate fluid related processes in the subsurface. Geophysical (including acoustic and electromagnetic) data confirmed the subsurface presence of signatures typical of fluids within the sediment. Shallow seismic profiling revealed a large shallow gas pocket and typical gas related indicators such as acoustic blanking and enhanced reflectors present underneath and around the large pockmark. Sulphate profiles indicate that gas from the shallow reservoir has been migrating upwards, at least recently. However, there are no chimney structures observed in the sub-bottom data and the migration pathways are not apparent. Electromagnetic data show slightly elevated electrical conductivity on the edges of the pockmarks and a drop below regional levels within the confines of the pockmark, suggesting changes in physical properties of the sediment. Nuclear Magnetic Resonance (NMR) experiments were employed to characterize the organic component of sediments from selected depths. Very strong microbial signatures were evident in all NMR spectra but microbes outside the pockmark appear to be much more active than inside. These observations coincide with spikes in conductivity and the lateral gas bearing body suggesting that there is an increase in microbial activity and biomass when gas is present.

Design of a thick-walled screen for flow equalization in microstructured reactors

A systematic computational fluid dynamics (CFD) approach has been applied to design the geometry of the channels of a three-dimensional (thick-walled) screen comprising upstream and downstream sets of elongated channels positioned at an angle of 90 degrees with respect to each other. Such a geometry of the thick-wall screen can effectively drop the ratio of the maximum flow velocity to mean flow velocity below 1.005 in a downstream microstructured reactor at low Reynolds numbers. In this approach the problem of flow equalization reduces to that of flow equalization in the first and second downstream channels of the thick-walled screen. In turn, this requires flow equalization in the corresponding cross-sections of the upstream channels. The validity of the proposed design method was assessed through a case study. The effect of different design parameters on the flow non-uniformity in the downstream channels has been established. The design equation is proposed to calculate the optimum values of the screen parameters. The CFD results on flow distribution were experimentally validated by Laser Doppler Anemometry measurements in the range of Reynolds numbers from 6 to 113. The measured flow non-uniformity in the separate reactor channels was below 2%.

Thick titania films for semiconductor photocatalysis

A brief overview of work carried out by this group on thick (> 1 mu m), optically clear, robust titania films prepared by a sol-gel method, as well as new results regarding these films, are described. Such films are very active as photocatalysts and able to destroy stearic acid with a quantum yield of 0.32%. The activity of such films is largely unaffected by annealing temperatures below 760 degrees C, but is drastically reduced above this temperature. The drop in photocatalyst activity of such films as a function of annealing temperature appears to correlate well with the change in porosity of the films and suggests that the latter parameter is very important in deciding the overall activity of such films. The importance of porosity in semiconductor photocatalysed cold combustion may be due to the effect it has on access of oxygen to the active sites, rather like the effect the position of a fire grate (open or closed) has on the rate of burning, i.e., hot combustion, that takes place in a fireplace.