Synthesis and characterisation of an N-heterocyclic carbene with spatially-defined steric impact

The synthesis and co-ordination chemistry of a new ‘bulky yet flexible’ N-heterocyclic carbene (“IPaul”) is reported. This carbene has spatially-defined steric impact; steric maps show that two quadrants are very bulky while the other two are quite open. The electronic properties of this carbene are very similar to those of other 1,3-diarylimidazol-2-ylidenes. Copper, silver, iridium, and nickel complexes of the new ligand have been prepared. In solution, the ligand adopts two different conformations, while X-ray crystallographic analyses of the transition metal complexes suggest that the syn-conformer is preferred in the solid state due to intermolecular interactions. The copper complex of this new ligand has been shown to be highly-active in the hydrosilylation of carbonyl compounds, when compared to the analogous IPr, IMes, IPr* and IPr*OMe complexes

Normal form analysis of bouncing cycles in isotropic rotor stator contact problems

This work considers analysis of sustained bouncing responses of rotating shafts with nonlinear lateral vibrations due to rotor stator contact. The insight that this is an internal resonance phenomena makes this an ideal system to be studied with the method of normal forms, which assumes that a system may be modelled primarily in terms of just its resonant response components. However, the presence of large non smooth nonlinearities due to impact and rub mean that the method must be extended. This is achieved here by incorporating an alternating frequency/time (AFT) step to capture nonlinear forces. Furthermore, the presence of gyroscopic terms leads to the need to handle complex modal variables, and a rotating coordinate frame must be used to obtain periodic responses. The process results in an elegant formulation that can provide reduced order models of a wide variety of rotor systems, with potentially many nonlinear degrees of freedom. The method is demonstrated by comparing against time simulation of two example rotors, demonstrating high precision on a simple model and approximate precision on a larger model

Proceedings of the 24th annual Central Plains irrigation conference

Presented at Proceedings of the 24th annual Central Plains irrigation conference held on February 21-22 in Colby, Kansas.Includes bibliographical references

Polar mesoscale cyclones in the northeast Atlantic: Comparing climatologies from ERA-40 and satellite imagery

Polar mesoscale cyclones over the subarctic are thought to be an important component of the coupled atmosphere–ocean climate system. However, the relatively small scale of these features presents some concern as to their representation in the meteorological reanalysis datasets that are commonly used to drive ocean models. Here polar mesocyclones are detected in the 40-Year European Centre for Medium-Range Weather Forecasts (ECMWF) Re-Analysis dataset (ERA-40) in mean sea level pressure and 500-hPa geopotential height, using an automated cyclone detection algorithm. The results are compared to polar mesocyclones detected in satellite imagery over the northeast Atlantic, for the period October 1993–September 1995. Similar trends in monthly cyclone numbers and a similar spatial distribution are found. However, there is a bias in the size of cyclones detected in the reanalysis. Up to 80% of cyclones larger than 500 km are detected in MSL pressure, but this hit rate decreases, approximately linearly, to ∼40% for 250-km-scale cyclones and to ∼20% for 100-km-scale cyclones. Consequently a substantial component of the associated air–sea fluxes may be missing from the reanalysis, presenting a serious shortcoming when using such reanalysis data for ocean modeling simulations. Eight maxima in cyclone density are apparent in the mean sea level pressure, clustered around synoptic observing stations in the northeast Atlantic. They are likely spurious, and a result of unidentified shortcomings in the ERA-40 data assimilation procedure

Dark matter halo concentrations in the Wilkinson Microwave Anisotropy Probe year 5 cosmology

We use a combination of three large N-body simulations to investigate the dependence of dark matter halo concentrations on halo mass and redshift in the WMAP year 5 cosmology. The median relation between concentration and mass is adequately described by a power-law for halo masses in the range 10^11 - 10^15 Msol/h and redshifts z < 2, regardless of whether the halo density profiles are fit using NFW or Einasto profiles. Compared with recent analyses of the Millennium Simulation, which uses a value of sigma_8 that is higher than allowed by WMAP5, z = 0 halo concentrations are reduced by factors ranging from 23 per cent at 10^11 Msol/h to 16 per cent at 10^14 Msol/h. The predicted concentrations are much lower than inferred from X-ray observations of groups and clusters.Comment: 6 pages, 4 figures, Accepted by MNRAS letters. Version 4: Typo fixe

Occupational and environmental hazard assessments for the isolation, purification and toxicity testing of cyanobacterial toxins

Cyanobacteria can produce groups of structurally and functionally unrelated but highly potent toxins. Cyanotoxins are used in multiple research endeavours, either for direct investigation of their toxicologic properties, or as functional analogues for various biochemical and physiological processes. This paper presents occupational safety guidelines and recommendations for personnel working in field, laboratory or industrial settings to produce and use purified cyanotoxins and toxic cyanobacteria, from bulk harvesting of bloom material, mass culture of laboratory isolates, through routine extraction, isolation and purification. Oral, inhalational, dermal and parenteral routes are all potential occupational exposure pathways during the various stages of cyanotoxin production and application. Investigation of toxicologic or pharmacologic properties using in vivo models may present specific risks if radiolabelled cyanotoxins are employed, and the potential for occupational exposure via the dermal route is heightened with the use of organic solvents as vehicles. Inter- and intra-national transport of living cyanobacteria for research purposes risks establishing feral microalgal populations, so disinfection of culture equipment and destruction of cells by autoclaving, incineration and/or chlorination is recommended in order to prevent viable cyanobacteria from escaping research or production facilities

The 1995 scientific assessment of the atmospheric effects of stratospheric aircraft

This report provides a scientific assessment of our knowledge concerning the impact of proposed high-speed civil transport (HSCT) aircraft on the atmosphere. It comes at the end of Phase 1 of the Atmospheric Effects of Stratospheric Aircraft element of the NASA High-Speed Research Program. The fundamental problem with stratospheric flight is that pollutant residence times are long because the stratosphere is a region of permanent temperature inversion with stable stratification. Using improved two-dimensional assessment models and detailed fleet emissions scenarios, the assessment examines the possible impact of the range of effluents from aircraft. Emphasis is placed on the effects of NO(x) and H2O on the atmospheric ozone content. Measurements in the plume of an in-flight Concorde supersonic transport indicated a large number of small particles. These measurements, coupled with model sensitivity studies, point out the importance of obtaining a more detailed understanding of the fate of sulfur in the HSCT exhaust. Uncertainties in the current understanding of the processes important for determining the overall effects of HSCT's on the atmosphere are discussed and partially quantified. Research directions are identified to improve the quantification of uncertainties and to reduce their magnitude