Chain extension in electrospun polystyrene fibres: a SANS study

Small angle neutron scattering techniques were used to quantify the size and shape of the chain conformation in electrospun fibres of atactic polystyrene prepared from solutions in methyl ethyl ketone. Aligned arrays of fibres were collected onto a rotating collector with tangential velocity varying between 0 ms-1 and approximately 15 ms-1. The measured radii of gyration of the polystyrene chains were found to be slightly higher than that expected for samples prepared from solutions in the concentrated regime. The ratio of the radius of gyration parallel and perpendicular to the chain axis was found to be approximately 1.05 in contrast to the substantial macroscopic shape transformation intrinsic to electrospinning. When the tangential velocity of the rotating collector was greater than the flight velocity of the fibres (ca. 4 ms-1), a further extension of the polymer chains was observed with a ratio of the radii of gyration increasing to 1.20 at the highest collector speeds. It is proposed that the heterogeneous processes involved, particularly solvent evaporation and the formation of a polymer skin during electrospinning play a significant role in determining the level of molecular anisotropy in the fibres.

A value chain approach to animal diseases risk management: technical foundations and practical framework for field application

Classical risk assessment approaches for animal diseases are influenced by the probability of release, exposure and consequences of a hazard affecting a livestock population. Once a pathogen enters into domestic livestock, potential risks of exposure and infection both to animals and people extend through a chain of economic activities related to producing, buying and selling of animals and products. Therefore, in order to understand economic drivers of animal diseases in different ecosystems and to come up with effective and efficient measures to manage disease risks from a country or region, the entire value chain and related markets for animal and product needs to be analysed to come out with practical and cost effective risk management options agreed by actors and players on those value chains. Value chain analysis enriches disease risk assessment providing a framework for interdisciplinary collaboration, which seems to be in increasing demand for problems concerning infectious livestock diseases. The best way to achieve this is to ensure that veterinary epidemiologists and social scientists work together throughout the process at all levels.

Spin-up and adjustment of the Antarctic Circumpolar Current and global pycnocline

A theory is presented for the adjustment of the Antarctic Circumpolar Current (ACC) and global pycnocline to a sudden and sustained change in wind forcing. The adjustment timescale is controlled by the mesoscale eddy diffusivity across the ACC, the mean width of the ACC, the surface area of the ocean basins to the north, and deep water formation in the North Atlantic. In particular, northern sinking may have the potential to shorten the timescale and reduce its sensitivity to Southern Ocean eddies, but the relative importance of northern sinking and Southern Ocean eddies cannot be determined precisely, largely due to limitations in the parameterization of northern sinking. Although it is clear that the main processes that control the adjustment timescale are those which counteract the deepening of the global pycnocline, the theory also suggests that the timescale can be subtly modified by wind forcing over the ACC and global diapycnal mixing. Results from calculations with a reduced-gravity model compare well with the theory. The multidecadal-centennial adjustment timescale implies that long observational time series will be required to detect dynamic change in the ACC due to anthropogenic forcing. The potential role of Southern Ocean mesoscale eddy activity in determining both the equilibrium state of the ACC and the timescale over which it adjusts suggests that the response to anthropogenic forcing may be different in coupled ocean-atmosphere climate models that parameterize and resolve mesoscale eddies.

Electron spin resonance study of puff-resolved free radical formation in mainstream cigarette smoke

Puff-by-puff resolved gas phase free radicals were measured in mainstream smoke from Kentucky 2R4F reference cigarettes using ESR spectroscopy. Three spin-trapping reagents were evaluated: PBN, DMPO and DEPMPO. Two procedures were used to collect gas phase smoke on a puff-resolved basis: i) the accumulative mode, in which all the gas phase smoke up to a particular puff was bubbled into the trap (i.e., the 5th puff corresponded to the total smoke from the 1st to 5th puffs). In this case, after a specified puff, an aliquot of the spin trap was taken and analysed; or, ii) the individual mode, in which the spin trap was analysed and then replaced after each puff. Spin concentrations were determined by double-integration of the first derivative of the ESR signal. This was compared with the integrals of known standards using the TEMPO free radical. The radicals trapped with PBN were mainly carbon-centred, whilst the oxygen-centred radicals were identified with DMPO and DEPMPO. With each spin trap, the puff-resolved radical concentrations showed a characteristic pattern as a function of the puff number. Based on the spin concentrations, the DMPO and DEPMPO spin traps showed better trapping efficiencies than PBN. The implication for gas phase free radical analysis is that a range of different spin traps should be used to probe complex free radical reactions in cigarette smoke.

Electron paramagnetic resonance investigation of the free radicals in the gas and particulate phases of cigarette smoke using spin-trapping techniques

Free radicals in cigarette smoke have been studied using spin trapping EPR techniques. 2R4F reference cigarettes were smoked using 35 ml puff volumes of 2 seconds duration, once every 60 seconds. The particulate phase of the smoke was separated from the gas phase by passing the smoke through a Cambridge filter pad. For both phases, free radicals were measured and identified. A range of spin-traps was employed: PBN, DMPO, DEPMPO, and DPPH-PBN. In the gas-phase, short-lived carbon- and oxygen- centered radicals were identified; the ratios between them changed during the smoking runs. For the first puffs, C-centered radicals predominated while for the later puffs, O-centered radicals were mainly observed. The particulate phase and the ‘tar’ were studied as well.