Clear the Air for Children: The Impact of Air Pollution on Children

This report looks at how children, particularly the most disadvantaged, are affected by air pollution. It points out that around 300 million children live in areas where the air is toxic – exceeding international limits by at least six times – and that children are uniquely vulnerable to air pollution, breathing faster than adults on average and taking in more air relative to their body weight. The report also notes that air pollution is a major contributing factor in the deaths of around 600,000 children under age 5 every year and threatens the health, lives and futures of millions more. It concludes with a set of concrete steps to take so that children can breathe clean, safe air

Ireland's Foreign Policy Adaptation to Europe: Principled and Pragmatic?

This article examines Ireland's foreign policy adaptation to Europe over the last forty years of EU membership. It looks at the types of policy and institutional changes that have occurred in Ireland's foreign relations over four time periods: the historical-institutional context of Irish foreign policy (1921-73); Ireland's accession and adaptation to Europe (1973-86); the Single European Act to the Maastricht Treaty and beyond (1986-2008); and the international economic system (2008-). In each phase of these developments, the article considers the pressure for adaptation (i.e. Europeanisation), the response of the Irish foreign policy 'establishment' and the impact on foreign policy, including Ireland's outlook on international affairs

Convergence and evaluation-complexity analysis of a regularized tensor-Newton method for solving nonlinear least-squares problems

Given a twice-continuously differentiable vector-valued function r(x), a local minimizer of ∥r(x)∥2 is sought. We propose and analyse tensor-Newton methods, in which r(x) is replaced locally by its second-order Taylor approximation. Convergence is controlled by regularization of various orders. We establish global convergence to a first-order critical point of ∥r(x)∥2, and provide function evaluation bounds that agree with the best-known bounds for methods using second derivatives. Numerical experiments comparing tensor-Newton methods with regularized Gauss-Newton and Newton methods demonstrate the practical performance of the newly proposed method

Seeing statistics at the upgraded 3.8m UK infrared telescope (UKIRT)

From 1991 until 1997, the 3.8m UK Infrared Telescope (UKIRT) underwent a programme of upgrades aimed at improving its intrinsic optical performance. This resulted in images with a FWHM of 0."17 at 2.2 um in September 1998. To understand and maintain the improvements to the delivered image quality since the completion of the upgrades programme, we have regularly monitored the overall atmospheric seeing, as measured by radial displacements of subaperture images (i.e. seeing-generated focus fluctuations), and the delivered image diameters. The latter have been measured and recorded automatically since the beginning of 2001 whenever the facility imager UFTI (UKIRT Fast Track Imager) has been in use. In this paper we report the results of these measurements. We investigate the relation between the delivered image diameter and the RMS atmospheric seeing (as measured by focus fluctuations, mentioned above). We find that the best seeing occurs in the second half of the night, generally after 2am HST and that the best seeing occurs in the summer between the months of July and September. We also find that the relationship between Zrms and delivered image diameter is uncertain. As a result Zrms frequently predicts a larger FWHM than that measured in the images. Finally, we show that there is no correlation between near-infrared seeing measured at UKIRT and sub-mm seeing measured at the Caltech Submillimetre Observatory (CSO).Comment: 10 pages to appear in the SPIE proceeding vol. 4484 on Observatory Operations to Maximize Scientific Retur

Development of electroactive polymers for application in anti-corrosion formulations.

Corrosion is a major environmental and economic problem with many modern manmade structures heavily relying on the utilisation of metals and alloys due to their extraordinary strength, mechanical and physical properties. Applications such as those seen in the construction industry, aerospace and marine industries, all of which need a constant protection and barriers against the harsh environmental conditions. Current methods of protection employ the use of chromates in paint formulations for the active anti-corrosive paints or the uses of non-active polymeric paints acting solely as a physical barrier preventing the diffusion of ions through to the metal surface. However ideas have recently come forward regarding the use of conductive and electro-active polymers. Theorised to not only prevent the diffusions of ions on a physical level but to also act as an electrochemical barrier by passivating the surface of the metal so that it can protect itself from further degradation caused by corrosive agents, one such polymer that has been put forward is Polyaniline (PANI). Through the process of doping, PANI can be made to conduct an electrical current through the formation of charge carriers by oxidising the PANI with a protonic acid which can be functionalised. Further investigation has found that the functionalisation of these acids can dramatically change the once insoluble material in common solvents soluble, increasing the processability and possible increase the applications of this materials. This thesis reports the synthetic routes used to obtain functionalised Sulphonic acids based on the precursor 5-Sulphoisophthalic acid by acid catalysed esterification’s are described. With the synthesis phosphoric acid diester carried out by several named reported methods and both series were progressed forward to dope PANI (polyaniline). The optical properties were analysed for all doped PANI in DCM showing that branched side chains produced the highest optical absorption at around 944 nm and some as thin films (21) and (25), showing optical band gaps of 1.21 eV. This thesis also reports the anti-corrosions properties for the doped PANI systems. Films were cast coating mild carbon steel and copper plates, along with a range of acrylic resin/doped PANI composite films, PVC/doped PANI composite films and a set of films for an epoxide resin/doped PANI (17) composite. Samples were subjected to accelerated corrosion tests and showed that the application of PANI to the metal surfaces was beneficial and displayed efficacious anti-corrosion properties, not only in the doped state (emeraldine salt) but also in its native undoped state (emeraldine base) where the polymer undergoes redox reactions at the metal interface passivating the surface and creating an electrochemical barrier system which the polymer itself is a component however corrosion inhibition is only truly effective when a physical barrier is used in combination. The results of the dopant synthesis, doped PANI systems and their composites in resins and the data from NMR spectroscopy, IR, elemental analysis, LC-Mass spectroscopy, mass spectroscopy, UV-Vis spectroscopy are presented in this thesis. The accelerated corrosion tests and the data from scanning electron microscopy (SEM) are also presented within this thesis

Reversible Encapsulation of Xenon and CH2Cl2 in a Solid-State Molecular Organometallic Framework (Guest@SMOM)

Reversible encapsulation of CH2Cl2 or Xe in a non-porous solid-state molecular organometallic framework of [Rh(Cy2PCH2PCy2)(NBD)][BArF4] occurs in single-crystal to single-crystal transformations. These processes are probed by solid-state NMR spectroscopy, including 129Xe SSNMR. Non-covalent interactions with the -CF3 groups, and hydrophobic channels formed, of [BArF4]− anions are shown to be important, and thus have similarity to the transport of substrates and products to and from the active site in metalloenzymes

Anomalous thermal expansion in 1D transition-metal cyanides: what makes the novel trimetallic cyanide Cu1/3Ag1/3Au1/3CN behave differently?

The structural dynamics of a quasi-one-dimensional (1D) mixed-metal cyanide, Cu1/3Ag1/3Au1/3CN, with intriguing thermal properties is explored. All the current known related compounds with straight-chain structures, such as group 11 cyanides CuCN, AgCN, AuCN and bimetallic cyanides MxM’1-xCN (M, M’ = Cu, Ag, Au), exhibit 1D negative thermal expansion (NTE) along the chains and positive thermal expansion (PTE) perpendicular to them. Cu1/3Ag1/3Au1/3CN exhibits similar PTE perpendicular to the chains, however PTE, rather than NTE, is also observed along the chains. In order to understand the origin of this unexpected behavior, inelastic neutron scattering (INS) measurements were carried out, underpinned by lattice-dynamical density-functional-theory (DFT) calculations. Synchrotron-based pair-distribution-function (PDF) analysis and 13C solid-state nuclear-magnetic-resonance (SSNMR) measurements were also performed to build an input structural model for the lattice dynamical study. The results indicate that transverse motions of the metal ions are responsible for the PTE perpendicular to the chains, as is the case for the related group 11 cyanides. However NTE along the chain due to the tension effect of these transverse motions is not observed. As there are different metal-to-cyanide bond lengths in Cu1/3Ag1/3Au1/3CN, the metals in neighboring chains cannot all be truly co-planar in a straight-chain model. For this system, DFT-based phonon calculations predict small PTE along the chain due to low-energy chain-slipping modes induced by a bond-rotation effect on the weak metallophilic bonds. However the observed PTE is greater than that predicted with the straight-chain model. Small bends in the chain to accommodate truly co-planar metals provide an alternative explanation for thermal behavior. These would mitigate the tension effect induced by the transverse motions of the metals and, as temperature increases and the chains move further apart, a straightening could occur resulting in the observed PTE. This hypothesis is further supported by unusual evolution in the phonon spectra, which suggest small changes in local symmetry with temperature