Transition metal ion co-ordination in hydrophilic polymer membrane

This thesis is concerned with the investigation of transition metal (TM) ion complexation with hydrophilic membranes composed of copolymers of 4-vinyl pyridine & 4-methyl-4'vinyl- 2,2'-bipyridine with 2-hydroxyethyl methacrylate. The Cu(II), CoCII) & Fe(II) complexes with these coordinating membranes were characterised by a variety of techniques, in order to assess the effect of the polymer on the properties of the complex, and vice versa. A detailed programme of work was instigated into the kinetics of formation for the polymer-bound tris(bipyridyl) iron(II) complex; the rate and extent of complex formation was found to be anion-dependent. This is explained in terms of the influence of the anion on the transport properties and water content of the membrane, the controlling factor in the development of the tris-complex being the equilibrium concentration of Fe(II) in the gel matrix. A series of transport studies were performed with a view to the potential application of complexing hydrogel membranes for aqueous TM ion separations. A number of salts were studied individually and shown to possess a range of permeabilities; the degree of interaction between particular metal-ion:ligand combinations is given by the lag-time observed before steady-state permeation is achieved. However, when two TM salts that individually display different transport properties were studied in combination, they showed similar lag-times & permeabilities, characteristic of the more strongly coordinating metal ion. This 'anti-selective' nature thus renders the membrane systems unsuitable for TM ion separations. Finally, attempts were made to synthesise and immobilise a series of N ,0-donor macrocyclic ligands into hydrogel membranes. Although the functionalisation reactions failed, limited transport data was obtained from membranes in which the ligands were physically entrapped within the polymer matrix.

Mesmerized by enlargement:the EU’s Eastern Neighborhood Policy and New Member State transition experience

The accession of the East-Central European (ECE) countries carried a promise of enhancing and enriching the EU’s Eastern policy. The new member states had the strongest interests among EU member states to ensure that countries in the East are prosperous, stable and democratic. Yet, EU’s Eastern policy has been largely criticised for its ineffectiveness. So why have they not been able to address the shortcomings in the EU’s Eastern policies? The article argues that the ECE countries supported the way the EU’s Eastern policies were conceived and implemented because they saw it as a potent vehicle to promote their own transition experience not only in the region but also within the EU. We argue that the ECE states have experienced three types of challenges when promoting their transition experience. First, uploading to the EU level remained largely at a rhetorical level. Second, there are conceptual and practical difficulties in defining what constitutes transition experience and harnessing it, as well as coordinating its transfer between the ECE states. Finally, while using transition experience as the basis for their development assistance strategies, the ECE countries actually insufficiently conceptualised the ‘development’ aspect in these policies. Being so driven by their own experience, they have not drawn the lessons from enlargement to use in a non-accession context, especially by incorporating the broader lessons with regard to development.