The Western European Variscan orogenic belt is thought to represent the final in a series of Paleozoic continental collisions that culminated with the amalgamation of the supercontinent Pangea. The Iberian segment of the Variscan belt is characterized by Cantabrian orocline, which is 180º and convex toward the west. Several lines of evidence are at odds with classical interpretation of the Cantabrian orocline as the core of the much larger ‘Ibero-Armorican’ arc, suggesting instead that it is structurally continuous with a second more southerly and complimentary orocline. Paleocurrent data collected from the Lower Ordovician Armorican Quartzite of the deformed Iberian Paleozoic passive margin sequence confirm the existence of the so-called Central Iberian orocline. Structural continuity between the Cantabrian and Central Iberian oroclines suggests that they formed contemporaneously and in the same fashion. Mesoscale vertical-axis folds deforming slaty cleavage and shear fabric within the Ediacaran Narcea Slates have a dominant vergence toward the hinge of the Cantabrian orocline, suggesting that its formation was in part accommodated by a mechanism of flexural shear during buckling of a linear belt in response to an orogen parallel principle compressive stress. The Cantabrian-Central Iberian coupled oroclines therefore palinspastically restore to an originally linear belt 2300 km in length. Provenance analysis of detrital zircons sampled from the Armorican Quartzite along a 1500-km-long segment of the palinplastically restored Iberian passive margin indicate that it originated in a paleogeographic position stretching east-west along the northern limits of north African Gondwana, from the Arabian-Nubian Shield to the Saharan hinterland. Paleomagnetic data and the distribution of Variscan ophiolites support a model of mid-Paleozoic separation of the Variscan autochthon (Armorican continental ribbon) from north Gondwana preceding or in conjunction with a 90º rotation required to reorient the ribbon to a Late Carboniferous north-south trend. Formation of the Iberian coupled oroclines accommodated 1100 km of orogen parallel shortening. The Western European Variscan belt, North American Cordillera, and Eastern European Alpine system are orogens similarly characterized by both coupled oroclines and paleomagnetic inclinations that are significantly shallower than cratonic reference values. Palinspastic restoration of the Alaskan and Carpathian–Balkan coupled oroclines fully resolves inclination anomalies within the Cordillera and Eastern Alpine system, respectively. Inclination anomalies within the Iberian Variscan belt are only partially resolved through palinspastic restoration of the Iberian coupled oroclines, but the sinuous geometry of the belt is not yet fully deciphered. Oroclines within the Western European Variscan belt, not the orogen itself, provide the true record of Pangean amalgamation. / Graduate

Macromolecular biomaterials often require covalent crosslinking to achieve adequate stability and mechanical strength for their given application. However, the use of auxiliary chemicals may be associated with long-term toxicity in the body. Oppositely-charged polyelectrolytes (PEs) have the advantage that they can self-crosslink electrostatically and those derived from marine organisms are an inexpensive alternative to glycosaminoglycans present in the extracellular matrix of human tissues. A range of different combinations of PEs and preparation conditions have been reported in the literature. However, although there has been some work on complex formation between chitosan (CS) and carrageenan (CRG), much of the work undertaken has ignored the effect of pH on the consequent physicochemical properties of self-crosslinked polyelectrolyte complex (PEC) gels, films and scaffolds. Chitosan is a positively-charged polysaccharide with NH3+ side groups derived from shrimp shells and, carrageenan is a negatively-charged polysaccharide with OSO3- side groups derived from red seaweed. These abundant polysaccharides possess advantageous properties such as biodegradability and low toxicity. However, at present, there is no clear consensus on the cell binding properties of CS and CRG or CS-CRG PEC materials. The aim of this study was to explore the properties of crosslinker-free PEC gels, solvent-cast PEC films and freeze-dried PEC scaffolds based on CS and CRG precursors for medical applications. The objective was to characterise the effect of pH of the production conditions on the physicochemical and biological properties of CS-CRG PECs. Experimental work focused on the interaction between PEs, the composition of PECs, the rheological properties of PEC gels and the mechanical properties of PEC films and scaffolds. In addition, cell and protein attachment to the PEC films was assessed to determine their interactions in a biological environment. For biomedical applications, these materials should ideally be stable when produced such that they can be processed to form either a film or a scaffold and have mechanical properties comparable to those of collagenous soft tissues. FTIR was used to confirm PEC formation. Zeta potential measurements indicated that the PECs produced at pH 2-6 had a high strength of electrostatic interaction with the highest occurring at pH 4-5. This resulted in stronger intra-crosslinking in the PEC gels which led to the formation of higher yield, solid content, viscosity and fibre content in PEC gels. The weaker interaction at pH 7-12 resulted in higher levels of CS incorporated into the complex and the formation of inter-crosslinking through entanglements between PEC units. This resulted in the production of strong and stiff PEC films and scaffolds appropriate for soft tissue implants. The PECs prepared at pH 7.4 and 9 also exhibited low swelling and mass loss, which was thought to be due to the high CS content and entanglements. From the range of samples tested, the PECs produced at pH 7.4 appeared to show the optimum combination of yield, stability and homogeneity for soft tissue implants. Biological studies were performed on CS, CRG and PECs prepared at pH 3, 5, 7.4 and 9. All of the PE and PEC films were found to be non-cytotoxic. When the response of three different cell types and a high binding affinity protein (tropoelastin) was evaluated; it was found that the CS-CRG PEC films displayed anti-adhesive properties. Based on these experimental observations and previous studies, a mechanistic model of the anti-adhesive behaviour of PEC surfaces was proposed. It was therefore concluded that the CS-CRG PECs produced might be suitable for non-biofouling applications.

No description available.