The larvae of Pollicipes pollicipes were succesfully reared in the laboratory and their morphological characteristics described and compared to the previously described P. polymerus. Attempts to induce apparently healthy cyprids to settle in quantity, using methodology commonly employed for balanomorph barnacles, were unsuccessful indicating the lack of some major settlement cue(s). The scalpellids P. pollicipes and Capitulum mitella were shown able to voluntarily relocate, with measured speeds of up to 50 gm d'', but the lepadid Lepas anatifera cannot do so. The scalpellids used different mechanisms for relocation although both involved growth and sloughing of basal integument. A stimulus for directed travel was not found but gravity and unidirectional flow were rejected. The cement of lepadomorphs was shown to dissolve very slowly in sterile seawater. Cement in flowing seawater tanks, or in the presence of bacterial isolates collected from the cement, or in the presence of protease concentrated from bacterial cultures, did not dissolve at faster rates, to that of sterile cement, than could be explained by the sample sizes. The proteinaceous cement of P. pollicipes was delivered as a liquid in nl quantities over a period of 5-20 minutes before curing which took around 2 hours. Cement masses cured in seawater were found to be zoned due to a variable volume of space within, whilst cement delivered and cured in air or nitrogen was homogeneous. It was determined that the more porous inner zone of cement masses was inhibited from curing fully as a result of an inability to displace water. The partially cured zone could be induced to cure fully, by heating to dryness from a minimal volume of water. The presence of water was determined to be essential for curing. Differential degrees of curing of cement masses allowed for various physical and histochemical treatments which support both the rejection of disulphide bonding and phenol tanning and the growing evidence of hydrophobic complexing as central to the solidification mechanism of barnacle cement.

The ring opening polymerization of D,L-lactide (DLLA) using multifunctional hydroxyl-terminated initiators and catalyst/coinitiator systems based on Sn(Oct)2 afforded the preparation of star-shaped, poly(D,L-lactide)s (PDLLA)s of controlled molar mass, narrow molar mass distributions, and well-defined chain end functionality. Various modifications of star-shaped PDLLA resulted in macromolecules with tailored functionalities for biomedical applications. Star-shaped PDLLAs were modified to contain photoreactive methacrylate end groups and subsequent photo-crosslinking was performed. Photo-crosslinked networks based on methacrylated star-shaped PDLLAs exhibited thermal properties and mechanical performance that were superior to current approved clinical adhesives. In addition, the thermal and mechanical properties of the networks were strongly dependent on the composition and molar mass of the star-shaped PDLLA precursors. Tensile strengths in the range of 8-21 MPa were obtained while the Young's modulus increased from 12 to 354 MPa and were higher for networks based on urethane containing polymers. Star-shaped PDLLAs bearing complementary adenine and thymine terminal units were also prepared. The hydrogen bonding associations between complementary PDLLA macromolecules depended strongly on molar mass and hence, the concentration of multiple hydrogen bonding units. 1H NMR spectroscopy confirmed the formation of hydrogen-bonded complexes with a 1:1 optimal stoichiometry and an association constant of 84 M-1. The hydrogen-bonded complexes also exhibited significantly higher solution viscosities than non-blended polymer solutions of similar molar mass and concentration. Thermoreversible associations of PDLLA-based complementary polymers were observed in the melt phase and the melt viscosity of a blended complex was consistently an order of magnitude higher than non-functionalized star-shaped PDLLA of similar molar mass. Furthermore, melt electrospinning of the hydrogen-bonded complexes successfully resulted in fibers of significantly larger diameter (9.8 ± 2.0 µm) compared to the individual precursors (PDLLA-A = 4.0 ± 0.6 µm and PDLLA-T = 4.4 ± 1.0 µm). These results suggested that thermoreversibility, as well as the strength of the hydrogen bonding interactions between the end groups of the tailored star-shaped PDLLA-based supramolecular polymers controlled the fiber diameter in the melt electrospinning process. Highly ordered microporous honeycomb structures were developed on photo-functional star-shaped PDLLA surfaces. The pore dimensions were dependent on polymer solution concentration, polymer molar mass and relative humidity. The combination of self-organizing and cross-linking techniques resulted in free-standing, PDLLA membranes with high chemical stability as well as higher mechanical strength for further material patterning. Amikacin, an antibiotic commonly used for treating infections was successfully encapsulated in star-shaped PDLLA fibers that were electrospun from solution. Preliminary results suggested that molecular architecture influenced the encapsulation of the antibiotic and subsequent drug release profile. / Ph. D.