Abstract of Dissertation Presented to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy TWO-DIMENSIONAL SELF-ASSEMBLY OF AMPHIPHILIC BLOCK COPOLYMERS AT THE AIR/WATER INTERFACE AND NANOPARTICLES FOR DRUG DETOXIFICATION APPLICATIONS By Thomas J. Joncheray December 2006 Chair: Randolph S. Duran Major Department: Chemistry The two-dimensional self-assembly at the air/water (A/W) interface of various block copolymers (dendrimer-like polystyrene-b-poly(tert-butylacrylate) (PS-b-PtBA) and polystyrene-b-poly(acrylic acid) (PS-b-PAA), linear and five-arm star poly(ethylene oxide)-b- poly(s-caprolactone) (PEO-b-PCL), and three-arm star triethoxysilane-functionalized polybutadiene-b-poly(ethylene oxide) (PB(Si(OEt)3)-b-PEO)) was investigated through surface pressure measurements isothermss, isobars, isochores, and compression-expansion hysteresis experiments) and atomic force microscopy (AFM) imaging. The PS-b-PtBA and the PS-b-PAA samples formed well-defined circular surface micelles at low surface pressures with low aggregation numbers (~ 3-5) compared to linear analogues before collapse of the PtBA chains and aqueous dissolution of the PAA segments take place around 24 and 5 mN/m, respectively. The linear PEO-b-PCL samples exhibited three phase transitions at 6.5, 10.5, and 13.5 mN/m corresponding respectively to PEO aqueous dissolution, PEO brush formation, and PCL crystallization. The two PEO phase transitions were not observed for the star-shaped PEO-b-PCL samples because of the negligible surface activity of the star-shaped PEO core compared to its linear analogue. The PB(Si(OEt)3)-b-PEO sample was cross-linked at the A/W interface by self-