A substrate-independent method has been devised for ring formation at solid surfaces. This entails the aminolysis reaction of allylamine with maleic anhydride pulsed plasma polymer films to yield terminal alkene groups at the surface. Subsequent exposure to 1,3-cyclohexadiene leads to a Diels-Alder type (4 + 2) cycloaddition reaction to give a mixture of endo- and exo-bicyclo[2.2.2]oct-2-ene rings.

Amine-terminated polyamidoamine (PAMAM) dendrimers can be immobilized onto anhydride-functionalized pulsed plasma polymer surfaces via amide linkage formation. The packing density of dendrimers at the surface can be tailored by programming the pulse duty cycle parameters during plasma polymerization. These PAMAM dendrimer layers are shown to be useful for a variety of surface-related phenomena, for example, fluorination, adhesion, and gas barrier enhancement.

The work in this thesis has concentrated upon the chemical functionalization of plasma polymer surfaces. The ability to deposit and then funotionalize these surface layers has practical implications for many different areas, such as biomedical uses and heterogeneous catalysis and many different functional groups can be attached to surfaces using the plasma polymer layer as an intermediate. A variety of substrates, from glass to polymer films have been studied. Two different monomers have been studied in this work. The majority of work was carried out using a maleic anhydride plasma polymer (MAPP), which can be deposited from maleic anhydride under pulsed plasma conditions. The second monomer used was allylamine, whose plasma polymer has previously been studied as a biomedical layer. For both of these monomers, a variety of functionalization reactions have been studied. In the case of the anhydride group the key reaction is that which occurs between the anhydride group and amines. The reaction of amines with the anhydride is through a ring opening of the anhydride group, leading to the formation of amic acid groups. This part of the thesis allowed an understanding of the mechanism of vapour phase reactions to be acquired. Once this understanding had been achieved, many more amine containing groups were studied, such as poly(amidoamine) (PAMAM) dendrimers, functionalized polystyrene particles, polycations and molecules containing double bonds were reacted with the MAPP surface. These functional molecules can be used for immobilizing metal particles, stabilizing colloids adhering surfaces and Diels-Alder reactions. In the case of the allylamine, a variety of different functionalization routes we studied. Formation of amide groups at the surface was studied using heptafluorobutryl chloride and carboxylic acid functionalized polystyrene beads. The ability of the allylamine plasma polymer layer to act as a polycationic layer was investigated with an anionic polymeric dye, DNA and gold colloids.

Vapor phase esterification of 2,2,2-trifluoroethanol, 4,4,4-trifluorobutanol, and ethanol with poly(ethylene-alt-maleic anhydride) copolymer surfaces has been followed by X-ray photoelectron spectroscopy (XPS). The rate of reaction and yield are found to be strongly dependent upon the nucleophilicity of the chosen alcohol.

Pulsed plasma polymerization of maleic anhydride leads to the deposition of well-defined anhydride functionalized films. These layers readily undergo reaction with amine-terminated nucleophiles to produce surface amide linkages that convert into cyclic imide groups upon heating. Potential applications include adhesion and biocompatibility.