Advancements in the biomedical field are driven by the design of novel materials with controlled physical and bio-interactive properties. To develop such materials, researchers rely on the use of highly efficient reactions for the assembly of advanced polymeric scaffolds that meet the demands of a functional biomaterial. In this thesis two main strategies for such materials have been explored; these include the use of off-stoichiometric thiol-ene networks and dendritic polymer scaffolds. In the first case, the highly efficient UV-induced thiol-ene coupling (TEC) reaction was used to create crosslinked polymeric networks with a predetermined and tunable excess of thiol or ene functionality. These materials rely on the use of readily available commercial monomers. By adopting standard molding techniques and simple TEC surface modifications, patterned surfaces with tunable hydrophobicity could be obtained. Moreover, these materials are shown to have great potential for rapid prototyping of microfluidic devices. In the second case, dendritic polymer scaffolds were evaluated for their ability to increase surface interactions and produce functional 3D networks. More specifically, a self-assembled dendritic monolayer approach was explored for producing highly functional dendronized surfaces with specific interactions towards pathogenic E. coli bacteria. Furthermore, a library of heterofunctional dendritic scaffolds, with a controllable and exact number of dual-purpose azide and ene functional groups, has been synthesized. These scaffolds were explored for the production of cell interactive hydrogels and primers for bone adhesive implants. Dendritic hydrogels decorated with a selection of bio-relevant moieties and with Young’s moduli in the same range as several body tissues could be produced by facile UV-induced TEC crosslinking. These gels showed low cytotoxic response and relatively rapid rates of degradation when cultured with normal human dermal fibroblast cells. When used as primers for bone adhesive patches, heterofunctional dendrimers with high azide-group content led to a significant increase in the adhesion between a UV-cured hydrophobic matrix and the wet bone surface (compared to patches without primers).

Functional polymeric scaffolds have been employed in biological applications as several utilities, from nano-sized drug delivery systems to concrete implants. The progression in biological fields essentially relies on finding an appropriate material to fulfil the critical requirements for various types of applications with great potential for tuning functionality and mechanical properties. Therefore, the generation of new materials in extensive libraries is desirable for researchers. In this thesis, two main varieties of functional scaffolds have been constructed; these include i) periodic structure isoporous membranes and ii) three dimension (₃D) crosslinked networks with programmable functionalities and mechanical properties. In the first case, a library of linear dendritic (LD) block copolymers was synthesised from biocompatible 2,2-bis(methylol)propionic acid (bis-MPA) dendrons and 2- hydroxyethyl methacrylate (HEMA) derivatives. These materials were successfully employed for the fabrication of isoporous membranes via the facile Breath Figure (BF) method. The dendritic periphery end groups control the manipulation of film morphology, as well as introduction of desired functionalities, either pre- or post- film formation. The introduction of azide functional group along the polymer backbone allows crosslinking reaction, which enhances the stability of the isoporous films. The stability towards temperature was improved from around its glass transition temperature (T_g) to 400 °C after crosslinking; simultaneously the porosity is maintained after immersion in the whole range of pH (1-14). These materials show great potential use as high performance isoporous membranes in futuristic applications such as micro-reactors, sensors and cell patterning platforms. In the second case, the facile fabrication of functional networks employs off-stoichiometric crosslinking, which resulted in residual reactive functional groups after film formation and networks with different crosslinking density. This straightforward off-stoichiometric concept is applied with commercially available materials and well-controlled dendritic-linear-dendritic (DLD) hybrid polymers, generating functional networks with different properties from high stiffness film to soft hydrogels. The network post-modification can be performed topologically and throughout the scaffold. Several crosslinking chemistries were employed for construction of hydrogels from DLD hybrid polymers. The Copper(I) Catalysed Azide-Alkyne Cycloaddition (CuAAC) click reaction results in hydrogels with higher compressive modulus compared to other hydrogels constructed from thiol-ene, thiol-yne and amine-N-hydroxysuccinimide (NHS) esters coupling methods with similar building blocks. These functional crosslinked networks are suitable for numerous applications including fabrication of microfluidic devices, cell culture platforms and bone adhesives.