This thesis covers the synthesis of conjugates of 2-Deoxy-D-ribose-5-phosphate aldolase (DERA) with suitable polymers and the subsequent immobilization of these conjugates in thin films via two different approaches. 2-Deoxy-D-ribose-5-phosphate aldolase (DERA) is a biocatalyst that is capable of converting acetaldehyde and a second aldehyde as acceptor into enantiomerically pure mono- and diyhydroxyaldehydes, which are important structural motifs in a number of pharmaceutically active compounds. Conjugation and immobilization renders the enzyme applicable for utilization in a continuously run biocatalytic process which avoids the common problem of product inhibition. Within this thesis, conjugates of DERA and poly(N-isopropylacrylamide) (PNIPAm) for immobilization via a self-assembly approach were synthesized and isolated, as well as conjugates with poly(N,N-dimethylacrylamide) (PDMAA) for a simplified and scalable spray-coating approach. For the DERA/PNIPAm-conjugates different synthesis routes were tested, including grafting-from and grafting-to, both being common methods for the conjugation. Furthermore, both lysines and cysteines were addressed for the conjugation in order to find optimum conjugation conditions. It turned out that conjugation via lysine causes severe activity loss as one lysine plays a key role in the catalyzing mechanism. [...]

Peptide-polymer conjugates are a hybrid class of materials that take advantage of natural and synthetic building blocks whose individual properties can be synergistically combined. Their modular design enables the incorporation of chemical functionalities, hierarchal control over assembly, as well as unique chemical, biological, and mechanical properties. These conjugates allow for the design of complex, highly responsive materials with applications in many fields. Within this dissertation, two different peptide-polymer conjugates are discussed.

This thesis describes the production of advanced materials comprising a wide array of polymer-based building blocks. These materials include bio-hybrid polymer-peptide conjugates, based on phenylalanine and poly(ethylene oxide), and polymers with intrinsic microporosity (PIMs). Polymer-peptides conjugates were previously synthesised using click chemistry. Due to the inherent disadvantages of the reported synthesis, a new, simpler, inexpensive protocol was sought. Three synthetic methods based on amidation chemistry were investigated for both oligopeptide and polymerpeptide coupling. The resulting conjugates produced were then assessed by various analytical techniques, and the new synthesis was compared with the established protocol. An investigation was also carried out focussing on polymer-peptide coupling via ester chemistry, involving deprotection of the carboxyl terminus of the peptide. Polymer-peptide conjugates were also assessed for their propensity to self-assemble into thixotropic gels in an array of solvent mixtures. Determination of the rules governing this particular self-assembly (gelation) was required. Initial work suggested that at least four phenylalanine peptide units were necessary for self-assembly, due to favourable hydrogen bond interactions. Quantitative analysis was carried out using three analytical techniques (namely rheology, FTIR, and confocal microscopy) to probe the microstructure of the material and provided further information on the conditions for self-assembly. Several polymers were electrospun in order to produce nanofibres. These included novel materials such as PIMs and the aforementioned bio-hybrid conjugates. An investigation of the parameters governing successful fibre production was carried out for PIMs, polymer-peptide conjugates, and for nanoparticle cages coupled to a polymer scaffold. SEM analysis was carried out on all material produced during these electrospinning experiments.