Yes / For the development of applications and novel uses for peptide nanostructures, robust routes for their surface functionalization, that ideally do not interfere with their self‐assembly properties, are required. Many existing methods rely on covalent functionalization, where building blocks are appended with functional groups, either pre‐ or post‐assembly. A facile supramolecular approach is demonstrated for the formation of functionalized nanofibers by combining the advantages of biocatalytic self‐assembly and surfactant/gelator co‐assembly. This is achieved by enzymatically triggered reconfiguration of free flowing micellar aggregates of pre‐gelators and functional surfactants to form nanofibers that incorporate and display the surfactants’ functionality at the surface. Furthermore, by varying enzyme concentration, the gel stiffness and supramolecular organization of building blocks can be varied. / FP7 Marie Curie Actions of the European Commission. Grant Number: 289723; EPSRC; HFSP; ERC; Leverhulme Trust

Cancer is a disease that varies dramatically from person to person due to the specifics of the individual's physiology and the source of the cancer. In most cases, the origin of the cancer can be determined but metastasis can lead to tumors anywhere and thus many cancers require treatment of the whole body. Since many of the drugs that are used to treat cancer are toxic to healthy cells as well as cancerous ones, there has been considerable interest in developing ways to convey the drug specifically to the cancer cells with minimal exposure to healthy cells. Colloid drug delivery vehicles have shown considerable progress toward this end, while also reducing degradation of the drug prior to delivery to targeted sites (particularly important for oligonucleotide and protein therapeutics), and controlling release rates. Toward the end of improved drug delivery, this thesis work investigates the encapsulation of DNA in gelatin microspheres (GMS) and the subsequent temperature controlled release of the encapsulated DNA from these GMS. DNA-loaded GMS were then used as templates for colloidal satellite assemblies and the released DNA was shown to competitively displace the original partner strands of immobilized DNA on the surface of the assemblies. To support these investigations, hybridization of DNA at colloidal surfaces was also investigated using in situ measurements and found to significantly deviate from solution behavior. DNA hybridization is of particular interest as means of controlling the functionality of colloidal structures because it is uniquely reversible and tunable as well as biocompatible. Gelatin was chosen as the encapsulation matrix for its superior biocompatibility, convenient gel to liquid phase transition at ~35 oC, and economical availability.