Many emerging technologies would greatly benefit from reliable methods for the production of functional materials with well-defined 3D nanoscale structure. Conceptually, approaches to produce such architectures are divided into two broad classes; top down and bottom up manufacture. In the top down approach, nanoscale structure is created through the controlled removal of material from a bulk starting object. Top down methods have a proven record of reliability in the fabrication of extended two dimensional arrays with fine control over nanoscale features. However, such approaches become increasingly cumbersome when attempting to define structure in three dimensions rather than two.

Bottom up methods promise a more reliable route to the formation of such materials. Here, molecular scale building units self-assemble to form a desired structure, driven by pre-defined interactions between individual motifs. Due to the highly specific molecular recognition properties of nucleic acids, along with their relatively simple synthesis and wide range of potential chemical modifications, DNA nanotechnology is now regarded as a prime route for the bottom up fabrication of nanostructured materials. However, current approaches to the formation of designed 3D DNA crystals are complicated by the difficulties in designing sub-units able to assemble in a predictable fashion over length-scales orders of magnitude larger than themselves. Amphiphiles are able to self-assemble into a variety of 3D crystalline phases driven by the frustrated micro-phase separation of hydrophobic and hydrophilic domains, with the structural properties reliant primarily on overall topology of the molecules rather than their exact chemical and geometrical features. Although the mechanism underlying amphiphile self-assembly is robust, it inherently limits control over the fine-scale structural details.

This thesis reports on a new class of self-assembling DNA motifs; amphiphilic cholesterol-functionalised DNA nanostars, \emph {C-stars}. C-stars combine key advantages of all-DNA motifs and conventional amphiphilic molecules -- allowing for the preparation of expanded crystalline frameworks with tunable properties and embedded functionality.