Title: DNA-Programmed Nanomaterials and Exploration of Their Chemical Activities
Description: DNA-based self-assembly has been developed as an ideal means to create precisely controllable and hierarchical materials from the bottom up due to DNA’s regularity, programmability and addressability. This dissertation demonstrates utilization of the powerful molecular tool to construct 0D, 1D, 2D, and 3D nanomaterials. In the first part of the dissertation, I overview the significance of anisotropic building blocks and discuss how to engineer them in a programmable manner (Chapter 1). I establish a general approach to pattern nanoparticles where DNA nanostructure is employed as a template to transfer prescribed molecular linkers onto an isotropic nanoparticle surface, generating so-called patchy nanoparticle (Chapter 2). I then show the manipulation of nanoscale patches constituted by DNA molecules to fabricate nano-polymeric assemblies (Chapters 3-4). Furthermore, I design sized-confined 2D DNA screens to display discrete nanoparticle patterns and manage dynamic switches of these patterns (Chapter 5).

Despite the advancements in fabricating sophisticated DNA nanoarchitectures, achievement of the original motivation of founding DNA nanotechnology, engineering protein nanostructures, is still hindered due to proteins’ heterogeneity and limited general methodologies to integrate them with DNA materials. In the second part of this dissertation, I present three studies towards DNA-based organization of two cascade enzymes, glucose oxidase and horseradish peroxidase, exhibiting the ability to manipulate proteins at DNA molecular scaffold (Chapter 6), 2D surface (Chapter 7) and 3D lattice (Chapter 8). In particular, the eighth chapter introduces a platform approach for creating by-design organizations of target enzymes decoupled from their inherent properties, paving way for engineering protein superlattice. In addition, all the studied well-defined enzymatic materials can be employed to investigate the correlation of biocatalytic functions with arbitrary enzyme organizations, which is able to resolve the long-running controversy over mechanisms of enzymatic activity enhancement due to DNA scaffolding.