Nanoparticle Superlattice Engineering with DNA

In this thesis, we describe a set of design rules for using programmable oligonucleotide interactions, elements of both thermodynamic and kinetic control, and an understanding of the dominant forces that are responsible for particle assembly to design and deliberately make a wide variety of nanoparticle-based superlattices. Like the rules for ionic solids developed by Linus Pauling, these rules are guidelines for determining relative nanoparticle superlattice stability, rather than rigorous mathematical descriptions. However, unlike Pauling's rules, the set of rules developed herein allow one to not just predict crystal stability, but also to deliberately and independently control the nanoparticle sizes, interparticle spacings, and crystallographic symmetries of a superlattice. In the first chapter of this thesis, a general background is given for using DNA as a tool in programmable materials synthesis. Chapter 2 demonstrates how altering oligonucleotide length and nanoparticle size can be used to control nanoparticle superlattice lattice parameters with nanometer-scale precision. In the third chapter, the kinetics of crystallization are examined, and a method to selectively stabilize kinetic products is presented. The data in chapter 4 prove that it is the overall hydrodynamic radius of a DNA-functionalized particle, rather than the sizes of the inorganic nanoparticles being assembled, that dictates particle packing behavior. Chapter 5 demonstrates how particles that exhibit non-equivalent packing behavior can be used to control superlattice symmetry, and chapter 6 utilizes these data to develop a phase diagram that predicts lattice stability a priori to synthesis. In chapter 7, the ability to functionalize a particle with multiple types of oligonucleotides is used to synthesize complex lattices, including ternary superlattices that are capable of dynamic symmetry conversion between a binary and a ternary state. The final chapter provides an outlook on other developments in DNA-programmed nanoparticle assembly not covered in this thesis, as well as future challenges for this field. Supplementary information to support the conclusions of the thesis, as well as provide technical details on how these materials are synthesized, are provided in appendices at the end of the thesis. As a whole, this methodology presents a major advance towards nanoparticle superlattice engineering, as it effectively separates the identity of a particle core (and thereby its physical properties) from the variables that control its assembly, enabling the synthesis of designer nanoparticle-based materials.