Session P46: Invited Session: DNA-Programmable Particle Assembly

Self-Replication of Nanoscale tiles and patterns

We want to make a ``non-biological'' system which can self-replicate. The idea is to design particles with specific and reversible and irreversible interactions, introduce seed motifs, and cycle the system in such a way that a copy is made. Repeating the cycle would double the number of offspring in each generation leading to exponential growth. Using the chemistry of DNA either on colloids or on DNA tiles makes the specific recognition part easy. In the case of DNA tiles we have in fact replicated the seed at least to the third generation. The DNA linkers can also be self-protected so that particles don't interact unless they are held together for sufficient time -- a nano-contact glue. Chemical modification of the DNA allows us to permanently crosslink hybridized strands for irreversible bonds and a new type of photolithography. We have also designed and produced colloidal particles that use novel ``lock and key'' geometries to get specific and reversible physical interactions.\\[4pt] With Tong Wang, Ruojie Sha, Remi Dreyfus, Mirjam E. Leunissen, Corinna Maass, David J. Pine, and Nadrian C. Seeman.   

Inverse Problem in Self-assembly

By decorating colloids and nanoparticles with DNA, one can introduce highly selective key-lock interactions between them. This leads to a new class of systems and problems in soft condensed matter physics. In particular, this opens a possibility to solve inverse problem in self-assembly: how to build an arbitrary desired structure with the bottom-up approach? I will present a theoretical and computational analysis of the hierarchical strategy in attacking this problem. It involves self-assembly of particular building blocks (``octopus particles''), that in turn would assemble into the target structure. On a conceptual level, our approach combines elements of three different brands of programmable self assembly: DNA nanotechnology, nanoparticle-DNA assemblies and patchy colloids. I will discuss the general design principles, theoretical and practical limitations of this approach, and illustrate them with our simulation results. Our crucial result is that not only it is possible to design a system that has a given nanostructure as a ground state, but one can also program and optimize the kinetic pathway for its self-assembly.   

Structural flexibility of DNA-Nanoparticle Assemblies

Encoding interactions between nanoparticles using DNA allows for creation of new classes of materials in which particles arrange in superlattices with the structure mainly defined by particle geometry and interactions between DNA shells. The phase behavior in these systems quite often can be rationalized using the interaction energy maximization argument for DNA provided key-lock recognition. However, a polymeric nature of DNA connections can bring about an unexpected phase behavior with structures typically not observed for non-directional interactions. In addition, DNA sensitivity to various specific and non-specific stimuli provides for precise lattice tunability within a given phase. We will provide several examples of phase change in systems of DNA interacting nanoparticles, where unusual, low dimensional structures form due to collective behavior of DNA chains. We will also discuss various ways to dynamically change superlattice parameters using physical variables such as electrostatic interactions or external osmotic pressure for continuous lattice tunability or using DNA machinery to program a step-wise change in the lattice parameter of the assemblies.   

Nanoparticle Superlattice Engineering with DNA

Recent developments in strategies for assembling nanomaterials have allowed us to draw a direct analogy between the assembly of solid state atomic lattices and the construction of nanoparticle superlattices. Herein, we present a set of six design rules for using DNA as a programmable linker to deliberately stabilize nine distinct colloidal crystal structures, with lattice parameters that are tailorable over the 25-150 nm size regime. These rules are analogous to those put forth by Pauling decades ago to explain the relative stability of lattices composed of atoms and small molecules. It is ideal to use DNA as a nanoscale bond to connect nanoparticles to achieve colloidal superlattice structures in this system, since its programmable nature allows for facile control over nanoparticle bond length and strength, and nanoparticle bond selectivity. This assembly method affords simultaneous and independent control over nanoparticle structure, crystallographic symmetry, and lattice parameters with nanometer scale precision. Further, we have developed a phase diagram that predicts the design parameters necessary to achieve a lattice with a given symmetry and lattice parameters a priori. The rules developed in this work present a major advance towards true materials by design, as they effectively separate the identity of a particle core (and thereby its physical properties) from the variables that control its assembly.   

Real-space crystallography and transformations of DNA-directed particle superlattices

DNA is a versatile tool for directing the controlled self-assembly of nanoscopic and microscopic objects. The interactions between microspheres due to the hybridization of DNA strands grafted to their surface have been measured and can be modeled in detail, using well-known polymer physics and DNA thermodynamics. Knowledge of the potential, in turn, enables the exploration of the complex phase diagram and self-assembly kinetics in simulation. In experiment, at high densities of long grafted DNA strands, and temperatures where the binding is reversible, these system readily form colloidal crystals having a diverse range of symmetries. For interactions that favor alloying between two same-sized colloidal species, our experimental observations compare favorably to a simulation framework that predicts the equilibrium phase behavior, crystal growth kinetics and solid-solid transitions. We will discuss the crystallography of the novel alloy structures formed and address how particle size and heterogeneity affect nucleation and growth rates.