Geometrically programmed self-limited assembly of tubules using DNA origami colloids

Abstract

Self-assembly is one of the most promising strategies for making functional materials at the nanoscale, yet new design principles for making self-limiting architectures, rather than spatially unlimited periodic lattice structures, are needed. To address this challenge, we explore the tradeoffs between addressable assembly and self-closing assembly of a specific class of self-limiting structures: cylindrical tubules. We make triangular subunits using DNA origami that have specific, valence-limited interactions and designed binding angles, and we study their assembly into tubules that have a self-limited width that is much larger than the size of an individual subunit. In the simplest case, the tubules are assembled from a single component by geometrically programming the dihedral angles between neighboring subunits. We show that the tubules can reach many micrometers in length and that their average width can be prescribed through the dihedral angles. We find that there is a distribution in the width and the chirality of the tubules, which we rationalize by developing a model that considers the finite bending rigidity of the assembled structure as well as the mechanism of self-closure. Finally, we demonstrate that the distributions of tubules can be further sculpted by increasing the number of subunit species, thereby increasing the assembly complexity, and demonstrate that using two subunit species successfully reduces the number of available end states by half. These results help to shed light on the roles of assembly complexity and geometry in self-limited assembly and could be extended to other self-limiting architectures, such as shells, toroids, or triply periodic frameworks.

Recent Advances in DNA Origami-Engineered Nanomaterials and Applications

“…Nevertheless, the superorigami still has the issues of restricted geometry, symmetry, and size. Alternatively, large origami superstructures can be created by polymerizing origami monomers through blunt-end, ,,, sticky-end, ,, or shape-complementary interactions . Third, in many optical applications, the optical components in the supercell of a lattice should not be regularly reiterated.…”

Building blocks of non-Euclidean ribbons: size-controlled self-assembly via discrete frustrated particles

“…which is derived in Appendix B, eqn ( 21)- (33). As we consider assemblies to form with open edges only along low energy directions in the bond lattice, it is straightforward to compute the edge energy per unit length…”

“…The restrictions placed on the elasticity and range of frustration accumulation by the interaction range suggest the feasible avenue for engineering self-limiting systems requires the combination of (larger) colloidal-scale particles bound by shorter range interactions. We point out a recent example of DNA origami particles 32,33,66 designed to be triangular subunits, B50 nm in size with controllable inter-particle geometry, and large w c d, assemblies driven by short-range base-stacking interactions, whose interactions range may be less than B1 nm. 67 Beyond the requirement of shorter-range interactions relative to subunit size, frustration-limitation will also require engineered colloidal particles with the combination of precise geometry binding and also stiffness comparable to or exceeding that from the short-range, base-stacking interactions.…”

“…[27][28][29] In principle, recent progress in the synthesis of colloidal-scale particles with programmed shape can allow for tunable shape frustration that can more fully test the continuum theory description of size control. 30,31 Notably, advances in DNA nanotechnology 32,33 as well as synthetic protein engineering [34][35][36][37] allow for both careful design and control of the shape frustration of self-assembling nanoscale units as well as new opportunities for programming the interactions to separately tune the strength of cohesion and costs associated with distinct modes of assembly deformation. However, due to the primary reliance on continuum descriptions of GFA, several basic challenges remain to relate emergent thermodynamic behaviors in a particular system of self-assembling frustrated subunits.…”

Building blocks of non-Euclidean ribbons: Size-controlled self-assembly via discrete, frustrated particles

“…[27][28][29] In principle, recent progress in the synthesis of colloidal-scale particles with programmed shape can allow for tunable shape frustration that can more fully test the continuum theory description of size control. [30,31] Notably, advances in DNA nanotechnology [32,33] as well as synthetic protein engineering [34][35][36][37] allow for both careful design and control of the shape frustration of self-assembling nanoscale units as well as new opportunities for programming the interactions to separately tune the strength of cohesion and costs associated with distinct modes of assembly deformation. However, due to the primary reliance on continuum descriptions of GFA, several basic challenges remain to relate emergent thermodynamic behaviors in a particular system of selfassembling frustrated subunits.…”