DNA Self-Assembly Mediated by Programmable Soft-Patchy Interactions

Abstract

Adding shape and interaction anisotropy to a colloidal particle offers exquisitely tunable routes to engineer a rich assortment of complex-architected structures. Inspired by the hierarchical self-assembly concept with block copolymers and DNA liquid crystals and exploiting the unique assembly properties of DNA, we report here the construction and self-assembly of DNA-based soft-patchy anisotropic particles with a high degree of modularity in the system's design. By programmable positioning of thermoresponsive polymeric patches on the backbone of a stiff DNA duplex with linear and star-shaped architecture, we reversibly drive the DNA from a disordered ensemble to a diverse array of long-range ordered multidimensional nanostructures with tunable lattice spacing, ranging from lamellar to bicontinuous double-gyroid and double-diamond cubic morphologies, through the alteration of temperature. Our results demonstrate that the proposed hierarchical self-assembly strategy can be applied to any kind of DNA nanoarchitecture, highlighting the design principles for integration of self-assembly concepts from the physics of liquid crystals, block copolymers, and patchy colloids into the continuously growing interdisciplinary research field of structural DNA nanotechnology.

Mono- and bilayer smectic liquid crystal ordering in dense solutions of “gapped” DNA duplexes

“…Recent simulations ( 26) also support the possibility of various lamellar self-assembly by rod-coil-rod triblocks. Very recently, lamellar and various bicontinuous phases have been characterized in coil-rod-coil DNA-polymer hybrids (27).…”

Self assembling cluster crystals from DNA based dendritic nanostructures

“…The key structural features of the proposed dendritic-like building blocks are their open structure and the chemical dissimilarity between the flexible Poxa chains and the stiff all-DNA dendrons. By linking together two stiff and highly charged dendritic blocks (all-DNA dendrons) through a long and flexible polymer chain (Poxa), in combination with the microphase separation mechanism driven by the immiscibility between the DNA and polymeric blocks 46 , we allow the centers of masses of different DNA-based constructs to coincide, without significant interpenetration of the dendrons. We shall demonstrate that the degree of segregation between all-DNA dendron and Poxa blocks can be temperature-controlled within the weak limit 47 , owning to Poxa’s LCST and triblock’s macromolecular architecture.…”

“…An intriguing aspect of this study is that the building block design, reliant on the block copolymer paradigm, confers our DNA-based triblock with temperature-responsiveness, resulting to cluster crystal structures with unexpected optical anisotropy and self-assembly transition pathways that can readily be controlled by altering the temperature. This confluence of self-assembly approaches from block copolymers 62 and DNA nanotechnology 63 has already been shown to be capable of furnishing temperature-regulated nanoscale structures with high levels of self-assembled structural complexity 46 . Given its versatile and robust character, the synthetic scheme reported here can easily be applied to any kind of all-DNA nanoscale architecture.…”

Endogenous microRNA triggered enzyme-free DNA logic self-assembly for amplified bioimaging and enhanced gene therapy via in situ generation of siRNAs

“…For these strategies, the integration of siRNAs into DNA nanostructures mainly relies on the hybridization or chemical modification, thus, the unavoidable leakage and degradation, as well as the limited payload capacity may diminish the gene therapy efficiency [ 13 – 15 ]. As an alternative method, in situ generation of siRNAs can significantly enhance the specificity and delivery stability, which thus provides a robust and powerful strategy for cancer therapy [ 16 , 17 ].…”