Programming the morphology of DNA origami crystals by magnesium ion strength

Abstract

Harnessing the programmable nature of DNA origami for controlling structural features in crystalline materials affords opportunities to bring crystal engineering to a remarkable level. However, the challenge of crystallizing a single type of DNA origami unit into varied structural outcomes remains, given the requirement for specific DNA designs for each targeted structure. Here, we show that crystals with distinct equilibrium phases and shapes can be realized using a single DNA origami morphology with an allosteric factor to modulate the binding coordination. As a result, origami crystals undergo phase transitions from a simple cubic lattice to a simple hexagonal (SH) lattice and eventually to a face-centered cubic (FCC) lattice. After selectively removing internal nanoparticles from DNA origami building blocks, the body-centered tetragonal and chalcopyrite lattice are derived from the SH and FCC lattices, respectively, revealing another phase transition involving crystal system conversions. The rich phase space was realized through the de novo synthesis of crystals under varying solution environments, followed by the individual characterizations of the resulting products. Such phase transitions can lead to associated transitions in the shape of the resulting products. Hexagonal prism crystals, crystals characterized by triangular facets, and twinned crystals are observed to form from SH and FCC systems, which have not previously been experimentally realized by DNA origami crystallization. These findings open a promising pathway toward accessing a rich phase space with a single type of building block and wielding other instructions as tools to develop crystalline materials with tunable properties.

Spacer-Programmed Two-Dimensional DNA Origami Assembly

“…18 Recently, it has been revealed that variations of ionic strengths could also lead to different DNA assembly structures, using identical building blocks. 19 other hand, DNA sticky-end design represents another essential factor affecting DNA origami assembly. Through orthogonal sticky-end designs, researchers have achieved various 2D DNA origami assemblies, 17,23−27 such as the fractal assembly of Mona Lisa's smile 17 or Leonardo da Vinci's Vitruvian Man.…”

“…Precise control over the DNA origami assembly is crucial for enhancing its diversity and stability. In earlier studies, on the one hand, researchers focused on the effect of classical chemical reaction parameters such as temperature, pH, and ionic strength on DNA origami assembly. Temperature affects the hybridization kinetics of DNA strands, playing a pivotal role in hierarchical assembly and seed-mediated assembly. , pH influences the formation of hydrogen bonds, which can be utilized to induce the transformation of DNA structures such as i-motif, pH-sensitive DNA triplex based on Hoogsteen interactions and DNA origami 3D crystals .…”

“…Temperature affects the hybridization kinetics of DNA strands, playing a pivotal role in hierarchical assembly and seed-mediated assembly. , pH influences the formation of hydrogen bonds, which can be utilized to induce the transformation of DNA structures such as i-motif, pH-sensitive DNA triplex based on Hoogsteen interactions and DNA origami 3D crystals . Recently, it has been revealed that variations of ionic strengths could also lead to different DNA assembly structures, using identical building blocks . On the other hand, DNA sticky-end design represents another essential factor affecting DNA origami assembly.…”

“…Precise control over the DNA origami assembly is crucial for enhancing its diversity and stability. In earlier studies, on the one hand, researchers focused on the effect of classical chemical reaction parameters such as temperature, 17 pH, 18 and ionic strength 19 on DNA origami assembly. Temperature affects the hybridization kinetics of DNA strands, playing a pivotal role in hierarchical assembly 17 and seed-mediated assembly.…”

Programming of Supercrystals Using Replicable DNA‐Functionalized Colloids

“…On the other hand, over the last two decades, great progress has been made in the field of colloidal crystal engineering with DNA in the bottom-up synthesis of threedimensionally ordered superlattice nanomaterials. [20][21][22][23][24][25] In this field, programmable atom equivalents (PAEs), [26][27][28] consisting of interior colloidal gold nanoparticles (AuNPs, the "atoms") conjugated with exterior DNA molecules (possessing active sticky ends that act as bonding elements to position nanoparticles) can assemble into ordered crystalline superlattices through thermal annealing [20][21][22][23][24][25][26][27][28] or roomtemperature catalytic assembly (termed catassembly) strategies. [29][30][31][32] Colloidal crystal engineering with DNA enables the preparation of various PAE crystals with different symmetries, lattice parameters, and crystal sizes or habits by regulating the type of bonding interactions (length and strength) between PAEs.…”