Assembly of Dynamic Supramolecular Polymers on a DNA Origami Platform

Abstract

Biological processes rely on transient interactions that govern assembly of biomolecules into higher order, multi‐component systems. A synthetic platform for the dynamic assembly of multicomponent complexes would provide novel entries to study and modulate the assembly of artificial systems into higher order topologies. Here, we establish a hybrid DNA origami‐based approach as an assembly platform that enables dynamic templating of supramolecular architectures. It entails the site‐selective recruitment of supramolecular polymers to the platform with preservation of the intrinsic dynamics and reversibility of the assembly process. The composition of the supramolecular assembly on the platform can be tuned dynamically, allowing for monomer rearrangement and inclusion of molecular cargo. This work should aid the study of supramolecular structures in their native environment in real‐time and incites new strategies for controlled multicomponent self‐assembly of synthetic building blocks.

Recent Advances in DNA Origami-Engineered Nanomaterials and Applications

“…Taking one step further, Schill et al. reported dynamic 1D supramolecular assemblies on DNA origami . Bipyridine-based C3-symmetry amphiphilic, discotic molecules were used as monomeric building blocks in the synthetic polymer system.…”

Complex DNA Architectonics─Self-Assembly of Amphiphilic Oligonucleotides into Ribbons, Vesicles, and Asterosomes

“…Biochemical processes generally rely on the precise arrangement of the molecular subunits within a hierarchically ordered supramolecular assembly held together by noncovalent, directional interactions . Illustrative examples are natural light-harvesting complexes, in which the spatial organization of the chromophores is crucial for an efficient transfer of excitation energy within large protein complexes. , In nanotechnology, DNA is widely used as a structural element for the bottom-up assembly of nanostructures because the scaffold of the DNA duplex serves as a versatile, robust, and yet highly reliable tool of spatial control. − The specificity and programmability of nucleic acid folding enables the bottom-up creation of multidimensional structures by the DNA origami approach. − Alternatively, DNA nanostructures can be constructed by a self-assembly approach using DNA tiles with sticky ends. − Despite their elegance, both approaches face some limitations, because they often require a set of many, even up to hundreds, different DNA sequences to assemble a desired nanostructure . The integration of unnatural nucleotide surrogates into oligonucleotides introduces additional functionality and extends the scope of application of DNA from the biological context to the field of materials sciences. − Chemically modified DNA conjugates were shown to form supramolecular polymers with potential applications, e.g., in biomedicine for drug delivery systems or in optoelectronic devices. − Recently, we reported the supramolecular assembly of amphiphilic DNA, bearing either phenanthrene or tetraphenylethylene (TPE) hydrophobic ends, into vesicle-shaped objects. , Hydrophobic interactions of DNA sticky ends, as well as spermine-mediated electrostatic interactions, , are among the driving forces that lead to the formation of these DNA-constructed vesicles.…”

Nanoscale patterning of polymers on DNA origami

“…2(b)). To perform the bioconjugation reaction of the NHS-functionalized polymers with the 5′amino oligonucleotide (complementary sticky A (StA c ; 5′-NH 2 -TTTTCTCTACCACCTACTA-3′) 13 or complementary sticky E (StE c ; 5′-NH 2 -CAGTCAGTCAGTCAGTCAGT-3′) 15 ) (Fig. 2c), the solvent has a high impact on the conversion.…”

“…As such, this technique grants access towards achieving precise geometric shapes that cannot be constructed via conventional polymer synthesis methods. 14,15 Three different kinds of monomer backbone (acrylates, methacrylates and acrylamides) were selected to underline the versatility of the approach. Technically, the production of 1-1 DNA-polymer conjugates can be performed via the grafting from or the grafting to method.…”