Short synthetic DNA has been tethered to many building blocks such as small organic molecules, dendrimers, polymers, and metallic nanoparticles, which can then form a variety of hybrid nanomaterials for many chemical and biological applications. Given the synthetic ease with which the sugar-phosphate backbone can be manipulated and the high sequence-specificity of nucleotide base pairing, DNA-functionalized supramolecular assemblies and nanostructures have also provided a fertile ground for the exploration of new nanomaterials design principles. For this purpose, small molecule-DNA hybrids (SMDHs), where the number, orientation, and length of the DNA arms attached to small organic cores can be precisely tuned, have emerged as a prominent testbed for the elucidation of DNA-directed supramolecular and nanoassembly principles. This presentation will showcase the nanoassembly behavior of trivalent small molecule-DNA hybrids (SMDH3s) as a function of core geometry, supramolecular flexibility, and the length of DNA and Tn spacer units between a core and DNA. A synergistic experimental-modeling study revealed that pyramidal and flexible SMDH3s facilitated intramolecular interactions to form well-defined caged dimers, while planar and rigid ones favored intermolecular interactions, resulting in ill-defined large aggregates. Interestingly, long DNA arms and long Tn spacer units hindered intramolecular interaction resulting in the formation of a significant amount of ill-defined structures. Such insights can serve as an enabling guideline for researchers to design and develop DNA-hybrid materials for a wide range of applications.

Structure-targeted, controlled assembly of small molecule-DNA hybrids through tuning small molecule core geometry, supramolecular flexibility, and length of DNA arms

256th National Meeting (2018)

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