DNA Guided Self-Assembly of Organic Materials

We have developed a highly versatile system for the organization of 2-dimensional (2D) materials on the nanoscale. This system is predicated on the use of DNA-based information as an organizing principle, and on our ability to design DNA to encapsulate and orient other molecular and nanoscopic species in a diverse and effective fashion. We apply branched DNA molecules, not simple linear DNA, to the formation of connected networks of materials in a predictable fashion [1]. We are able to build robust DNA 2D assemblies. Each of these assemblies can be filled as desired, with any molecules, macromolecules or nanoparticles that can be derivatized to interact, bond or bind with the DNA.<br/><br/>In earlier work, chemistry was developed to enable covalent attachment of organic groups to the 2’-O-ribosyl position of RNA nucleotides. Such an attachment strategy minimizes distortion in DNA duplexes by directing appended groups to minimize unfavorable steric interactions with A-form helical structures. A variety of synthetic approaches were examined, involving modifications at different points in DNA oligonucleotide synthesis. Much of the chemistry was tested in the context of appended oligomers of nylon and poly(ethyleneglycol).<br/><br/>Monodisperse oligomers of electroactive organic polymers were synthesized and appended to DNA oligonucleotides. An octamer of polyaniline, which shows rich electrochemical behavior, was incorporated into a rhombohedral DNA lattice. The resulting crystal showed excellent optical response consistent with cycling between its redox forms [2]. It was later studied in a smaller assembly showing reconfigurable excitonic interactions [3]. A heptamer molecule related to poly(phenylenevinylene) was included in a DNA crystal and found to show strong polarization properties [4].<br/><br/>This presentation will describe unpublished work on the synthesis and assembly of DNA-GNR chimeras within DNA nanostructures.<br/><br/>[1] Seeman, N. C. "Nucleic Acid Junctions and Lattices," <i>J. Theor. Biol. </i><b>1982, </b><i>99</i>, 237-247.<br/>[2] X. Wang<i> et al.</i>, Angew. Chem. Int. Ed. Engl. <b>56</b>, 6445-6448 (2017).<br/>[3] X. Wang<i> et al.</i>, ACS Nano, <b>16</b>, 1301-1307 (2022).<br/>[4] X. Wang<i> et al.</i>, Angew. Chem. Int. Ed. Engl<i>.</i> <b>61</b>, e202115155 (2022).