Noteborn, Willem E.M.Willem E.M.NotebornWondergem, Joeri A.J.Joeri A.J.WondergemIurchenko, AnastasiiaAnastasiiaIurchenkoChariyev-Prinz, FarhadFarhadChariyev-PrinzDonato, DominiqueDominiqueDonatoVoets, Ilja K.Ilja K.VoetsHeinrich, DorisDorisHeinrichKieltyka, Roxanne E.Roxanne E.Kieltyka2022-03-052022-03-052018https://publica.fraunhofer.de/handle/publica/25367210.1021/acs.macromol.7b02610Nucleic acid-polymer conjugates are an attractive class of materials endowed with tunable and responsive character. Herein, we exploit the dynamic character of nucleic acids in the preparation of hybrid DNA-covalent polymers with extendable grafts by the hybridization chain reaction. Addition of DNA hairpins to an initiator DNA-dextran graft copolymer resulted in the growth of the DNA grafts as evidenced by various characterization techniques over several length scales. Additionally, aggregation of the initiator DNA-graft copolymer before the hybridization chain reaction was observed resulting in the formation of kinetically trapped aggregates several hundreds of nanometers in diameter that could be disrupted by a preheating step at 60 °C prior to extension at room temperature. Materials of increasing viscosity were rapidly formed when metastable DNA hairpins were added to the initiator DNA-dextran grafted copolymer with increasing concentration of the components in the mixture. This study shows the potential for hierarchical self-assembly of DNA-grafted polymers through the hybridization chain reaction and opens the door for biomedical applications where viscosity can be used as a readout.en547journal article