Synthetic polymers are ubiquitous in the modern world, but our ability to exert control over the molecular conformation of individual polymers is very limited. In particular, although the programmable self-assembly of oligonucleotides and proteins into artificial nanostructures has been demonstrated, we currently lack the tools to handle other types of synthetic polymers individually and thus the ability to utilize and study their single-molecule properties. Here we show that synthetic polymer wires containing short oligonucleotides that extend from each repeat can be made to assemble into arbitrary routings. The wires, which can be more than 200 nm in length, are soft and bendable, and the DNA strands allow individual polymers to self-assemble into predesigned routings on both two- and three-dimensional DNA origami templates. The polymers are conjugated and potentially conducting, and could therefore be used to create molecular-scale electronic or optical wires in arbitrary geometries.
Subscribe to Journal
Get full journal access for 1 year
only $4.92 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
Heeger, A. J. Semiconducting and metallic polymers: the fourth generation of polymeric materials. Synthetic Met. 125, 23–42 (2001).
Heeger, A. J. Semiconducting polymers: the third generation. Chem. Soc. Rev. 39, 2354–2371 (2010).
Facchetti, A. π-Conjugated polymers for organic electronics and photovoltaic cell applications. Chem. Mater. 23, 733–758 (2011).
Baeg, K.-J. et al. High speeds complementary integrated circuits fabricated with all-printed polymeric semiconductors. J. Polym. Sci. B 49, 62–67 (2011).
Gong, S., Yang, C. & Qin, J. Efficient phosphorescent polymer light-emitting diodes by suppressing triplet energy back transfer. Chem. Soc. Rev. 41, 4797–4807 (2012).
Zheng, H. et al. All-solution processed polymer light-emitting diode displays. Nature Commun. 4, 1–7 (2013).
Günes, S., Neugebauer, H. & Sariciftci, N. S. Conjugated polymer-based organic solar cells. Chem. Rev. 107, 1324–1338 (2007).
Thomas, S. W., Joly, G. D. & Swager, T. M. Chemical sensors based on amplifying fluorescent conjugated polymers. Chem. Rev. 107, 1339–1386 (2007).
Barbara, P. F., Gesquiere, A. J., Park, S. J. & Lee, Y. J. Single-molecule spectroscopy of conjugated polymers. Acc. Chem. Res. 38, 602–610 (2005).
Hugel, T. et al. Single-molecule optomechanical cycle. Science 296, 1103–1106 (2002).
Kawai, S. et al. Quantifying the atomic-level mechanics of single long physisorbed molecular chains. Proc. Natl Acad. Sci. USA 111, 3968–3972 (2014).
Taniguchi, M. et al. Self-organized interconnect method for molecular devices. J. Am. Chem. Soc. 128, 15062–15063 (2006).
Lafferentz, L. et al. Conductance of a single conjugated polymer as a continuous function of its length. Science 323, 1193–1197 (2009).
Shimomura, T. et al. Conductivity measurement of insulated molecular wire formed by molecular nanotube and polyaniline. Synthetic Met. 153, 497–500 (2005).
Kiriy, A. et al. Cascade of coil–globule conformational transitions of single flexible polyelectrolyte molecules in poor solvent. J. Am. Chem. Soc. 124, 13454–13462 (2002).
Shimomura, T., Akai, T., Abe, T. & Ito, K. Atomic force microscopy observation of insulated molecular wire formed by conducting polymer and molecular nanotube. J. Chem. Phys. 116, 1753–1756 (2002).
Ouchi, M., Badi, N., Lutz, J.-F. & Sawamoto, M. Single-chain technology using discrete synthetic macromolecules. Nature Chem. 3, 917–924 (2011).
Müllen, K. Evolution of graphene molecules: structural and functional complexity as driving forces behind nanoscience. ACS Nano 8, 6531–6541 (2011).
Palma, C.-A. & Samori, P. Blueprinting macromolecular electronics. Nature Chem. 3, 431–436 (2011).
Lörtscher, E. Wiring molecules into circuits. Nature Nanotech. 8, 381–384 (2013).
Peng, H., Zhang, L., Soeller, C. & Travas-Sejdic, J. Conducting polymers for electrochemical DNA sensing. Biomaterials 30, 2132–2148 (2009).
Lo, P. K. & Sleiman, H. F. Nucleobase-templated polymerization: copying the chain length and polydispersity of living polymers into conjugated polymers. J. Am. Chem. Soc. 131, 4182–4183 (2009).
Rothemund, P. W. K. Folding DNA to create nanoscale shapes and patterns. Nature 440, 297–302 (2006).
Tørring, T., Voigt, N. V., Nangreave, J., Yan, H. & Gothelf, K. V. DNA origami: a quantum leap for self-assembly of complex structures. Chem. Soc. Rev. 40, 5636–5646 (2011).
Sacca, B. & Niemeyer, C. M. Functionalization of DNA nanostructures with proteins. Chem. Soc. Rev. 40, 5910–5921 (2011).
Wang, Z. G. & Ding, B. Engineering DNA self-assemblies as templates for functional nanostructures. Acc. Chem. Res. 47, 1654–1662 (2014).
Maune, H. T. et al. Self-assembly of carbon nanotubes into two-dimensional geometries using DNA origami templates. Nature Nanotech. 5, 61–66 (2010).
Chaix, C., Minard-Basquin, C., Delair, T., Pichot, C. & Mandrand, B. Oligonucleotide synthesis on maleic anhydride copolymers covalently bound to silica spherical support and characterization of the obtained conjugates. J. Appl. Polym. Sci. 70, 2487 (1998).
Henckens, A., Duyssens, I., Lutsen, L., Vanderzande, D. & Cleij, T. J. Synthesis of poly(p-phenylene vinylene) and derivatives via a new precursor route, the dithiocarbamate route. Polymer 47, 123–131 (2006).
Vandenbergh, J. et al. Synthesis and characterization of water-soluble poly(p-phenylene vinylene) derivatives via the dithiocarbamate precursor route. Eur. Polym. J. 47, 1827–1835 (2011).
Minard-Basquin, C., Chaix, C., Pichot, C. & Mandrand, B. Oligonucleotide−polymer conjugates: effect of the method of synthesis on their structure and performance in diagnostic assays. Bioconjugate Chem. 11, 795–805 (2000).
Volcke, C. et al. Influence of DNA condensation state on transfection efficiency in DNA/polymer complexes: an AFM and DLS comparative study. J. Biotechnol. 125, 11–21 (2006).
Zhang, S. et al. Coexistence of ribbon and helical fibrils originating from hIAPP20–29 revealed by quantitative nanomechanical atomic force microscopy. Proc. Natl Acad. Sci. USA 110, 2798–2803 (2013).
Pfeffer, C. et al. Filamentous bacteria transport electrons over centimetre distances. Nature 491, 218–221 (2012).
Sinensky, A. K. & Belcher, A. M. Label-free and high-resolution protein/DNA nanoarray analysis using Kelvin probe force microscopy. Nature Nanotech. 2, 653–659 (2007).
Ke, Y., Lindsay, S., Chang, Y., Liu, Y. & Yan, H. Self-assembled water-soluble nucleic acid probe tiles for label-free RNA hybridization assays. Science 319, 180–183 (2008).
Shih, W. M. & Lin, C. Knitting complex weaves with DNA origami. Curr. Opin. Chem. Biol. 20, 276–282 (2010).
Douglas, S. M. et al. Self-assembly of DNA into nanoscale three-dimensional shapes. Nature 459, 414–418 (2009).
Iinuma, R. et al. Polyhedra self-assembled from DNA tripods and characterized with 3D DNA-PAINT. Science 344, 65–69 (2014).
Jungmann, R. et al. Multiplexed 3D cellular super-resolution imaging with DNA-PAINT and Exchange-PAINT. Nature Methods 11, 313 (2014).
Jungmann, R. et al. Single-molecule kinetics and super-resolution microscopy by fluorescence imaging of transient binding on DNA origami. Nano Lett. 10, 4756–4761 (2010).
Kao, H. P. & Verkman, A. S. Tracking of single fluorescent particles in three dimensions: use of cylindrical optics to encode particle position. Biophys. J. 67, 1291–1300 (1994).
Huang, B., Wang, W., Bates, M. & Zhuang, X. Three-dimensional super-resolution imaging by stochastic optical reconstruction microscopy. Science 319, 810–813 (2008).
Burns, P. L. et al. Chemical tuning of the electronic properties of poly(p-phenylenevinylene)-based copolymers. J. Am. Chem. Soc. 115, 10117–10124 (1993).
Kershner, R. J. et al. Placement and orientation of individual DNA shapes on lithographically patterned surfaces. Nature Nanotech. 4, 557–561 (2009).
We thank P.W.K. Rothemund for discussions. This work was funded by the Danish National Research Foundation (Centre for DNA Nanotechnology, DNRF81), Sino-Danish Centre for Education and Research, Carlsberg Foundation, Danish Research Council (V.B.) (Sapere Aude Starting Grant (A.N.Z. and V.B.), STENO grant and an individual post-doctorate grant (R.O.)), Villum Foundation (Young Investigator Program (M.D.)), and the Lundbeck Foundation (A.N.Z). R.J. acknowledges support from the Deutsche Forschungsgemeinschaft through the Emmy Noether program (DFG JU 2957/1–1) and the Max Planck Society. W.M.S. acknowledges support for the contributions to his laboratory from the National Science Foundation (CCF-1317291), Army Research Office (W911NF-12-1-0420) and the Wyss Institute for Biologically Inspired Engineering.
The authors declare no competing financial interests.
About this article
Cite this article
Knudsen, J., Liu, L., Bank Kodal, A. et al. Routing of individual polymers in designed patterns. Nature Nanotech 10, 892–898 (2015). https://doi.org/10.1038/nnano.2015.190
Chemical Reviews (2021)
Nature Reviews Methods Primers (2021)
Programmed catalysis within stimuli-responsive mechanically unlocked nanocavities in DNA origami tiles
Chemical Science (2021)
Angewandte Chemie International Edition (2021)
ACS Nano (2021)