Abstract
Covalent bridges play a crucial role in the folding process of sequence-defined biopolymers. This feature, however, has not been recreated in synthetic polymers because, apart from some simple regular arrangements (such as block co-polymers), these macromolecules generally do not exhibit a controlled primary structure—that is, it is difficult to predetermine precisely the sequence of their monomers. Herein, we introduce a versatile strategy for preparing foldable linear polymer chains. Well-defined polymers were synthesized by the atom transfer radical polymerization of styrene. The controlled addition of discrete amounts of protected maleimide at precise times during the synthesis enabled the formation of polystyrene chains that contained positionable reactive alkyne functions. Intramolecular reactions between these functions subsequently led to the formation of different types of covalently folded polymer chains. For example, tadpole (P-shaped), pseudocyclic (Q-shaped), bicyclic (8-shaped) and knotted (α-shaped) macromolecular origamis were prepared in a relatively straightforward manner.
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References
Anfinsen, C. B. Principles that govern the folding of protein chains. Science 181, 223–230 (1973).
Dobson, C. M. Protein folding and misfolding. Nature 426, 884–890 (2003).
Flory, P. J. & Yoon, D. Y. Molecular morphology in semicrystalline polymers. Nature 272, 226–229 (1978).
Sadler, D. M. New explanation for chain folding in polymers. Nature 326, 174–177 (1987).
Gellman, S. H. Foldamers: a manifesto. Acc. Chem. Res. 31, 173–180 (1998).
Hill, D. J., Mio, M. J., Prince, R. B., Hughes, T. S. & Moore, J. S. A field guide to foldamers. Chem. Rev. 101, 3893–4011 (2001).
Huc, I. Aromatic oligoamide foldamers. Eur. J. Org. Chem. 17–29 (2004).
Yashima, E., Maeda, K., Iida, H., Furusho, Y. & Nagai, K. Helical polymers: synthesis, structures, and functions. Chem. Rev. 109, 6102–6211 (2009).
Miwa, K., Furusho, Y. & Yashima, E. Ion-triggered spring-like motion of a double helicate accompanied by anisotropic twisting. Nature Chem. 2, 444–449 (2010).
Badi, N. & Lutz, J.-F. Sequence control in polymer synthesis. Chem. Soc. Rev. 38, 3383–3390 (2009).
Lutz, J.-F. Polymer chemistry: a controlled sequence of events. Nature Chem. 2, 84–85 (2010).
Lutz, J.-F. Sequence-controlled polymerizations: the next Holy Grail in polymer science? Polym. Chem. 1, 55–62 (2010).
van Gorp, J. J., Vekemans, J. & Meijer, E. W. Facile synthesis of a chiral polymeric helix; folding by intramolecular hydrogen bonding. Chem. Commun. 60–61 (2004).
Meudtner, R. M. & Hecht, S. Responsive backbones based on alternating triazole–pyridine/benzene copolymers: from helically folding polymers to metallosupramolecularly crosslinked gels. Macromol. Rapid Commun. 29, 347–351 (2008).
Yu, T. B., Bai, J. Z. & Guan, Z. B. Cycloaddition-promoted self-assembly of a polymer into well-defined beta sheets and hierarchical nanofibrils. Angew. Chem. Int. Ed. 48, 1097–1101 (2009).
Harth, E. et al. A facile approach to architecturally defined nanoparticles via intramolecular chain collapse. J. Am. Chem. Soc. 124, 8653–8660 (2002).
Foster, E. J., Berda, E. B. & Meijer, E. W. Metastable supramolecular polymer nanoparticles via intramolecular collapse of single polymer chains. J. Am. Chem. Soc. 131, 6964–6966 (2009).
Berda, E. B., Foster, E. J. & Meijer, E. W. Toward controlling folding in synthetic polymers: fabricating and characterizing supramolecular single-chain nanoparticles. Macromolecules 43, 1430–1437 (2010).
Grayson, S. M. Macromolecular chemistry: polymers kept in the loop. Nature Chem. 1, 178–179 (2009).
Laurent, B. A. & Grayson, S. M. An efficient route to well-defined macrocyclic polymers via ‘click’ cyclization. J. Am. Chem. Soc. 128, 4238–4239 (2006).
Schappacher, M. & Deffieux, A. Synthesis of macrocyclic copolymer brushes and their self-assembly into supramolecular tubes. Science 319, 1512–1515 (2008).
Tezuka, Y. & Oike, H. Topological polymer chemistry. Prog. Polym. Sci. 27, 1069–1122 (2002).
Lonsdale, D. E. & Monteiro, M. J. Various polystyrene topologies built from tailored cyclic polystyrene via CuAAC reactions. Chem. Commun. 7945–7947 (2010).
Pfeifer, S. & Lutz, J.-F. A facile procedure for controlling monomer sequence distribution in radical chain polymerizations. J. Am. Chem. Soc. 129, 9542–9543 (2007).
Pfeifer, S. & Lutz, J.-F. Development of a library of N-substituted maleimides for the local functionalization of linear polymer chains. Chem. Eur. J. 14, 10949–10957 (2008).
Satoh, K., Matsuda, M., Nagai, K. & Kamigaito, M. AAB-sequence living radical chain copolymerization of naturally occurring limonene with maleimide: an end-to-end sequence-regulated copolymer. J. Am. Chem. Soc. 132, 10003–10005 (2010).
Berthet, M. A., Zarafshani, Z., Pfeifer, S. & Lutz, J.-F. Facile synthesis of functional periodic copolymers: a step toward polymer-based molecular arrays. Macromolecules 43, 44–50 (2010).
Ida, S., Terashima, T., Ouchi, M. & Sawamoto, M. Selective radical addition with a designed heterobifunctional halide: a primary study toward sequence-controlled polymerization upon template effect. J. Am. Chem. Soc. 131, 10808–10809 (2009).
Pfeifer, S., Zarafshani, Z., Badi, N. & Lutz, J.-F. Liquid-phase synthesis of block copolymers containing sequence-ordered segments. J. Am. Chem. Soc. 131, 9195–9197 (2009).
Kramer, J. W. et al. Polymerization of enantiopure monomers using syndiospecific catalysts: a new approach to sequence control in polymer synthesis. J. Am. Chem. Soc. 131, 16042–16044 (2009).
Satoh, K., Ozawa, S., Mizutani, M., Nagai, K. & Kamigaito, M. Sequence-regulated vinyl copolymers by metal-catalysed step-growth radical polymerization. Nature Commun. 1, 6 (2010).
Matyjaszewski, K. & Tsarevsky, N. V. Nanostructured functional materials prepared by atom transfer radical polymerization. Nature Chem. 1, 276–288 (2009).
Ouchi, M., Terashima, T. & Sawamoto, M. Transition metal-catalyzed living radical polymerization: toward perfection in catalysis and precision polymer synthesis. Chem. Rev. 109, 4963–5050 (2009).
Siemsen, P., Livingston, R. C. & Diederich, F. Acetylenic coupling: a powerful tool in molecular construction. Angew. Chem. Int. Ed. 39, 2633–2657 (2000).
Himo, F. et al. Copper(I)-catalyzed synthesis of azoles. DFT study predicts unprecedented reactivity and intermediates. J. Am. Chem. Soc. 127, 210–216 (2004).
Hawker, C. J. & Wooley, K. L. The convergence of synthetic organic and polymer chemistries. Science 309, 1200–1205 (2005).
Lutz, J.-F. 1,3-Dipolar cycloadditions of azides and alkynes: a universal ligation tool in polymer and materials science. Angew. Chem. Int. Ed. 46, 1018–1025 (2007).
Hanni, K. D. & Leigh, D. A. The application of CuAAC ‘click’ chemistry to catenane and rotaxane synthesis. Chem. Soc. Rev. 39, 1240–1251 (2010).
Kricheldorf, H. R. Cyclic polymers: synthetic strategies and physical properties. J. Polym. Sci. A 48, 251–284 (2010).
Roovers, J. & Toporowski, P. M. Synthesis of high molecular weight ring polystyrenes. Macromolecules 16, 843–849 (1983).
Alberty, K. A., Hogen-Esch, T. E. & Carlotti, S. Synthesis and characterization of macrocyclic vinyl-aromatic polymers. Molecular weight-dependent glass transition temperatures and emission of macrocyclic polystyrene. Macromol. Chem. Phys. 206, 1035–1042 (2005).
Benoit, D., Hawker, C. J., Huang, E. E., Lin, Z. & Russell, T. P. One-step formation of functionalized block copolymers. Macromolecules 33, 1505–1507 (2000).
Antonietti, M. & Fölsch, K. J. Synthesis and characterization of ‘eight-shaped’ polystyrene. Makromol. Chem. Rapid Commun. 9, 423–430 (1988).
Acknowledgements
The Fraunhofer Society is acknowledged for financial support. J.F.L. thanks the European Research Council for support (Project SEQUENCES). J.F.L. thanks A. Laschewsky (Universität Potsdam), C. Wieland (Universität Potsdam), P.J. Lutz (ICS Strasbourg) and M. Maaloum (Université de Strasbourg) for discussions.
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J.F.L designed the experiments, analysed the data and wrote the paper. B.V.K.J.S. and N.F. performed the experiments and analysed the data. J.F. contributed analysis tools. All authors discussed the results and commented on the manuscript.
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Schmidt, B., Fechler, N., Falkenhagen, J. et al. Controlled folding of synthetic polymer chains through the formation of positionable covalent bridges. Nature Chem 3, 234–238 (2011). https://doi.org/10.1038/nchem.964
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DOI: https://doi.org/10.1038/nchem.964
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