Abstract
Despite the remarkable progress made in the self-assembly of nano- and microscale architectures with well-defined sizes and shapes, a self-organization-based synthesis of hollow toroids has, so far, proved to be elusive. Here, we report the synthesis of polymer microrings made from rectangular, flat and rigid-core monomers with anisotropically predisposed alkene groups, which are crosslinked with each other by dithiol linkers using thiol-ene photopolymerization. The resulting hollow toroidal structures are shape-persistent and mechanically robust in solution. In addition, their size can be tuned by controlling the initial monomer concentrations, an observation that is supported by a theoretical analysis. These hollow microrings can encapsulate guest molecules in the intratoroidal nanospace, and their peripheries can act as templates for circular arrays of metal nanoparticles.
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References
Antonietti, M. Self-organization of functional polymers. Nature Mater. 2, 9–10 (2003).
Matyjaszewski, K. Architecturally complex polymers with controlled heterogeneity. Science 333, 1104–1105 (2011).
Bucknall, D. G. & Anderson, H. L. Polymers get organized. Science 302, 1904–1905 (2003).
Park, I-S. et al. Designer nanorings with functional cavities from self-assembling β-sheet peptides. Chem. Asian J. 6, 452–458 (2011).
Yagai, S. et al. Self-organization of hydrogen-bonding naphthalene chromophores into J-type nanorings and H-type nanorods: impact of regioisomerism. Angew. Chem. Int. Ed. 51, 6643–6647 (2012).
Chandrasekhar, N. & Chandrasekar, R. Reversibly shape-shifting organic optical waveguides: formation of organic nanorings, nanotubes, and nanosheets. Angew. Chem. Int. Ed. 51, 3556–3561 (2012).
Huang, Z. et al. Pulsating tubules from noncovalent macrocycles. Science 337, 1521–1526 (2012).
Pochan, D. J. et al. Toroidal triblock copolymer assemblies. Science 306, 94–97 (2004).
Schenning, A. P. H. J., Benneker, F. B. G., Geurts, H. P. M., Liu, X. Y. & Nolte, R. J. M. Porphyrin wheels. J. Am. Chem. Soc. 118, 8549–8552 (1996).
Takazawa, K. Micrometer-sized rings self-assembled from thiacyanine dye molecules and their waveguiding properties. Chem. Mater. 19, 5293–5301 (2007).
Carroll, G. T., Jongejan, M. G. M., Pijper, D. & Feringa, B. L. Spontaneous generation and patterning of chiral polymeric surface toroids. Chem. Sci. 1, 469–472 (2010).
Schappacher, M. & Deffieux, A. Synthesis of macrocyclic copolymer brushes and their self-assembly into supramolecular tubes. Science 319, 1512–1515 (2008).
Schappacher, M. & Deffieux, A. Imaging of catenated, figure-of-eight, and trefoil knot polymer rings. Angew. Chem. Int. Ed. 48, 5930–5933 (2009).
Schappacher, M. & Deffieux, A. Atomic force microscopy imaging and dilute solution properties of cyclic and linear polystyrene combs. J. Am. Chem. Soc. 130, 14684–14689 (2008).
Bielawski, C. W., Benitez, D. & Grubbs, R. H. An ‘endless’ route to cyclic polymers. Science 297, 2041–2044 (2002).
Boydston, A. J., Holcombe, T. W., Unruh, D. A., Fréchet, J. M. J. & Grubbs, R. H. A direct route to cyclic organic nanostructures via ring-expansion metathesis polymerization of a dendronized macromonomer. J. Am. Chem. Soc. 131, 5388–5389 (2009).
Xia, Y., Boydston, A. J. & Grubbs, R. H. Synthesis and direct imaging of ultrahigh molecular weight cyclic brush polymers. Angew. Chem. Int. Ed. 50, 5882–5885 (2011).
Zhang, K., Lackey, M. A., Wu, Y. & Tew, G. N. Universal cyclic polymer templates. J. Am. Chem. Soc. 133, 6906–6909 (2011).
Alexander, L., Dhaliwal, K., Simpson, J. & Bradley, M. Dunking doughnuts into cells—selective cellular translocation and in vivo analysis of polymeric micro-doughnuts. Chem. Commun. 44, 3507–3509 (2008).
Hud, N. V. & Vilfan, I. D. Toroidal DNA condensates: unraveling the fine structure and the role of nucleation in determining size. Annu. Rev. Biophys. Biomol. Struct. 34, 295–318 (2005).
Zhou, W., Bai, X., Wang, E. & Xie, S. Synthesis, structure, and properties of single-walled carbon nanotubes. Adv. Mater. 21, 4565–4583 (2009).
Martel, R., Shea, H. R. & Avouris, P. Rings of single-walled carbon nanotubes. Nature 398, 299 (1999).
Sano, M., Kamino, A., Okamura, J. & Shinkai, S. Ring closure of carbon nanotubes. Science 293, 1299–1301 (2001).
Song, L. et al. Large-scale synthesis of rings of bundled single-walled carbon nanotubes by floating chemical vapor deposition. Adv. Mater. 18, 1817–1821 (2006).
Kim, D. et al. Direct synthesis of polymer nanocapsules with a noncovalently tailorable surface. Angew. Chem. Int. Ed. 46, 3471–3474 (2007).
Kim, E. et al. Solvent-responsive polymer nanocapsules with controlled permeability: encapsulation and release of a fluorescent dye by swelling and deswelling. Chem. Commun. 45, 1472–1474 (2009).
Kim, E. et al. Facile, template-free synthesis of stimuli-responsive polymer nanocapsules for targeted drug delivery. Angew. Chem. Int. Ed. 49, 4405–4408 (2010).
Kim, D. et al. Direct synthesis of polymer nanocapsules: self-assembly of polymer hollow spheres through irreversible covalent bond formation. J. Am. Chem. Soc. 132, 9908–9919 (2010).
Hota, R. et al. Self-assembled, covalently linked, hollow phthalocyanine nanospheres. Chem. Sci. 4, 339–344 (2013).
Balasubramanian, R., Kalaitzis, Z. M. & Cao, W. Solvent dependent morphologies in thiol-ene photopolymerization: a facile route to the synthesis of resorcinarene nanocapsules. J. Mater. Chem. 20, 6539–6543 (2010).
Baek, K. et al. Free-standing, single-monomer-thick two-dimensional polymers through covalent self-assembly in solution. J. Am. Chem. Soc. 135, 6523–6528 (2013).
Hoyle, C. E. & Bowman, C. N. Thiol-ene click chemistry. Angew. Chem. Int. Ed. 49, 1540–1573 (2010).
Balasubramanian, R., Prayakarao, S., Han, S. & Cao, W. Tunable gold nanostructures with nanocapsules as template reaction vessels. RSC Adv. 2, 11668–11671 (2012).
Acknowledgements
This work was supported by the Institute for Basic Science (IBS; CA1303) and the World Class University Project (R31–2008–000–10059–0) in Korea. W.S. acknowledges support from the Korea Research Foundation (NRF-2013R1A1A2008900) and the Brain–Korea 21 Program. C.G.P. acknowledges support from POSCO through the Korean Steel NanoFusion Program. The authors thank J.M. Kim, Z. Hassan and D. Shetty for discussions.
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K.K. and J.L. conceived and designed the project. J.L. carried out most of the experimental work. K.B. and R.N. provided invaluable guidance. Y.H.K. provided expertise with NMR analysis. G.Y., N.L. and C.G.P. performed the TEM experiments. M.K. and W.S. performed theoretical studies of the formation of the microrings. K.K., W.S., R.N., K.B. and J.L. wrote the manuscript.
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Lee, J., Baek, K., Kim, M. et al. Hollow nanotubular toroidal polymer microrings. Nature Chem 6, 97–103 (2014). https://doi.org/10.1038/nchem.1833
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DOI: https://doi.org/10.1038/nchem.1833
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