Abstract
Nature has evolved complex enzyme architectures that facilitate the synthesis and manipulation of the biopolymers DNA and RNA, including enzymes capable of attaching to the biopolymer substrate and performing several rounds of catalysis before dissociating1,2,3,4,5. Many of these ‘processive’ enzymes have a toroidal shape and completely enclose the biopolymer while moving along its chain, as exemplified by the DNA enzymes T4 DNA polymerase holoenzyme6 and λ-exonucleoase7. The overall architecture of these systems resembles that of rotaxanes, in which a long molecule or polymer is threaded through a macrocycle. Here we describe a rotaxane that mimics the ability of processive enzymes to catalyse multiple rounds of reaction while the polymer substrate stays bound. The catalyst consists of a substrate binding cavity incorporating a manganese(III) porphyrin complex that oxidizes alkenes within the toroid cavity, provided a ligand has been attached to the outer face of the toroid to both activate the porphyrin complex and shield it from being able to oxidize alkenes outside the cavity. We find that when threaded onto a polybutadiene polymer strand, this catalyst epoxidizes the double bonds of the polymer, thereby acting as a simple analogue of the enzyme systems.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 51 print issues and online access
$199.00 per year
only $3.90 per issue
Buy this article
- Purchase on SpringerLink
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Breyer, W. A. & Matthew, B. M. A structural basis for processivity. Protein Sci. 10, 1699–1711 (2001)
Kool, E. T., Morales, J. C. & Guckian, K. M. Mimicking the structure and function of DNA: Insights into DNA stability and replication. Angew. Chem. Int. Edn Engl. 39, 990–1009 (2000)
Benkovic, S. J., Valentine, A. M. & Salinas, F. Replisome-mediated DNA replication. Annu. Rev. Biochem. 70, 181–208 (2001)
Lin, S. M., Lloyd, R. S. & Roberts, R. J. Nucleases, 2nd edn (Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY, 1993)
Kool, E. T. Recognition of DNA, RNA, and proteins by circular oligonucleotides. Acc. Chem. Res. 31, 502–510 (1998)
Trakselis, M. A., Alley, S. C., Abel-Santos, E. & Benkovic, S. J. Creating a dynamic picture of the sliding clamp during T4 DNA polymerase holoenzyme assembly by using fluorescence resonance energy transfer. Proc. Natl Acad. Sci. USA 98, 8368–8375 (2001)
Kovall, R. & Matthews, B. W. Toroidal structure of lambda-exonuclease. Science 277, 1824–1827 (1997)
Ashton, P. R. et al. A light-fueled “piston cyclinder” molecular-level machine. J. Am. Chem. Soc. 120, 11190–11191 (1998)
Sauvage, J.-P. Transition metal-containing rotaxanes and catenanes in motion: towards molecular machines and motors. Acc. Chem. Res. 31, 611–619 (1998)
Davis, A. P. Synthetic molecular motors. Nature 401, 120–121 (1999)
Schalley, C. A., Beizai, K. & Vögtle, F. On the way to rotaxane-based molecular motors: studies in molecular mobility and topological chirality. Acc. Chem. Res. 34, 465–476 (2001)
Bissell, R. A., Córdova, E., Kaifer, A. E. & Stoddart, J. F. A chemically and electrochemically switchable molecular shuttle. Nature 369, 133–137 (1994)
Jiménez, M. C., Dietrich-Buchecker, C. & Sauvage, J.-P. Towards synthetic molecular muscles: Contraction and stretching of a linear rotaxane dimer. Angew. Chem. Int. Edn Engl. 39, 3284–3287 (2000)
Collier, C. P. et al. Electronically configurable molecular-based logic gates. Science 285, 391–394 (1999)
Harada, A., Li, J. & Kamachi, M. The molecular necklace: a rotaxane containing many threaded α-cyclodextrins. Nature 356, 325–327 (1992)
Shen, Y. X., Xie, D. & Gibson, H. W. Polyrotaxanes based on polyurethane backbones and crown ether cyclics. 1. Synthesis. J. Am. Chem. Soc. 116, 537–548 (1994)
Rowan, A. E., Aarts, P. P. M. & Koutstaal, K. W. M. Novel porphyrin-viologen rotaxanes. Chem. Commun., 611–612 (1998)
Elemans, J. A. A. W. et al. Porphyrin clips derived from diphenylglycoluril. Synthesis, conformational analysis, and binding properties. J. Org. Chem. 64, 7009–7016 (1999)
Meunier, B. Metalloporphyrins as versatile catalysts for oxidation reactions and oxidative DNA cleavage. Chem. Rev. 92, 1411–1456 (1992)
Elemans, J. A. A. W., Bijsterveld, E. J. A., Rowan, A. E. & Nolte, R. J. M. A host-guest epoxidation catalyst with enhanced activity and stability. Chem. Commun., 2443–2444 (2000)
Tornaritis, M. J. & Coutsolelos, A. G. Metalloporphyrins catalyse cis-polybutadiene to polyepoxide. Polymer 33, 1771–1772 (1992)
Sacco, H. C., Iamamoto, Y. & Lindsay Smith, J. R. Alkene epoxidation with iodosylbenzene catalysed by polyionic supports. J. Chem. Soc. Perkin Trans. 2, 181–190 (2001)
Tsuda, Y., Takahashi, K., Yamaguchi, T., Matsui, S. & Komura, T. Catalytic epoxidation of cyclohexene by covalently linked manganese porphyrin-viologen complex. J. Mol. Catal. A: Chem. 130, 285–295 (1998)
Hollis, B. W. 25-Hydroxyvitamin D3-1α-hydroxylase in porcine hepatic tissue: Subcellular localization to both mitochondria and microsomes. Proc. Natl Acad. Sci. USA 87, 6009–6013 (1990)
Guengerich, F. P. Reactions and significance of cytochrome P-450 enzymes. J. Biol. Chem. 266, 10019–10022 (1991)
Perkins, T. T., Mitsis, P. G., Dalal, R. V. & Block, S. M. Watching enzymes move along DNA one at a time. Biophys. J. 80, 1464 Part 2 (2001)
Brouwer, A. M. et al. Photoinduction of fast, reversible translational motion in a hydrogen-bonded molecular shuttle. Science 291, 2124–2128 (2001)
Farrington, J. A., Ledwith, A. & Stam, M. F. Cation-radicals: Oxidation of methoxide ion with 1,1v-dimethyl-4,4v-bipyridylium dichloride (paraquat dichloride). J. Chem. Soc. Chem. Commun., 259–260 (1969)
Acknowledgements
We thank J. Foekema and I. M. Dixon for preliminary studies and discussions. This research was supported by a NRSC Catalysis grant, a NWO Vidi grant (A.E.R.) and an EC Marie Curie fellowship (P.T.).
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Competing interests
The authors declare that they have no competing financial interests.
Supplementary information
Rights and permissions
About this article
Cite this article
Thordarson, P., Bijsterveld, E., Rowan, A. et al. Epoxidation of polybutadiene by a topologically linked catalyst. Nature 424, 915–918 (2003). https://doi.org/10.1038/nature01925
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1038/nature01925
This article is cited by
-
Ratcheting synthesis
Nature Reviews Chemistry (2023)
-
Editing of polymer backbones
Nature Reviews Chemistry (2023)
-
Paramagnetic relaxation enhancement NMR as a tool to probe guest binding and exchange in metallohosts
Nature Communications (2022)
-
A tape-reading molecular ratchet
Nature (2022)
-
A rational entry to cyclic polymers via spontaneous and selective cyclization reactions
Polymer Journal (2021)
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.