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Metal–nucleic acid cages

Abstract

Metal–nucleic acid cages are a promising new class of materials. Like metallo-supramolecular cages, these systems can use their metals for redox, photochemical, magnetic and catalytic control over encapsulated cargo. However, using DNA provides the potential to program pore size, geometry, chemistry and addressability, and the ability to symmetrically and asymmetrically position transition metals within the three-dimensional framework. Here we report the quantitative construction of metal–DNA cages, with the site-specific incorporation of a range of metals within a three-dimensional DNA architecture. Oligonucleotide strands containing specific environments suitable for transition-metal coordination were first organized into two DNA triangles. These triangles were then assembled into a DNA prism with linking strands. Metal centres were subsequently incorporated into the prisms at the pre-programmed locations. This unprecedented ability to position transition metals within a three-dimensional framework could lead to metal–DNA hosts with applications for the encapsulation, sensing, modification and release of biomolecules and nanomaterials.

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Figure 1: Schematic representation of the construction of three-dimensional DNA prism TP and subsequent site-specific metallation.
Figure 2: Construction and site-specific metallation of the triangle T1.
Figure 3: Characterization of the triangular prism TP.
Figure 4: Characterization of the site-specific metallation of TP to form TP.M6.
Figure 5: Pre-metallation of T1 and T2 and their assembly into TP.Cu(I)6.

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References

  1. Aldaye, F. A., Palmer, A. L. & Sleiman, H. F. Assembling materials with DNA as the guide. Science 321, 1795–1799 (2008).

    Article  CAS  Google Scholar 

  2. Lin, C., Liu, Y., Rinker, S. & Yan, H. DNA tile based self-assembly: building complex nanoarchitectures. ChemPhysChem 7, 1641–1647 (2006).

    Article  CAS  Google Scholar 

  3. Gothelf, K. V. & LaBean, T. H. DNA-programmed assembly of nanostructures. Org. Biomol. Chem. 3, 4023–4037 (2005).

    Article  CAS  Google Scholar 

  4. Seeman, N. An overview of structural DNA nanotechnology. Mol. Biotechnol. 37, 246–257 (2007).

    Article  CAS  Google Scholar 

  5. Aldaye, F. A. & Sleiman, H. F. Modular access to structurally switchable 3D discrete DNA assemblies. J. Am. Chem. Soc. 129, 13376–13377 (2007).

    Article  CAS  Google Scholar 

  6. Shih, W. M., Quispe, J. D. & Joyce, G. F. A 1.7-kilobase single-stranded DNA that folds into a nanoscale octahedron. Nature 427, 618–621 (2004).

    Article  CAS  Google Scholar 

  7. Heilemann, M. et al. Reconfigurable, braced, three-dimensional DNA nanostructures. Nature Nanotech. 3, 93–96 (2008).

    Article  Google Scholar 

  8. He, Y. et al. Hierarchical self-assembly of DNA into symmetric supramolecular polyhedra. Nature 452, 198–201 (2008).

    Article  CAS  Google Scholar 

  9. Mitchell, N. et al. A DNA nanostructure for the functional assembly of chemical groups with tunable stoichiometry and defined nanoscale geometry. Angew. Chem. Int. Ed. 48, 525–527 (2009).

    Article  CAS  Google Scholar 

  10. Mastroianni, A. J., Claridge, S. A. & Alivisatos, A. P. Pyramidal and chiral groupings of gold nanocrystals assembled using DNA scaffolds. J. Am. Chem. Soc. 131, 8455–8459 (2009).

    Article  CAS  Google Scholar 

  11. Tanaka, K. et al. A discrete self-assembled metal array in artificial DNA. Science 229, 1212–1213 (2003).

    Article  Google Scholar 

  12. Tanaka, K. et al. Programmable self-assembly of metal ions inside artificial DNA duplexes. Nature Nanotech. 1, 190–194 (2006).

    Article  CAS  Google Scholar 

  13. Clever, G. H., Kaul, C. & Carell, T. DNA-metal base pairs. Angew. Chem. Int. Ed. 46, 6226–6236 (2007).

    Article  CAS  Google Scholar 

  14. Mitra, D., Di Cesare, N. & Sleiman, H. F. Self-assembly of cyclic metal-DNA nanostructures using ruthenium tris(bipyridine)-branched oligonucleotides. Angew. Chem. Int. Ed. 43, 5804–5808 (2004).

    Article  CAS  Google Scholar 

  15. Yang, H. & Sleiman, H. F. Templated synthesis of highly stable, electroactive, and dynamic metal-DNA branched junctions. Angew. Chem. Int. Ed. 47, 2443–2446 (2008).

    Article  CAS  Google Scholar 

  16. Yoshizawa, M. & Fujita, M. Self-assembled coordination cage as a molecular flask. Pure Appl. Chem. 77, 1107–1112 (2005).

    Article  CAS  Google Scholar 

  17. Seidel, S. R. & Stang, P. High-symmetry coordination cages via self-assembly. Acc. Chem. Res. 35, 972–983 (2002).

    Article  CAS  Google Scholar 

  18. Pluth, M. D., Bergman, R. G. & Raymond, K. N. Acid catalysis in basic solution: A supramolecular host promotes orthoformate hydrolysis. Science 316, 85–88 (2007).

    Article  CAS  Google Scholar 

  19. Rowsell, J. L. C. et al. Gas adsorption sites in a large-pore metal-organic framework. Science 309, 1350–1354 (2005).

    Article  CAS  Google Scholar 

  20. Chandler, B. D., Cramb, D. T. & Shimizu, G. K. H Microporous metal-organic frameworks formed in a stepwise manner from luminescent building blocks. J. Am. Chem. Soc. 128, 10403–10412 (2006).

    Article  CAS  Google Scholar 

  21. Ghosh, S. K. et al. A bistable porous coordination polymer with a bond-switching mechanism showing reversible structural and functional transformations. Angew. Chem. Int. Ed. 47, 8843–8847 (2008).

    Article  CAS  Google Scholar 

  22. Aldaye, F. A. & Sleiman, H. F. Dynamic DNA templates for discrete gold nanoparticle assemblies: control of geometry, modularity, write/erase and structural switching. J. Am. Chem. Soc. 129, 4130–4131 (2007).

    Article  CAS  Google Scholar 

  23. Champin, B., Mobian, P. & Sauvage, J.-P. Transition metal complexes as molecular machine prototypes. Chem. Soc. Rev. 36, 358–366 (2007).

    Article  CAS  Google Scholar 

  24. Armaroli, N. et al. Absorption and emission properties of a 2-catenand, its protonated forms, and its complexes with Li+, Cu+, Ag+, Co+, Ni2+, Zn2+, Pd2+ and Cd2+: tuning of the luminescence over the whole visible spectral region. J. Chem. Soc. Dalton Trans. 21, 3241–3247 (1993).

    Article  Google Scholar 

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Acknowledgements

The authors thank NSERC, CFI, CSACS, CIHR and CIFAR for financial support, Jean-Pierre Sauvage for helpful discussion and J. Hedberg for help in preparing graphical illustrations. I.R. is recipient of a CIHR New Investigator award. G.D.H. thanks McGill University for a Tomlinson fellowship and C.K.M. thanks CIHR for a Chemical Biology scholarship. H.F.S. is a Cottrell Scholar of the Research Corporation.

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H.F.S., H.Y., C.K.M. and F.A.A. designed the project. I.R., G.D.H. and C.K.M. collected and analysed electron microscope data. H.Y., C.K.M., G.D.H. and A.Z.R. primarily contributed to the production of experimental results. H.F.S., H.Y. and C.K.M. were primarily responsible for preparing the manuscript and all authors have agreed to the content of the manuscript.

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Correspondence to Hanadi F. Sleiman.

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Yang, H., McLaughlin, C., Aldaye, F. et al. Metal–nucleic acid cages. Nature Chem 1, 390–396 (2009). https://doi.org/10.1038/nchem.290

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