Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Spontaneous assembly and real-time growth of micrometre-scale tubular structures from polyoxometalate-based inorganic solids

Abstract

We report the spontaneous and rapid growth of micrometre-scale tubes from crystals of a metal oxide-based inorganic solid when they are immersed in an aqueous solution containing a low concentration of an organic cation. A membrane immediately forms around the crystal, and this membrane then forms micrometre-scale tubes that grow with vast aspect ratios at controllable rates along the surface on which the crystal is placed. The tubes are composed of an amorphous mixture of polyoxometalate-based anions and organic cations. It is possible for liquid to flow through the tubes, and for the direction of growth and the overall tube diameter to be controlled. We demonstrate that tube growth is driven by osmotic pressure within the membrane sack around the crystal, which ruptures to release the pressure. These robust, self-growing, micrometre-scale tubes offer opportunities in many areas, including the growth of microfluidic devices and the self-assembly of metal oxide-based semipermeable membranes for diverse applications.

This is a preview of subscription content, access via your institution

Relevant articles

Open Access articles citing this article.

Access options

Buy article

Get time limited or full article access on ReadCube.

$32.00

All prices are NET prices.

Figure 1: The molecular building blocks used to form microtubes.
Figure 2: Spontaneous tube formation from crystals.
Figure 3: Micromanipulation is used to control tube growth and branching.
Figure 4: Different tube-fusion events upon collision.
Figure 5: Control of tube growth direction in a two-electrode system.
Figure 6: Injection of fluorescein isothiocyanate dye into a tube.

References

  1. Cölfen, H. & Mann, S. Higher-order organization by mesoscale self-assembly and transformation of hybrid nanostructures. Angew. Chem. Int. Ed. 42, 2350–2365 (2003).

    Article  Google Scholar 

  2. Mann, S. Life as a nanoscale phenomenon. Angew. Chem. Int. Ed. 47, 5306–5320 (2008).

    Article  CAS  Google Scholar 

  3. Banfield, J. F., Welch, S. A., Zhang, H., Ebert, T. T. & Penn, R. L. Aggregation-based crystal growth and microstructure development in natural iron oxyhydroxide biomineralization products. Science 289, 751–754 (2000).

    Article  CAS  Google Scholar 

  4. Liu, T. B., Diemann, E., Li, H. L., Dress, A. W. M. & Müller, A. Self-assembly in aqueous solution of wheel-shaped Mo154 oxide clusters into vesicles. Nature 426, 59–62 (2003).

    Article  CAS  Google Scholar 

  5. Capito, R. M., Azeveo, H. S., Velichko, Y. S., Mata, A. & Stupp, S. L. Self-assembly of large and small molecules into hierarchically ordered sacs and membranes. Science 319, 1812–1816 (2008).

    Article  CAS  Google Scholar 

  6. Zhang, J., Song, Y. S., Cronin, L. & Liu, T. B. Self-assembly of organic–inorganic hybrid amphiphilic surfactants with large polyoxometalates as polar head groups. J. Am. Chem. Soc. 130, 14408–14409 (2008).

    Article  CAS  Google Scholar 

  7. Chichak, K. S. et al. Molecular Borromean rings. Science 304, 1308–1312 (2004).

    Article  CAS  Google Scholar 

  8. Maselko, J. & Strizhak, P. Spontaneous formation of cellular chemical system that sustains itself far from thermodynamic equilibrium. J. Phys. Chem. B 108, 4937–4939 (2004).

    Article  CAS  Google Scholar 

  9. Cairns-Smith, A.-G. Chemistry and the missing era of evolution. Chem. Eur. J. 14, 3830–3839 (2008).

    Article  CAS  Google Scholar 

  10. Yang, L. F., Dolnik, M., Zhabotinsky, A. M. & Epstein, I. R. Oscillatory clusters in a model of the photosensitive Belousov–Zhabotinsky reaction system with global feedback. Phys. Rev. E 62, 6414–6420 (2000).

    Article  CAS  Google Scholar 

  11. Collins, C., Zhou, W., Mackay, A. K. & Klinowski, J. The ‘silica garden’: a hierarcharical nanostructure. Chem. Phys. Lett. 286, 88–92 (1998).

    Article  CAS  Google Scholar 

  12. Cartwright, J. H. E., Garcí-Ruiz, J. M., Novella, M. L., & Otálora, F. Formation of chemical gardens. J. Colloid Interface Sci. 256, 351–359 (2002).

    Article  CAS  Google Scholar 

  13. Thouvenel-Romans, S. & Steinbock, O. Oscillatory growth of silica tubes in chemical gardens. J. Am. Chem. Soc. 125, 4338–4341 (2003).

    Article  CAS  Google Scholar 

  14. Ritchie, C. et al. Reversible redox reactions in an extended polyoxometalate framework solid. Angew. Chem. Int. Ed. 47, 6881–6884 (2008).

    Article  CAS  Google Scholar 

  15. Parenty, A. D. C., Smith, L. V., Pickering, A. L., Long, D.-L. & Cronin, L. General one-pot, three-step methodology leading to an extended class of N-heterocyclic cations: spontaneous nucleophilic addition, cyclization, and hydride loss. J. Org. Chem. 69, 5934–5946 (2004).

    Article  CAS  Google Scholar 

  16. Parenty, A. D. C. et al. Discovery of an imidazo-phenanthridine synthon produced in a five-step one-pot reaction leading to a new family of heterocycles with novel physical properties. Chem. Commun. 1194–1196 (2006).

  17. Long, D.-L., Burkholder, E. & Cronin, L. Polyoxometalate clusters, nanostructures and materials: from self assembly to designer materials and devices. Chem. Soc. Rev. 36, 105–121 (2007).

    Article  CAS  Google Scholar 

  18. Müller, A., Shah, S. Q. N., Bögge, H. & Schmidtmann, M. Molecular growth from a Mo176 to a Mo248 cluster. Nature 397, 48–50 (1999).

    Article  Google Scholar 

  19. Long, D.-L., Abbas, H., Kögerler, P. & Cronin, L. Confined electron-transfer reactions within a molecular metal oxide ‘Trojan Horse’. Angew. Chem. Int. Ed. 44, 3415–3419 (2005).

    Article  CAS  Google Scholar 

  20. Rhule, J. T., Neiwert, W. A., Hardcastle, K. I., Do, B. T. & Hill, C. L. Ag5PV2Mo10O40, a heterogeneous catalyst for air-based selective oxidation at ambient temperature. J. Am. Chem. Soc. 123, 12101–12102 (2001).

    Article  CAS  Google Scholar 

  21. Long, D.-L. & Cronin, L. Towards polyoxometalate-integrated nano systems. Chem. Eur. J. 12, 3698–3706 (2006).

    Article  CAS  Google Scholar 

  22. Song, Y.-F. et al. Design of hydrophobic polyoxometalate hybrid assemblies beyond surfactant encapsulation. Chem. Eur. J. 14, 2349–2354 (2008).

    Article  CAS  Google Scholar 

  23. Long, D.-L., Streb, C., Song, Y.-F., Mitchell, S. G. & Cronin, L. Unravelling the complexities of polyoxometalates in solution using mass spectrometry: protonation versus heteroatom inclusion. J. Am. Chem. Soc. 130, 1830–1832 (2008).

    Article  CAS  Google Scholar 

  24. Song, Y.-F. et al. From polyoxometalate building blocks to polymers and materials: the silver connection. J. Mater Chem. 17, 1903–1908 (2007).

    Article  CAS  Google Scholar 

  25. Song, Y.-F., Long, D.-L. & Cronin, L. Non covalently connected frameworks with nanoscale channels assembled from a tethered polyoxometalate–pyrene hybrid. Angew. Chem. Int. Ed. 46, 3900–3904 (2007).

    Article  CAS  Google Scholar 

  26. Xin, Z. et al. Keggin POM microtubes: a coincident product of crystal growth and species transformation. Inorg. Chem. 45, 8856–8858 (2006).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors would like to thank the Leverhulme Trust (London), the Royal Society, the University of Glasgow, WestCHEM and the EPSRC for funding.

Author information

Authors and Affiliations

Authors

Contributions

L.C. conceived and designed the experiments, analysed the data, and prepared the manuscript, with help from C.S., C.R. and G.C. C.R. synthesized the clusters and the tubes, A.P. synthesized the cations, G.C., C.R., H.Y. and Y.S. performed the experiments with the tubes, and H.Y. fabricated the patterned structures. C.S. and D.M. performed the electron microscopy.

Corresponding author

Correspondence to Leroy Cronin.

Supplementary information

Supplementary Information

Supplementary information (PDF 3462 kb)

Supplementary Information

Supplementary Video S1 (WMV 4182 kb)

Supplementary Information

Supplementary Video S2 (WMV 4951 kb)

Supplementary Information

Supplementary Video S3 (WMV 4704 kb)

Supplementary Information

Supplementary Video S4 (WMV 5000 kb)

Supplementary Information

Supplementary Video S5 (WMV 1811 kb)

Supplementary Information

Supplementary Video S6 (WMV 4958 kb)

Supplementary Information

Supplementary Video S7 (WMV 2774 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Ritchie, C., Cooper, G., Song, YF. et al. Spontaneous assembly and real-time growth of micrometre-scale tubular structures from polyoxometalate-based inorganic solids. Nature Chem 1, 47–52 (2009). https://doi.org/10.1038/nchem.113

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nchem.113

This article is cited by

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing