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.

  • Letter
  • Published:

Light–induced disassembly of self-assembled vesicle-capped nanotubes observed in real time

Nature Nanotechnology volume 6, pages 547–552 (2011)Cite this article

Subjects

Abstract

Molecular self-assembly is the basis for the formation of numerous artificial nanostructures1,2. The self-organization of peptides3,4,5,6, amphiphilic molecules composed of fused benzene rings7,8,9,10 and other functional molecules11,12,13,14,15 into nanotubes is of particular interest. However, the design of dynamic, complex self-organized systems that are responsive to external stimuli remains a significant challenge16. Here, we report self-assembled, vesicle-capped nanotubes that can be selectively disassembled by irradiation. The walls of the nanotubes are 3-nm-thick bilayers and are made from amphiphilic molecules with two hydrophobic legs that interdigitate when the molecules self-assemble into bilayers. In the presence of phospholipids, a phase separation between the phospholipids and the amphiphilic molecules creates nanotubes, which are end-capped by vesicles that can be chemically altered or removed and reattached without affecting the nanotubes. The presence of a photoswitchable and fluorescent core in the amphiphilic molecules allows fast and highly controlled disassembly of the nanotubes on irradiation, and distinct disassembly processes can be observed in real time using fluorescence microscopy.

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

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Schematic representation of assembly and disassembly of vesicle-capped nanotubes.
Figure 2: Structure and properties of amphiphilic switch 1 and self-assembled nanotube morphologies.
Figure 3: Analysis of changes to morphology.
Figure 4: Images of changes in tubular morphology as a function of time.

Similar content being viewed by others

References

  1. Whitesides, G. M. & Grzybowski, B. Self-assembly at all scales. Science 295, 2418–2421 (2002).

    Article  CAS  Google Scholar 

  2. Du, J. & O'Reilly, R. K. Advances and challenges in smart and functional polymer vesicles. Soft Matter 5, 3544–3561 (2009).

    Article  CAS  Google Scholar 

  3. Ghadiri, M. R., Granja, J. R. & Buehler, L. K. Artificial transmembrane ion channels from self-assembling peptide nanotubes. Nature 369, 301–304 (1994).

    Article  CAS  Google Scholar 

  4. Reches, M. & Gazit, E. Casting metal nanowires within discrete self-assembled peptide nanotubes. Science 300, 625–627 (2003).

    Article  CAS  Google Scholar 

  5. Adler-Abramovich, L. et al. Self-assembled arrays of peptide nanotubes by vapour deposition. Nature Nanotech. 4, 849–854 (2009).

    Article  CAS  Google Scholar 

  6. Lin, Y., Qiao, Y., Tang, P., Li, Z. & Huang, J. Controllable self-assembled laminated nanoribbons from dipeptide-amphiphile bearing azobenzene moiety. Soft Matter 7, 2762–2769 (2011).

    Article  CAS  Google Scholar 

  7. Hill, J. P. et al. Self-assembled hexa-peri-hexabenzocoronene graphitic nanotube. Science 304, 1481–1483 (2004).

    Article  CAS  Google Scholar 

  8. Borzsonyi, G. et al. Water-soluble J-type rosette nanotubes with giant molar ellipticity. J. Am. Chem. Soc. 132, 15136–15139 (2010).

    Article  CAS  Google Scholar 

  9. Yin, M. et al. Functionalization of self-assembled hexa-peri-hexabenzocoronene fibers with peptides for bioprobing. J. Am. Chem. Soc. 131, 14618–14619 (2009).

    Article  CAS  Google Scholar 

  10. Zhang, W., Jin, W., Fukushima, T., Ishii, N. & Aida, T. Metal-ion-coated graphitic nanotubes: controlled self-assembly of a pyridyl-appended gemini-shaped hexabenzocoronene amphiphile. Angew. Chem. Int. Ed. 48, 4747–4750 (2009).

    Article  CAS  Google Scholar 

  11. Shao, H. et al. Amphiphilic self-assembly of an n-type nanotube. Angew. Chem. Int. Ed. 49, 7688–7691 (2010).

    Article  CAS  Google Scholar 

  12. Kim, H. et al. Self-dissociating tubules from helical stacking of noncovalent macrocycles. Angew. Chem. Int. Ed. 49, 8471–8475 (2010).

    Article  CAS  Google Scholar 

  13. Eisele, D. M., Knoester, J., Kirstein, S., Rabe, J. P. & Vanden Bout, D. A. Uniform exciton fluorescence from individual molecular nanotubes immobilized on solid substrates. Nature Nanotech. 4, 658–663 (2009).

    Article  CAS  Google Scholar 

  14. Palmer, L. C. & Stupp, S. I. Molecular self-assembly into one-dimensional nanostructures. Acc. Chem. Res. 41, 1674–1684 (2008).

    Article  CAS  Google Scholar 

  15. Jin, W. et al. Self-assembled graphitic nanotubes with one-handed helical arrays of a chiral amphiphilic molecular graphene. Proc. Natl Acad. Sci. USA 102, 10801–10806 (2005).

    Article  CAS  Google Scholar 

  16. Roy, D., Cambre, J. N. & Sumerlin, B. S. Future perspectives and recent advances in stimuli-responsive materials. Prog. Polym. Sci. 35, 278–301 (2010).

    Article  CAS  Google Scholar 

  17. Service, R. F. How far can we push chemical self-assembly. Science 309, 95 (2005).

    Article  CAS  Google Scholar 

  18. Vollmer, M. S., Clark, T. D., Steinem, C. & Ghadiri, M. R. Photoswitchable hydrogen-bonding in self-organized cylindrical peptide systems. Angew. Chem. Int. Ed. 38, 1598–1601 (1999).

    Article  CAS  Google Scholar 

  19. Goodwin, A. P., Mynar, J. L., Ma, Y. Z., Fleming, G. R. & Frechet, J. M. J. Synthetic micelle sensitive to IR light via a two-photon process. J. Am. Chem. Soc. 127, 9952–9953 (2005).

    Article  CAS  Google Scholar 

  20. Mynar, J. L. et al. Two-photon degradable supramolecular assemblies of linear-dendritic copolymers. Chem. Commun. 20, 2081–2082 (2007).

    Article  Google Scholar 

  21. Parthasarathy, P. et al. Spatially controlled assembly of nanomaterials at the nanoscale. J. Nanosci. Nanotech. 9, 650–654 (2009).

    Article  CAS  Google Scholar 

  22. Wang, Y., Xu, H. & Zhang, X. Tuning the amphiphilicity of building blocks: controlled self-assembly and disassembly for functional supramolecular materials. Adv Mater. 21, 2849–2864 (2009).

    Article  CAS  Google Scholar 

  23. Muraoka, T., Koh, C., Cui, H. & Stupp, S. I. Light-triggered bioactivity in three dimensions. Angew. Chem. Int. Ed. 48, 5946–5949 (2009).

    Article  CAS  Google Scholar 

  24. Browne, W. R., Pollard, M. M., de lange, B., Meetsma, A. & Feringa, B. L. Reversible three-state switching of luminescence: a new twist to electro and photochromic behavior. J. Am. Chem. Soc. 128, 12412–12413 (2006).

    Article  CAS  Google Scholar 

  25. Coleman, A. C. et al. In situ generation of wavelength-shifting donor–acceptor mixed-monolayer-modified surfaces. Angew. Chem. Int. Ed. 49, 6580–6584 (2010).

    Article  CAS  Google Scholar 

  26. Pearlman, D. A. et al. Amber, a package of computer programs for applying molecular mechanics, normal-mode analysis, molecular-dynamics and free-energy calculations to simulate the structural and energetic properties of molecules. Comput. Phys. Commun. 91, 1–41 (1995).

    Article  CAS  Google Scholar 

  27. Tahara, Y. & Fujiyoshi, Y. A new method to measure bilayer thickness — cryoelectron microscopy of frozen-hydrated liposomes and image simulation. Micron 25, 141–149 (1994).

    Article  CAS  Google Scholar 

  28. Stuart, M. C. A. & Boekema, E. J. Two distinct mechanisms of vesicle-to-micelle and micelle-to-vesicle transition are mediated by the packing parameter of phospholipid-detergent systems. Biochim. Biophys. Acta Biomembr. 1768, 2681–2689 (2007).

    Article  CAS  Google Scholar 

  29. Brown, D. A. & London, E. Functions of lipid rafts in biological membranes. Annu. Rev. Cell Dev. Biol. 14, 111–136 (1998).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors thank the Zernike Institute for Advanced Materials (A.C.C. and J.T.M.) for funding and the US National Science Foundation (NSF) for an NSF International Postdoctoral Fellowship OISE-0853019 (J.M.B.). This project was supported by The Netherlands Organization for Scientific Research (NWO-CW) and the European Research Council (grant no. 227897).

Author information

Authors and Affiliations

  1. Center for Systems Chemistry, Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, Groningen, 9747 AG, The Netherlands

    Anthony C. Coleman, John M. Beierle, Marc C. A. Stuart, Beatriz Maciá, Giuseppe Caroli, Derk Jan van Dijken, Jiawen Chen, Wesley R. Browne & Ben L. Feringa

  2. Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, Groningen, 9747 AG, The Netherlands

    Anthony C. Coleman, Jacek T. Mika, Wesley R. Browne & Ben L. Feringa

  3. Department of Electron Microscopy, Groningen Biomolecular Science and Biotechnology Institute, University of Groningen, Nijenborgh 7, Groningen, 9747 AG, The Netherlands

    Marc C. A. Stuart

Authors
  1. Anthony C. Coleman
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. John M. Beierle
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Marc C. A. Stuart
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Beatriz Maciá
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Giuseppe Caroli
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Jacek T. Mika
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Derk Jan van Dijken
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Jiawen Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Wesley R. Browne
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Ben L. Feringa
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

B.L.F. conceived the research. B.L.F., A.C.C., J.M.B., W.R.B. and B.M. designed the experiments. Synthesis of the amphiphile was carried out by B.M., D.J.v.D. and J.C. Solution photochemical studies, switching studies and tube generation were carried out by A.C.C. and B.M. Cryo-TEM was carried out by M.C.A.S. Molecular models were generated by G.C. Confocal microscope and epifluorescence studies were carried out by J.M.B. and J.T.M. A.C.C., J.M.B., W.R.B. and B.L.F. co-wrote the paper. All authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Ben L. Feringa.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 4284 kb)

Supplementary information

Supplementary movie 1 (WMV 2764 kb)

Supplementary information

Supplementary movie 2 (WMV 1020 kb)

Supplementary information

Supplementary movie 3 (WMV 2817 kb)

Supplementary information

Supplementary movie 4 (WMV 2606 kb)

Supplementary information

Supplementary movie 5 (WMV 7582 kb)

Supplementary information

Supplementary movie 6 (WMV 8176 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Coleman, A., Beierle, J., Stuart, M. et al. Light–induced disassembly of self-assembled vesicle-capped nanotubes observed in real time. Nature Nanotech 6, 547–552 (2011). https://doi.org/10.1038/nnano.2011.120

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nnano.2011.120

This article is cited by

Search

Advanced 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