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.

  • Article
  • Published:

Mechanically induced chemiluminescence from polymers incorporating a 1,2-dioxetane unit in the main chain

Nature Chemistry volume 4, pages 559–562 (2012)Cite this article

Subjects

Abstract

Nature uses mechanochemical transduction processes to achieve diverse and vital functions, such as hearing, cellular adhesion and gating of ion channels. One fascinating example of biological mechanotransduction is the emission of light on mechanical stimulation. However, molecular-level transduction of force into luminescence in a synthetic system remains a challenge. Here, we show that bis(adamantyl)-1,2-dioxetane emits visible light when force is applied to a polymer chain or network in which this unit is incorporated. Bright-blue luminescence was observed on sonication of solutions of dioxetane-containing linear polymers and on the straining of polymer networks with dioxetane crosslinkers. Light is emitted from the adamantanone-excited state that forms on opening of the four-membered dioxetane ring. Increased sensitivity and colour tuning were achieved by energy transfer to suitable acceptors. High spatial and temporal resolutions highlight the potential to study the failure of polymeric materials in unprecedented detail.

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: Concept and chemical structures used.
Figure 2: Stress and light intensity versus time during stretching of bulk films.
Figure 3: Luminescence spectra obtained during stretching of films of PMA-2-PMA that contain different acceptors.

Similar content being viewed by others

References

  1. Gillespie, P. G. & Walker, R. G. Molecular basis of mechanosensory transduction. Nature 413, 194–202 (2001).

    Article  CAS  Google Scholar 

  2. Friedland, J. C., Lee, M. H. & Boettiger, D. Mechanically activated integrin switch controls α5β1 function. Science 323, 642–644 (2009).

    Article  CAS  Google Scholar 

  3. Haddock, S. H. D., Moline, M. A. & Case, J. F. Bioluminescence in the sea. Annu. Rev. Mar. Sci. 2, 443–493 (2010).

    Article  Google Scholar 

  4. Potisek, S. L., Davis, D. A., Sottos, N. R., White, S. R. & Moore, J. S. Mechanophore-linked addition polymers. J. Am. Chem. Soc. 129, 13808–13809 (2007).

    Article  CAS  Google Scholar 

  5. Davis, D. A. et al. Force-induced activation of covalent bonds in mechanoresponsive polymeric materials. Nature 459, 68–72 (2009).

    Article  CAS  Google Scholar 

  6. Piermattei, A., Karthikeyan, S. & Sijbesma, R. P. Activating catalysts with mechanical force. Nature Chem. 1, 133–137 (2009).

    Article  CAS  Google Scholar 

  7. Caruso, M. M. et al. Mechanically-induced chemical changes in polymeric materials. Chem. Rev. 109, 5755–5798 (2009).

    Article  CAS  Google Scholar 

  8. Beyer, M. K. & Clausen-Schaumann, H. Mechanochemistry: the mechanical activation of covalent bonds. Chem. Rev. 105, 2921–2948 (2005).

    Article  CAS  Google Scholar 

  9. Black, A. L., Lenhardt, J. M. & Craig, S. L. From molecular mechanochemistry to stress-responsive materials. J. Mater. Chem. 21, 1655–1663 (2011).

    Article  CAS  Google Scholar 

  10. Butyagin, P. Y. et al. About luminescence accompanied mechanical deformation and rupture of polymers. Vysokomol. Soed. A. 12, 290–299 (1970).

    CAS  Google Scholar 

  11. Dodeigne, C., Thunus, L. & Lejeune, R. Chemiluminescence as diagnostic tool. A review. Talanta 51, 415–439 (2000).

    Article  CAS  Google Scholar 

  12. Rongen, H. A. H., Hoetelmans, R. M. W., Bult, A. & Van Bennekom, W. P. Chemiluminescence and immunoassays. J. Pharm. Biomed. Anal. 12, 433–462 (1994).

    Article  CAS  Google Scholar 

  13. Schuster, G. B. et al. Adamantylideneadamantane-1,2-dioxetane. An investigation of the chemiluminescence and decomposition kinetics of an unusually stable 1,2-dioxetane. J. Am. Chem. Soc. 97, 7110–7118 (1975).

    Article  CAS  Google Scholar 

  14. Meijer, E. W. & Wynbergl, H. The synthesis and chemiluminescence of a stable 1,2-dioxetane. J. Chem. Educ. 59, 1071–1072 (1982).

    Article  CAS  Google Scholar 

  15. Turro, N. J. et al. Tetramethyl-1,2-dioxetane. Experiments in chemiexcitation, chemiluminescence, photochemistry, chemical dynamics, and spectroscopy. Acc. Chem. Res. 7, 97–105 (1974).

    Article  CAS  Google Scholar 

  16. Beck, S. & Koster, H. Applications of dioxetane chemiluminescent probes to molecular biology. Anal. Chem. 62, 2258–2270 (1990).

    Article  CAS  Google Scholar 

  17. Lenhardt, J. M., Black, A. L. & Craig, S. L. gem-Dichlorocyclopropanes as abundant and efficient mechanophores in polybutadiene copolymers under mechanical stress. J. Am. Chem. Soc. 131, 10818–10819 (2009).

    Article  CAS  Google Scholar 

  18. Kryger, M. J., Munaretto, A. M. & Moore, J. S. Structure–mechanochemical activity relationships for cyclobutane mechanophores. J. Am. Chem. Soc. 133, 18992–18998 (2011).

    Article  CAS  Google Scholar 

  19. Klukovich, H. M., Kean, Z. S., Iacono, S. T. & Craig, S. L. Mechanically induced scission and subsequent thermal remending of perfluorocyclobutane polymers. J. Am. Chem. Soc. 133, 17882–17888 (2011).

    Article  CAS  Google Scholar 

  20. Wiggins, K. M., Syrett, J. A., Haddleton, D. M. & Bielawski, C. W. Mechanically facilitated retro [4+2]cycloadditions. J. Am. Chem. Soc. 133, 7180–7189 (2011).

    Article  CAS  Google Scholar 

  21. Song, Y-K. et al. Fluorescence sensing of microcracks based on cycloreversion of a dimeric anthracene moiety. J. Mater. Chem. 22, 1380–1386 (2012).

    Article  CAS  Google Scholar 

  22. Brantley, J. N., Wiggins, K. M. & Bielawski, C. W. Unclicking the click: mechanically facilitated 1,3-dipolar cycloreversions. Science 333, 1606–1609 (2011).

    Article  CAS  Google Scholar 

  23. Percec, V. et al. Ultrafast synthesis of ultrahigh molar mass polymers by metal-catalyzed living radical polymerization of acrylates, methacrylates, and vinyl chloride mediated by SET at 25 °C. J. Am. Chem. Soc. 128, 14156–14165 (2006).

    Article  CAS  Google Scholar 

  24. Bechara, E. J. H. & Wilson, T. Alkyl substituent effects on dioxetane properties. Tetraethyl-, dicyclohexylidene-, and 3,4-dimethyl-3,4-di-n-butyldioxetanes. A discussion of decomposition mechanisms. J. Org. Chem. 45, 5261–5268 (1980).

    Article  CAS  Google Scholar 

  25. Brown, H. R. A molecular interpretation of the toughness of glassy polymers. Macromolecules 24, 2752–2756 (1991).

    Article  CAS  Google Scholar 

  26. Mikos, A. G. & Peppas, N. A. Polymer chain entanglements and brittle fracture. J. Chem. Phys. 88, 1337–1342 (1988).

    Article  CAS  Google Scholar 

  27. Mohammadi, N., Klein, A. & Sperling, L. H. Polymer chain rupture and the fracture behavior of glassy polystyrene. Macromolecules 26, 1019–1026 (1993).

    Article  CAS  Google Scholar 

  28. Lee, C. K. et al. Force-induced redistribution of a chemical equilibrium. J. Am. Chem. Soc. 132, 16107–16111 (2010).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by grants from the Netherlands Organization for Scientific Research. We thank H. J. Zhu for help with recording the videos, and L. E. Govaert and S. C. Meskers for helpful discussions.

Author information

Authors and Affiliations

  1. Institute for Complex Molecular Systems, Eindhoven University of Technology, PO Box 513, Eindhoven, 5600, MB, The Netherlands

    Yulan Chen, A. J. H. Spiering, S. Karthikeyan, E. W. Meijer & Rint P. Sijbesma

  2. Department of Mechanical Engineering, Materials Technology, Eindhoven University of Technology, PO Box 513, Eindhoven, 5600, MB, The Netherlands

    Gerrit W. M. Peters

Authors
  1. Yulan Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. A. J. H. Spiering
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. S. Karthikeyan
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Gerrit W. M. Peters
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. E. W. Meijer
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Rint P. Sijbesma
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

R.P.S. and E.W.M. conceived the concept, R.P.S. directed the research, Y.C., A.J.H.S., S.K. and G.W.M.P designed and performed the experiments and analysed the data. All of the authors participated in writing the paper.

Corresponding author

Correspondence to Rint P. Sijbesma.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 847 kb)

Supplementary Movie 1

Supplementary Movie 1 (AVI 2233 kb)

Supplementary Movie 2

Supplementary Movie 2 (AVI 4409 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Chen, Y., Spiering, A., Karthikeyan, S. et al. Mechanically induced chemiluminescence from polymers incorporating a 1,2-dioxetane unit in the main chain. Nature Chem 4, 559–562 (2012). https://doi.org/10.1038/nchem.1358

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nchem.1358

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