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Dynamic actuation of glassy polymersomes through isomerization of a single azobenzene unit at the block copolymer interface

Nature Chemistry volume 10, pages 659–666 (2018)Cite this article

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An Author Correction to this article was published on 28 June 2018

This article has been updated

Abstract

Nature has engineered exquisitely responsive systems where molecular-scale information is transferred across an interface and propagated over long length scales. Such systems rely on multiple interacting, signalling and adaptable molecular and supramolecular networks that are built on dynamic, non-equilibrium structures. Comparable synthetic systems are still in their infancy. Here, we demonstrate that the light-induced actuation of a molecularly thin interfacial layer, assembled from a hydrophilic-azobenzene-hydrophobic diblock copolymer, can result in a reversible, long-lived perturbation of a robust glassy membrane across a range of over 500 chemical bonds. We show that the out-of-equilibrium actuation is caused by the photochemical trans–cis isomerization of the azo group, a single chemical functionality, in the middle of the interfacial layer. The principles proposed here are implemented in water-dispersed nanocapsules, and have implications for on-demand release of embedded cargo molecules.

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Fig. 1: Structure and self-assembly of block copolymer P2.
Fig. 2: Encapsulation ability and stimuli-responsive behaviour of P2 vesicles.
Fig. 3: P2 vesicles demonstrating non-equilibrium behaviour.
Fig. 4: Mechanistic investigations of the non-equilibrium behavior of the assembly.

Change history

  • 28 June 2018

    In the version of this Article originally published, multiple changes to the “Results and discussion” section were required. In paragraph 1, “(Supplementary Fig. 1)” should have read “(Fig. 1e–j and Supplementary Fig. 1)”; in the first sentence of paragraph 3, “(R6G)” should have read “(R6G, Fig. 2i)”; in paragraph 6 in the sentence beginning “Temporal release of hydrophilic...”, Supplementary Fig. 4 should have been cited after “360 nm”; in paragraph 9, in the sentence beginning “To test this...”, “Fig. 4e” should have read “Fig. 4a”; in paragraph 10, in the sentence beginning “When the irradiation...”, “(Fig. 4a–d)” should have read “(Fig. 4d,e)”; in paragraph 11, in the sentence beginning “Pristine PLA”, “P1” should have read “P2”; and in the penultimate paragraph, in the sentence beginning “Moreover, a control PEG-PLA...”, “block copolymer” should have been followed by (P5); Fig. 4g should have been Fig. 4c; “hydrophobic azobenzene small molecules” should have been followed by (12); and Fig. 4f should have been Fig. 4b. Finally, Supplementary Videos 1 and 2 were missing from the Article. All of these corrections have been made to the online versions.

References

  1. Natansohn, A. & Rochon, P. Photoinduced motions in azobenzene-based amorphous polymers: possible photonic devices. Adv. Mater. 11, 1387–1391 (1999).

    Article  CAS  Google Scholar 

  2. Yamada, M. et al. Photomobile polymer materials: towards light-driven plastic motors. Angew. Chem. Int. Ed. 47, 4986–4988 (2008).

    Article  CAS  Google Scholar 

  3. Swallen, S. F. et al. Organic glasses with exceptional thermodynamic and kinetic stability. Science 315, 353–356 (2007).

    Article  CAS  PubMed  Google Scholar 

  4. Singh, S., Ediger, M. D. & de Pablo, J. J. Ultrastable glasses from in silico vapour deposition. Nat. Mater. 12, 139–144 (2013).

    Article  CAS  PubMed  Google Scholar 

  5. Dalal, S. S., Walters, D. M., Lyubimov, I., de Pablo, J. J. & Ediger, M. D. Tunable molecular orientation and elevated thermal stability of vapor-deposited organic semiconductors. Proc. Natl Acad. Sci. USA 112, 4227–4232 2015).

    Article  CAS  PubMed  Google Scholar 

  6. Bin, Y., Xia, T., Patrick, A. & Yue, Z. Light responsive block co-polymer vesicles based on a photo softening effect. Soft Matter 7, 10001–10009 (2011).

    Article  CAS  Google Scholar 

  7. Gelebart, A. H. et al. Making waves in a photoactive polymer film. Nature 546, 632–636 (2017).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  8. Dong, R., Zhu, B., Zhou, Y., Yana, D. & Zhu, X. Reversible photoisomerization of azobenzene containing polymeric systems driven by visible light. Polym. Chem. 4, 912–915 2013).

    Article  CAS  Google Scholar 

  9. Wang, G., Tong, X. & Zhao, Y. Preparation of azobenzene-containing amphiphilic diblock copolymers for light-responsive micellar aggregates. Macromolecules 37, 8911–8917 (2004).

    Article  CAS  Google Scholar 

  10. Liu, X. & Jiang, M. Optical switching of self-assembly: micellization and micelle–hollow-sphere transition of hydrogen-bonded polymers. Angew. Chem. Int. Ed. 45, 3846–3850 (2006).

    Article  CAS  Google Scholar 

  11. Feng, Z., Lin, L., Yan, Z. & Yu, Y. Dual responsive block copolymer micelles functionalized by NIPAM and azobenzene. Macromol. Rapid Commun. 31, 640–644 (2010).

    Article  CAS  PubMed  Google Scholar 

  12. Kuiper, J. M. & Engberts, B. F. N. H-aggregation of azobenzene substituted amphiphiles in vesicular membranes. Langmuir 20, 1152–1160 (2004).

    Article  CAS  PubMed  Google Scholar 

  13. Pencer, J. & Hallett, F. R. Effects of vesicle size and shape on static and dynamic light scattering measurements. Langmuir 19, 7488–7497 (2003).

    Article  CAS  Google Scholar 

  14. O’Reilly, R. K., Hawker, C. J. & Wooley, K. L. Cross-linked block copolymer micelles: functional nanostructures of great potential and versatility. Chem. Soc. Rev. 35, 1068–1083 (2006).

    Article  CAS  PubMed  Google Scholar 

  15. Lee, S. M., Chen, H., Dettmer, C. M., O’Halloran, T. V. & Nguyen, S. T. Polymer-caged lipsome: pH-responsive delivery system with high stability. J. Am. Chem. Soc. 129, 15096–15097 (2007).

    Article  CAS  PubMed  Google Scholar 

  16. Savariar, E. N., Aathimanikandan, S. V. & Thayumanavan, S. Supramolecular assemblies from amphiphilic homopolymers: testing the scope. J. Am. Chem. Soc. 128, 16224–16230 (2006).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  17. Beharry, A. A. & Woolley, G. A. Azobenzene photoswitches for biomolecules. Chem. Soc. Rev. 40, 4422–4437 (2011).

    Article  CAS  PubMed  Google Scholar 

  18. Merino, E. & Ribagorda, M. Control over molecular motion using the cis–trans photoisomerization of the azo group. Beilstein J. Org. Chem. 8, 1071–1090 (2012).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  19. Gabor, G. & Fischer, E. Spectra and cis–trans isomerism in highly bipolar derivatives of azobenzene. J. Phys. Chem. 75, 581–583 (1971).

    Article  CAS  Google Scholar 

  20. Bandara, H. M. D. & Burdette, S. C. Photoisomerization in different classes of azobenzene. Chem. Soc. Rev. 41, 1809–1825 (2012).

    Article  CAS  PubMed  Google Scholar 

  21. Fialkowski, M. et al. Principles and implementations of dissipative (dynamic) self-assembly. J. Phys. Chem. B 110, 2482–2496 (2006).

    Article  CAS  PubMed  Google Scholar 

  22. Boekhoven, J. et al. Dissipative self-assembly of a molecular gelator by using a chemical fuel. Angew. Chem. Int. Ed. 49, 4825–4828 (2010).

    Article  CAS  Google Scholar 

  23. Mattia, E. & Otto, S. Supramolecular systems chemistry. Nat. Nanotech. 10, 111–119 (2015).

    Article  CAS  Google Scholar 

  24. Natansohn, A. & Rochon, P. Photoinduced motions in azo-containing polymers. Chem. Rev. 102, 4139–4175 (2002).

    Article  CAS  PubMed  Google Scholar 

  25. Marder, S. R. et al Large 1st hyperpolarizabilities in push–pull polyenes by tuning of the bond-length alteration and aromaticity. Science 263, 511–514 1994).

    Article  CAS  PubMed  Google Scholar 

  26. Jorgensen, W. L., Maxwell, D. S. & Tirado-Rives, J. Development and testing of the OPLS all atom force field on conformational energetics and properties of organic liquids. J. Am. Chem. Soc. 118, 11225–11236 (1996).

    Article  CAS  Google Scholar 

  27. Kaminski, G. A., Friesner, R. A., Tirado-Rives, J. & Jorgensen, W. L. Evaluation and reparametrization of the OPLS-AA force field for proteins via comparison with accurate quantum chemical calculations on peptides. J. Phys. Chem. B 105, 6474–6487 (2001).

    Article  CAS  Google Scholar 

  28. Dorgan, J. R., Lehermeier, H. & Mang, M. Thermal and rheological properties of commercial-grade poly(lactic acid). J. Polym. Environ. 8, 1–9 (2000).

    Article  Google Scholar 

  29. Auras, R., Harte, B. & Selke, S. An overview of polylactides as packaging materials. Macromol. Biosci. 4, 835–864 (2004).

    Article  CAS  PubMed  Google Scholar 

  30. Younes, H. & Cohn, D. Phase separation in poly(ethyleneglycol)/poly(lactic acid) blends. Eur. Polym. J. 24, 765–773 (1988).

    Article  CAS  Google Scholar 

  31. Zhao, H. et al. Preparation and characterization of PEG/PLA multiblock and triblock copolymer. Bull. Korean Chem. Soc. 33, 1638–1642 (2012).

    Article  CAS  Google Scholar 

  32. Fang, G. J. Athermal photofluidization of glasses. Nat. Commun. 4, 1–9 (2013).

    Google Scholar 

  33. Qiu, Y., Antony, L. W., de Pablo, J. J. & Ediger, M. D. Photostability can be significantly modulated by molecular packing in glasses. J. Am. Chem. Soc. 138, 11282–11289 (2016).

    Article  CAS  PubMed  Google Scholar 

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Acknowledgements

The authors thank the US Army Research Office for funding through the MURI program (W911NF-15-1-0568).

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Author notes

  1. These authors contributed equally: Mijanur Rahaman Molla, Poornima Rangadurai and Lucas Antony

Authors and Affiliations

  1. Department of Chemistry, University of Massachusetts, Amherst, MA, USA

    Mijanur Rahaman Molla, Poornima Rangadurai, Subramani Swaminathan & S. Thayumanavan

  2. Institute for Molecular Engineering, University of Chicago, Chicago, IL, USA

    Lucas Antony & Juan J. de Pablo

  3. Molecular and Cellular Biology Program, University of Massachusetts, Amherst, MA, USA

    S. Thayumanavan

  4. Center for Bioactive Delivery, Institute for Applied Life Sciences, University of Massachusetts, Amherst, MA, USA

    S. Thayumanavan

Authors
  1. Mijanur Rahaman Molla
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  5. Juan J. de Pablo
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Contributions

S.T. conceived and supervised the project. M.R.M. initiated the project. M.R.M. and P.R. performed all the experiments, with help from S.S. J.d.P. initiated the simulations and computational studies. L.A. performed all the simulation studies. All authors contributed to the discussion of the results and preparation of the manuscript.

Corresponding author

Correspondence to S. Thayumanavan.

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Supplementary information

Supplementary information

Supplementary synthesis and characterization details and analysis, Schemes 1–3, and Figures 1–16

Supplementary Movie 1

Real-time movie showing that no reaction occurred between hexamathylene diamine encapsulated within the aqueous lumen of the supramolecular capsule formed by P2 and sebacoyl chloride dissolved in hexane.

Supplementary Movie 2

Real-time movie of nylon formation between hexamathylene released from the supramolecular capsule formed by P2 upon light irradiation and sebacoyl chloride dissolved in hexane.

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Molla, M.R., Rangadurai, P., Antony, L. et al. Dynamic actuation of glassy polymersomes through isomerization of a single azobenzene unit at the block copolymer interface. Nature Chem 10, 659–666 (2018). https://doi.org/10.1038/s41557-018-0027-6

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