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Functional Polymers

Polythiophene nanoparticles that display reversible multichromism in aqueous media

Polymer Journal volume 49, pages429–437(2017)Cite this article

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Abstract

Conjugated polymer nanoparticles in aqueous media have received much attention because of their specific electronic, optical and medicinal properties. However, flexible hydrophilic chains such as oligo(ethylene oxide) groups on the outer surface of the nanoparticles may induce increases in the particle size resulting from the aggregation of nanoparticles in water. We designed a bolaamphiphilic monomer to produce polythiophene nanoparticles. The resulting nanoparticles exhibit multichromic responses to solvent, temperature and acid/base that can be detected by the naked eye. The nanoparticles, with an average diameter of 170 nm and a large zeta potential of −66.6 mV, remain stable in tetrahydrofuran/water mixtures even after 8 months. As the concentration of water increases, the nanoparticles turn from yellow to violet because the molecular conformation of the thiophene units changes. The nanoparticles dispersed in water display a reversible thermochromic response between 20 and 90 °C, which originates from their different morphologies of an amorphous solid below and an isotropic liquid above their melting point of 60 °C. Adding hydrobromic acid yields an almost colorless dispersion because of the formation of polarons (p-doping), and the nanoparticles revert to their initial violet dispersion upon bubbling with ammonia gas owing to the dedoping of the polythiophene nanoparticles.

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References

  1. 1

    Thomas, S. W., Joly, G. D. & Swager, T. M. Chemical sensors based on amplifying fluorescent conjugated polymers. Chem. Rev. 107, 1339–1386 (2007).

    Google Scholar 

  2. 2

    Hoeben, F. J. M., Jonkheijm, P., Meijer, E. W. & Schenning, A. P. H. J. About supramolecular assemblies of π-conjugated systems. Chem. Rev. 105, 1491–1546 (2005).

    Google Scholar 

  3. 3

    Aida, T., Meijer, E. W. & Stupp, S. I. Functional supramolecular polymers. Science 335, 813–817 (2012).

    Google Scholar 

  4. 4

    Stuart, M. A. C., Huck, W. T., Genzer, J., Müller, M., Ober, C., Stamm, M., Sukhorukov, G. B., Szleifer, I., Tsukruk, V. V., Urban, M., Winnik, F., Zauscher, S., Luzinov, I. & Minko, S. Emerging applications of stimuli-responsive polymer materials. Nat. Mater. 9, 101–113 (2010).

    Google Scholar 

  5. 5

    Lee, J., Pyo, M., Lee, S. H., Kim, J., Ra, M., Kim, W. Y., Park, B. J., Lee, C. W. & Kim, J. M. Hydrochromic conjugated polymers for human sweat pore mapping. Nat. Commun. 5, 3736 (2014).

    Google Scholar 

  6. 6

    Lee, J., Chang, H. T., An, H., Ahn, S., Shim, J. & Kim, J. M. A Protective Layer Approach to Solvatochromic Sensors. Nat. Commun. 4, 2461 (2013).

    Google Scholar 

  7. 7

    Lee, E., Hammer, B., Kim, J. K., Page, Z., Emrick, T. & Hayward, R. C. Hierarchical helical assembly of conjugated poly(3-hexylthiophene)-block-poly(3-triethylene glycol thiophene) diblock copolymers. J. Am. Chem. Soc. 133, 10390–10393 (2011).

    Google Scholar 

  8. 8

    Lévesque, I., Bazinet, P. & Roovers, J. Optical properties and dual electrical and ionic conductivity in poly(3-methylhexa(oxyethylene)oxy-4-methylthiophene). Macromolecules 33, 2952–2957 (2000).

    Google Scholar 

  9. 9

    Turchetti, D. A., Domingues, R. A., Zanlorenzi, C., Nowacki, B., Atvars, T. D. Z. & Akcelrud, L. C. A photophysical interpretation of the thermochromism of a polyfluorene derivative-europium complex. J. Phys. Chem. C 118, 30079–30086 (2014).

    Google Scholar 

  10. 10

    Richards, C. E. & Phillips, R. T. Solvatochromic effects on the photoinduced charge-transfer states in donor-acceptor substituted polydioctylfluorenes. Chem. Phys. Chem. 12, 2831–2835 (2011).

    Google Scholar 

  11. 11

    Pecher, J. & Mecking, S. Nanoparticles of conjugated polymers. Chem. Rev. 110, 6260–6279 (2010).

    Google Scholar 

  12. 12

    Tuncel, D. & Demir, H. V. Conjugated polymer nanoparticles. Nanoscale 2, 484–494 (2010).

    Google Scholar 

  13. 13

    Ong, B. S., Wu, Y., Liu, P. & Gardner, S. Structurally ordered polythiophene nanoparticles for high-performance organic thin-film transistors. Adv. Mater. 17, 1141–1144 (2005).

    Google Scholar 

  14. 14

    Palner, M., Pu, K., Shao, S. & Rao, J. Semiconducting polymer nanoparticles with persistent near-infrared luminescence for in vivo optical imaging. Angew. Chem. Int. Ed. 54, 11477–11480 (2015).

    Google Scholar 

  15. 15

    Pu, K., Shuhendler, A. J., Jokerst, J. V., Mei, J., Gambhir, S. S., Bao, Z. & Rao, J. Semiconducting polymer nanoparticles as photoacoustic molecular imaging probes in living mice. Nat. Nanotechnol. 9, 233–239 (2014).

    Google Scholar 

  16. 16

    Xiong, L., Shuhendler, A. J. & Rao, J. Self-luminescing BRET-FRET near-infrared dots for in vivo lymph-node mapping and tumour imaging. Nat. Commun. 3, 1193 (2012).

    Google Scholar 

  17. 17

    Wu, C. & Chiu, D. T. Highly fluorescent semiconducting polymer dots for biology and medicine. Angew. Chem. Int. Ed. 52, 3086–3109 (2013).

    Google Scholar 

  18. 18

    Moon, J. H., Mendez, E., Kim, Y. & Kaur, A. Conjugated polymer nanoparticles for small interfering RNA delivery. Chem. Commun. 47, 8370–8372 (2011).

    Google Scholar 

  19. 19

    Das, S., Samanta, S., Chatterjee, D. P. & Nandi, A. K. Thermosensitive water-soluble poly(ethylene glycol)-based polythiophene graft copolymers. J. Polym. Sci. Part A 51, 1417–1427 (2013).

    Google Scholar 

  20. 20

    Moon, J. H., Deans, R., Krueger, E. & Hancock, L. F. Capture and detection of a quencher labeled oligonucleotide by poly(phenylene ethynylene) particles. Chem. Commun. 104–105 (2003).

  21. 21

    Brustolin, F., Goldoni, F., Meijer, E. W. & Sommerdijk, N. A. J. M. Highly ordered structures of amphiphilic polythiophenes in aqueous media. Macromolecules 35, 1054–1059 (2002).

    Google Scholar 

  22. 22

    Gilbert, T. W., Sellaro, T. L. & Badylak, S. F. Decellularization of tissues and organs. Biomaterials 27, 3675–3683 (2006).

    Google Scholar 

  23. 23

    Garvalov, B. K., Foss, F., Henze, A. T., Bethani, I., Gräf-Höchst, S., Singh, D., Filatova, A., Dopeso, H., Seidel, S., Damm, M., Acker-Palmer, A. & Acker, T. PHD3 regulates EGFR internalization and signalling in tumours. Nat. Commun. 5, 5577 (2014).

    Google Scholar 

  24. 24

    Wu, X., Liu, H., Liu, J., Haley, K. N., Treadway, J. A., Larson, J. P., Ge, N., Peale, F. & Bruchez, M. P. Immunofluorescent labeling of cancer marker Her2 and other cellular targets with semiconductor quantum dots. Nat. Biotechnol. 21, 41–46 (2003).

    Google Scholar 

  25. 25

    Mei, J. & Bao, Z. Side chain engineering in solution-processable conjugated polymers. Chem. Mater. 26, 604–615 (2014).

    Google Scholar 

  26. 26

    Chandler, D. Interfaces and the driving force of hydrophobic assembly. Nature 437, 640–647 (2005).

    Google Scholar 

  27. 27

    Wu, C., Szymanski, C. & McNeill, J. Preparation and encapsulation of highly fluorescent conjugated polymer nanoparticles. Langmuir 22, 2956–2960 (2006).

    Google Scholar 

  28. 28

    Qin, G. & Cai, C. Oxidative degradation of oligo(ethylene glycol)-terminated monolayers. Chem. Commun. 5112–5114 (2009).

  29. 29

    Matthews, J. R., Goldoni, F., Schenning, A. P. H. J. & Meijer, E. W. Non-ionic polythiophenes: a non-aggregating folded structure in water. Chem. Commun. 5503–5505 (2005).

  30. 30

    Crosby, G. A. & Demas, J. N. Measurement of photoluminescence quantum yields. Review. J. Phys. Chem. 75, 991–1024 (1971).

    Google Scholar 

  31. 31

    Li, C., Numata, M., Bae, A. H., Sakurai, K. & Shinkai, S. Self-assembly of supramolecular chiral insulated molecular wire. J. Am. Chem. Soc. 127, 4548–4549 (2005).

    Google Scholar 

  32. 32

    Lai, S. K., O'Hanlon, D. E., Harrold, S., Man, S. T., Wang, Y. Y., Cone, R. & Hanes, J. Rapid transport of large polymeric nanoparticles in fresh undiluted human mucus. Proc. Natl. Acad. Sci. USA 104, 1482–1487 (2007).

    Google Scholar 

  33. 33

    Chen, K., Liang, D., Tian, J., Shi, L. & Zhao, H. In-situ polymerization at the interfaces of micelles: a ‘grafting from’ method to prepare micelles with mixed coronal chains. J. Phys. Chem. B 112, 12612–12617 (2008).

    Google Scholar 

  34. 34

    Lévesque, I. & Leclerc, M. Ionochromic and thermochromic phenomena in a regioregular polythiophene derivative bearing oligo(oxyethylene) side chains. Chem. Mater. 8, 2843–2849 (1996).

    Google Scholar 

  35. 35

    Kim, Y. H., Hotta, S. & Heeger, A. J. Infrared photoexcitation and doping studies of poly(3-methylthienylene). Phys. Rev. B 36, 7486–7490 (1987).

    Google Scholar 

  36. 36

    Yamamoto, J. & Furukawa, Y. Electronic and vibrational spectra of positive polarons and bipolarons in regioregular poly(3-hexylthiophene) doped with ferric chloride. J. Phys. Chem. B 119, 4788–4794 (2015).

    Google Scholar 

  37. 37

    Kim, Y. H., Spiegel, D., Hotta, S. & Heeger, A. J. Photoexcitation and doping studies of poly(3-hexylthienylene). Phys. Rev. B 38, 5490–5495 (1988).

    Google Scholar 

  38. 38

    Pron, A., Louarn, G., Lapkowski, M., Zagorska, M., Glowczy-Zubek, J. & Lefrant, S. ‘In situ’ Raman spectroelectrochemical studies of poly(3,3'-dibutoxy-2,2'-bithiophene). Macromolecules 28, 4644–4649 (1995).

    Google Scholar 

Download references

Acknowledgements

We thank Dr Daisuke Hashizume and Ms Tomoka Kikitsu of the Materials Characterization Support Unit, RIKEN Center for Emergent Matter Science (CEMS), for the X-ray diffraction and TEM measurements and for their valuable comments and discussion. We also thank Professor Yu Nagase and Mr Tomoki Mimura of Tokai University for the GPC measurements and their comments. We acknowledge Dr Keisuke Tajima of the Emergent Functional Polymers Research Team, RIKEN CEMS, for the electrical conductivity measurements. We also thank Dr Zhaomin Hou and Dr Masayoshi Nishiura of the Organometallic Chemistry Laboratory, RIKEN, for the thermogravimetric analysis and DSC measurements. We thank Mr Takeo Soejima of the Applicative Solution Laboratory Division, JASCO, for the Raman measurements and technical support. This work was partially supported by a Grant-in-Aid for Scientific Research (C) (No. 15K05639) to MK from the Ministry of Education, Culture, Sports, Science and Technology of Japan.

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Affiliations

  1. Emergent Bioengineering Materials Research Team, RIKEN Center for Emergent Matter Science, RIKEN, Saitama, Japan

    Krishnachary Salikolimi, Masuki Kawamoto, Pan He & Yoshihiro Ito

  2. Department of Biological Sciences, Tokyo Metropolitan University, Tokyo, Japan

    Krishnachary Salikolimi, Toshiro Aigaki & Yoshihiro Ito

  3. Nano Medical Engineering Laboratory, RIKEN, Saitama, Japan

    Masuki Kawamoto & Yoshihiro Ito

  4. Photocatalysis International Research Center, Tokyo University of Science, Chiba, Japan

    Masuki Kawamoto

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  1. Krishnachary Salikolimi
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  2. Masuki Kawamoto
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Correspondence to Masuki Kawamoto or Yoshihiro Ito.

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Salikolimi, K., Kawamoto, M., He, P. et al. Polythiophene nanoparticles that display reversible multichromism in aqueous media. Polym J 49, 429–437 (2017). https://doi.org/10.1038/pj.2017.5

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