Skip to main content
Log in

pH-responsive AIE-active Polyethylene-based Block Copolymers

  • Article
  • Published:
Chinese Journal of Polymer Science Aims and scope Submit manuscript

Abstract

A novel synthetic strategy towards pH-responsive aggregation-induced emission (AIE)-active tetraphenylethene (TPE)-functionalized polyethylene-based block copolymers is presented. Tris(3-(4-(1,2,2-triphenylvinyl)phenoxy)propyl)borane was used to initiate the polyhomologation of dimethylsulfoxonium methylide to afford well-defined α-TPE-ω-OH linear polyethylenes (PE). The terminal hydroxyl groups were transformed to atom transfer radical polymerization (ATRP) initiating sites by esterification with α-bromoisobutyryl bromide, followed by polymerization of tert-butyl acrylate (tBA) to provide TPE-PE-b-PtBA block copolymers. After hydrolysis of the tBu group to COOH group, the corresponding pH-responsive TPE-PE-b-PAA block copolymers were obtained. All synthesized block copolymers revealed AIE behavior either in solution or bulk. Due to the pH-responsivity of PAA chains, the aggregation state at different pH and consequently the fluorescence intensity changed. Also, the synthesized block copolymers exhibited ion-specificity fluorescence properties.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. Bünzli, J. C. G. Lanthanide luminescence for biomedical analyses and imaging. Chem. Rev. 2010, 110, 2729–2755.

    Article  CAS  PubMed  Google Scholar 

  2. Jüstel, T.; Nikol, H.; Ronda, C. New developments in the field of luminescent materials for lighting and displays. Angew. Chem. Int. Ed. 1998, 37, 3084–3103.

    Article  Google Scholar 

  3. Schmidt, A.; Anderson, M.; Armstrong, N. R. Electronic states of vapor deposited electron and hole transport agents and luminescent materials for light-emitting diodes. J. Appl. Phys. 1995, 78, 5619–5625.

    Article  CAS  Google Scholar 

  4. Bredol, M.; Kynast, U.; Ronda, C. Designing luminescent materials. Adv. Mater. 1991, 3, 361–367.

    Article  CAS  Google Scholar 

  5. Luo, J.; Xie, Z.; Lam, J. W.; Cheng, L.; Chen, H.; Qiu, C.; Kwok, H. S.; Zhan, X.; Liu, Y.; Zhu, D. Aggregation-induced emission of 1-methyl-1,2,3,4,5-pentaphenylsilole. Chem. Commun. 2001, 1740, 1740–1741.

    Article  Google Scholar 

  6. Förster, T.; Kasper, K. Ein konzentrationsumschlag der fluoreszenz des pyrens. Zeitschrift für Elektrochemie, Berichte der Bunsengesellschaft für physikalische Chemie 1955, 59, 976–980.

    Google Scholar 

  7. Feng, H. T.; Yuan, Y. X.; Xiong, J. B.; Zheng, Y. S.; Tang, B. Z. Macrocycles and cages based on tetraphenylethylene with aggregation-induced emission effect. Chem. Soc. Rev. 2018, 47, 7452–7476.

    Article  CAS  PubMed  Google Scholar 

  8. Mei, J.; Leung, N. L.; Kwok, R. T.; Lam, J. W. Y.; Tang, B. Z. Aggregation-induced emission: Together we shine, united we soar! Chem. Rev. 2015, 115, 11718–11940.

    Article  CAS  PubMed  Google Scholar 

  9. Hong, Y.; Lam, J. W. Y.; Tang, B. Z. Aggregation-induced emission. Chem. Soc. Rev. 2011, 40, 5361–5388.

    Article  CAS  PubMed  Google Scholar 

  10. Qin, A.; Lam, J. W. Y.; Tang, B. Z. Luminogenic polymers with aggregation-induced emission characteristics. Prog. Polym. Sci. 2012, 37, 182–209.

    Article  CAS  Google Scholar 

  11. Hu, R.; Leung, N. L.; Tang, B. Z. AIE macromolecules: Syntheses, structures and functionalities. Chem. Soc. Rev. 2014, 43, 4494–4562.

    Article  CAS  PubMed  Google Scholar 

  12. 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. Emerging applications of stimuli-responsive polymer materials. Nat. Mater. 2010, 9, 101–113.

    Article  CAS  PubMed  Google Scholar 

  13. Liu, F.; Urban, M. W. Recent advances and challenges in designing stimuli-responsive polymers. Prog. Polym. Sci. 2010, 35, 3–23.

    Article  CAS  Google Scholar 

  14. Lendlein, A.; Shastri, V. P. Stimuli-sensitive polymers. Adv. Mater. 2010, 22, 3344–3347.

    Article  CAS  PubMed  Google Scholar 

  15. De las Heras Alarcón, C.; Pennadam, S.; Alexander, C. Stimuli responsive polymers for biomedical applications. Chem. Soc. Rev. 2005, 34, 276–285.

    Article  PubMed  Google Scholar 

  16. Roth, P. J.; Lowe, A. B. Stimulus-responsive polymers. Polym. Chem. 2017, 8, 10–11.

    Article  CAS  Google Scholar 

  17. Kocak, G.; Tuncer, C.; Bütün, V. pH-responsive polymers. Polym. Chem. 2017, 8, 144–176.

    Article  CAS  Google Scholar 

  18. Wei, M.; Gao, Y.; Li, X.; Serpe, M. J. Stimuli-responsive polymers and their applications. Polym. Chem. 2017, 8, 127–143.

    Article  CAS  Google Scholar 

  19. McLaurin, E. J.; Bradshaw, L. R.; Gamelin, D. R. Dual-emitting nanoscale temperature sensors. Chem. Mater. 2013, 25, 1283–1292.

    Article  CAS  Google Scholar 

  20. Cui, Y.; Song, R.; Yu, J.; Liu, M.; Wang, Z.; Wu, C.; Yang, Y.; Wang, Z.; Chen, B.; Qian, G. Dual-emitting MOF dye composite for ratiometric temperature sensing. Adv. Mater. 2015, 27, 1420–1425.

    Article  CAS  PubMed  Google Scholar 

  21. Zhang, Z.; Hadjichristidis, N. Temperature and pH-dual responsive AIE-active core crosslinked polyethylene-poly (methacrylic acid) multimiktoarm star copolymers. ACS Macro Lett. 2018, 7, 886–891.

    Article  CAS  Google Scholar 

  22. Shea, K. J. Polyhomologation: The living polymerization of ylides. Chem. Eur. J. 2000, 6, 1113–1119.

    Article  CAS  PubMed  Google Scholar 

  23. Shea, K.; Walker, J.; Zhu, H.; Paz, M.; Greaves, J. Polyhomologation A living polymethylene synthesis. J. Am. Chem. Soc. 1997, 119, 9049–9050.

    Article  CAS  Google Scholar 

  24. Luo, J.; Shea, K. J. Polyhomologation. A living C1 polymerization. Acc. Chem. Res. 2010, 43, 1420–1433.

    Article  CAS  PubMed  Google Scholar 

  25. Wang, D.; Hadjichristidis, N. Terpolymers from borane-initiated copolymerization of triphenyl arsonium and sulfoxonium ylides: An unexpected light emission. Angew. Chem. 2019, 131, 6361–6365.

    Article  Google Scholar 

  26. Jiang, Y.; Zhang, Z.; Wang, D.; Hadjichristidis, N. An efficient and general strategy toward the synthesis of polyethylene-based cyclic polymers. Macromolecules 2018, 51, 3193–3202.

    Article  CAS  Google Scholar 

  27. Xue, Y.; Lu, H. C.; Zhao, Q. L.; Huang, J.; Xu, S. G.; Cao, S. K.; Ma, Z. Polymtmylene-b-poly(ttyeene-co-2,3,4,5,6-pentafluoro styrene) copolymers: Synthesis and fabrication of their porous films. Polym. Chem. 2013, 4, 307–312.

    Article  CAS  Google Scholar 

  28. He, Q.; Ren, J.; Ren, J.; Pang, K.; Ma, Z.; Zhu, X.; Song, R. Polymethylene-b-poly(acrylic acid) diblock copolymers: Aggregation and crystallization in the presence of CaCl2. Eur. Polym. J. 2017, 95, 174–185.

    Article  CAS  Google Scholar 

  29. Wang, H.; Xu, F.; Cui, K.; Zhang, H.; Huang, J.; Zhao, Q.; Jiang, T.; Ma, Z. Synthesis of polymethylene-b-poly(vinyl acetate) block copolymer via visible light induced radical polymerization and its application. RSC Adv. 2017, 7, 42484–42490.

    Article  CAS  Google Scholar 

  30. Xue, Y.; Zhang, S. S.; Cui, K.; Huang, J.; Zhao, Q. L.; Lan, P.; Cao, S. K.; Ma, Z. New polymethylene-based AB2 star copolymers synthesized via a combination of polyhomologation of ylides and atom transfer radical polymerization. RSC Adv. 2015, 5, 7090–7097.

    Article  CAS  Google Scholar 

  31. Wang, D.; Hadjichristidis, N. Allyl borates: A novel class of polyhomologation initiators. Chem. Commun. 2017, 53, 1196–1199.

    Article  CAS  Google Scholar 

  32. Zhang, H.; Banerjee, S.; Faust, R.; Hadjichristidis, N. Living cationic polymerization and polyhomologation: An ideal combination to synthesize functionalized polyethylene-polyisobutylene block copolymers. Polym. Chem. 2016, 7, 1217–1220.

    Article  CAS  Google Scholar 

  33. Zhang, Z.; Altaher, M.; Zhang, H.; Wang, D.; Hadjichristidis, N. Synthesis of well-defined polyethylene-based 3-miktoarm star copolymers and terpolymers. Macromolecules 2011, 49, 2630–2638.

    Article  CAS  Google Scholar 

  34. Zhang, Z.; Gnanou, Y.; Hadjichristidis, N. Well-defined 4-arm stars with hydroxy-terminated polyethylene, polyethylene-b-polycaprolactone and polyethylene-b-(polymethyl methacrylate) 2 arms. Polym. Chem. 2011, 7, 5507–5511.

    Article  CAS  Google Scholar 

  35. Zhang, Z.; Zhang, H.; Gnanou, Y.; Hadjichristidis, N. Polyhomologation based on in situ generated boron-thexyl-silaboracyclic initiating sites: A novel strategy towards the synthesis of polyethylene-based complex architectures. Chem. Commun. 2015, 51, 9936–9938.

    Article  CAS  Google Scholar 

  36. Zhang, H.; Gnanou, Y.; Hadjichristidis, N. Well-defined polyethylene molecular brushes by polyhomologation and ring opening metathesis polymerization. Polym. Chem. 2014, 5, 6431–6434.

    Article  CAS  Google Scholar 

  37. Wang, D.; Zhang, Z.; Hadjichristidis, N. C1 polymerization: A unique tool towards polyethylene-based complex macromolecular architectures. Polym. Chem. 2017, 8, 4062–4073.

    Article  CAS  Google Scholar 

  38. Jiang, Y.; Hadjichristidis, N. Tetraphenylethene-functionalized polyethylene-based polymers with aggregation-induced emission. Macromolecules 2019, 52, 1955–1964.

    Article  CAS  Google Scholar 

  39. Corey, E.; Chaykovsky, M. Dimethyloxosulfonium methylide ((CH3)2SOCH2) and dimethylsulfonium methylide ((CH3)2SCH2). Formation and application to organic synthesis. J. Am. Chem. Soc. 1965, 87, 1353–1364.

    Article  CAS  Google Scholar 

  40. Zhang, H.; Alkayal, N.; Gnanou, Y.; Hadjichristidis, N. Anionic polymerization and polyhomologation: An ideal combination to synthesize polyethylene-based block copolymers. Chem. Commun. 2013, 49, 8952–8954.

    Article  CAS  Google Scholar 

  41. Guan, X.; Zhang, D.; Meng, L.; Zhang, Y.; Jia, T.; Jin, Q.; Wei, Q.; Lu, D.; Ma, H. Various tetraphenylethene-based aiegens with four functional polymer arms: Versatile synthetic approach and photophysical properties. Ind. Eng. Chem. Res. 2017, 56, 680–686.

    Article  CAS  Google Scholar 

  42. Chen, F.; Li, C.; Wang, X.; Liu, G.; Zhang, G. pH and ion-species sensitive fluorescence properties of star polyelectrolytes containing a triphenylene core. Soft Matter 2012, 8, 6364–6370.

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The research reported in this publication was supported by King Abdullah University of Science and Technology (KAUST).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Nikos Hadjichristidis.

Additional information

Invited article for special issue of “Ionic Polymerization”

Electronic supplementary material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Jiang, Y., Hadjichristidis, N. pH-responsive AIE-active Polyethylene-based Block Copolymers. Chin J Polym Sci 37, 930–935 (2019). https://doi.org/10.1007/s10118-019-2330-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10118-019-2330-0

Keywords

Navigation