Skip to main content
Log in

Synthesis and optical properties of pH-responsive conjugated polyampholytes

  • Articles
  • Published:
Macromolecular Research Aims and scope Submit manuscript

Abstract

Conjugated polyampholytes (CPAs) containing both positive and negative ionic groups in their side-chains were designed and synthesized. Two types of random copolymers were prepared by the incorporation of fluorene, phenylene and 2,1,3-benzothiadiazole (BT) moieties in the main chain. Both quaternary ammonium bromide and carboxylic acid functionalities were introduced successfully in the side-chain through sequential protection, quaternization and deprotection reactions. The resulting ionic polymers were soluble in water and their optical characteristics were examined by changing pH. The fluorescence resonance energy transfer (FRET)-sensitized BT emission of the polymers increased with increasing solution pH. Under basic conditions, deprotonation of the carboxylic acid groups induced intra- and/or interchain aggregation via electrostatic complexation between the cationic ammonium and anionic carboxylate groups. The FRET ratio between the green and blue emissions showed a linear relationship with solution pH. This new type of water-soluble fluorescent bioassays and bioimaging applications through bioconjugation with a targeting moiety.

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.

Institutional subscriptions

Similar content being viewed by others

References

  1. T. M. Swager, Acc. Chem. Res., 31, 201 (1998).

    Article  CAS  Google Scholar 

  2. D. T. McQuade, A. E. Pullen, and T. M. Swager, Chem. Rev., 100, 2537 (2000).

    Article  CAS  Google Scholar 

  3. S. W. Thomas, G. D. Joly, and T. M. Swager, Chem. Rev., 107, 1339 (2007).

    Article  CAS  Google Scholar 

  4. H. A. Ho, M. Boissinot, M. G. Bergeron, G. Corbeil, K. Doré, D. Boudreau, and M. Leclerc, Angew. Chem., Int. Ed., 41, 1548 (2002).

    Article  CAS  Google Scholar 

  5. B. Liu and G. C. Bazan, J. Am. Chem. Soc., 126, 1942 (2004).

    Article  CAS  Google Scholar 

  6. M. Stork, B. S. Gaylord, A. J. Heeger, and G. C. Bazan, Adv. Mater., 14, 361 (2002).

    Article  CAS  Google Scholar 

  7. D. W. Lee and T. M. Swager, Synlett, 149 (2004).

  8. L. Chen, D. W. McBranch, H. Wang, R. Helgeson, F. Wudl, and D. Whitten, Proc. Natl. Acad. Sci. U.S.A., 96, 12287 (1999).

    Article  CAS  Google Scholar 

  9. F. Garnier, Y. H. Korri, P. Srivastava, B. Mandrand, and T. Delair, Synth. Met., 100, 89 (1999).

    Article  CAS  Google Scholar 

  10. A. Duarte, K.-Y. Pu, B. Liu, and G. C. Bazan, Chem. Mater., 23, 501 (2011).

    Article  CAS  Google Scholar 

  11. H. Jiang, P. Taranekar, J. R. Reynolds, and K. S. Schanze, Angew. Chem. Int. Ed., 48, 4300 (2009).

    Article  CAS  Google Scholar 

  12. P. S. Heeger and A. J. Heeger, Proc. Natl. Acad. Sci. U.S.A., 96, 12219 (1999).

    Article  CAS  Google Scholar 

  13. O. K. Nag, M. Kang, S. Hwang, H. Suh, and H. Y. Woo, J. Phys. Chem. B, 113, 5788 (2009).

    Article  CAS  Google Scholar 

  14. M. Kang, O. K. Nag, R. R. Nayak, S. Hwang, H. Suh, and H. Y. Woo, Macromolecules, 42, 2708 (2009).

    Article  CAS  Google Scholar 

  15. J. You, J. Kim, T. Park, B. Kim, and E. Kim, Adv. Funct. Mater., 22, 1417 (2012).

    Article  CAS  Google Scholar 

  16. K. Lee, L. K. Povlich, and J. Kim, Adv. Funct. Mater., 17, 2580 (2007).

    Article  CAS  Google Scholar 

  17. K. Haskins-Glusac, M. R. Pinto, C. Tan, and K. S. Schanze, J. Am. Chem. Soc., 126, 14964 (2004).

    Article  CAS  Google Scholar 

  18. M. Kang, O. K. Nag, S. Hwang, I. Kim, H. Yang, K. Kyhm, and H. Y. Woo, Phys. Chem. Chem. Phys., 12, 15482 (2010).

    Article  CAS  Google Scholar 

  19. R. L. Phillips, I.-B. Kim, B. E. Carson, B. R. Tidbeck, Y. Bai, T. L. Lowary, L. M. Tolbert, and U. H. F. Bunz, Macromole-cules, 41, 7316 (2008).

    Article  CAS  Google Scholar 

  20. R. L. Phillips, O. R. Miranda, C. C. You, V. M. Rotello, and U. H. Bunz, Angew. Chem. Int. Ed., 47, 2590 (2008).

    Article  CAS  Google Scholar 

  21. M. D. Disney, J. Zheng, T. M. Swager, and P. H. Seeberger, J. Am. Chem. Soc., 126, 13343 (2004).

    Article  CAS  Google Scholar 

  22. X. Feng, Y. Tang, X. Duan, L. Liu, and S. Wang, J. Mater. Chem., 20, 1312 (2010).

    Article  CAS  Google Scholar 

  23. K. Y. Pu and B. Liu, Biosens. Bioelectron., 24, 1067 (2009).

    Article  CAS  Google Scholar 

  24. K. Lee, J.-M. Rouillard, T. Pham, E. Gulari, and J. Kim, Angew. Chem. Int. Ed., 119, 4751 (2007).

    Article  Google Scholar 

  25. F. Feng, Y. Tang, F. He, M. Yu, X. Duan, S. Wang, Y. Li, and D. Zhu, Adv. Mater., 19, 3490 (2007).

    Article  CAS  Google Scholar 

  26. F. Rininsland, W. Xia, S. Wittenburg, X. Shi, C. Stankewicz, K. Achyuthan, D. McBranch, and D. Whitten, Proc. Natl. Acad. Sci. U.S.A., 101, 15295 (2004).

    Article  CAS  Google Scholar 

  27. H. Shi, R. T. Kwok, J. Liu, B. Xing, B. Z. Tang, and B. Liu, J.Am. Chem. Soc., 134, 17972 (2012).

    Article  CAS  Google Scholar 

  28. Y. Liu and K. S. Schanze, Anal. Chem., 81, 231 (2009).

    Article  Google Scholar 

  29. B. Liu, T. T. T. Dan, and G. C. Bazan, Adv. Funct. Mater., 17, 2432 (2007).

    Article  CAS  Google Scholar 

  30. S. Wang and G. C. Bazan, Adv. Mater., 15, 1425 (2003).

    Article  CAS  Google Scholar 

  31. K. Y. Pu, S. Y. Pan, and B. Liu, J. Phys. Chem. B, 112, 9295 (2008).

    Article  CAS  Google Scholar 

  32. Y. Wang, R. Zhan, T. Li, K.-Y. Pu, Y. Wang, Y. C. Tan, and B. Liu, Langmuir, 28, 889 (2011).

    Article  Google Scholar 

  33. K.-Y. Pu and B. Liu, Macromolecules, 41, 6636 (2008).

    Article  CAS  Google Scholar 

  34. B. Kim, I. H. Jung, M. Kang, H.-K. Shim, and H. Y. Woo, J. Am. Chem. Soc., 134, 3133 (2012).

    Article  CAS  Google Scholar 

  35. B. L. Nguyen, J.-E. Jeong, I. H. Jung, B. Kim, V. S. Le, I. Kim, K. Kyhm, and H. Y. Woo, Adv. Funct. Mater., 24, 1748 (2014).

    Article  CAS  Google Scholar 

  36. Y. Zhang, B. Liu, and Y. Cao, Chem. Asian J., 3, 739 (2008).

    Article  CAS  Google Scholar 

  37. J. Wang, D. Wang, E. K. Miller, D. Moses, G. C. Bazan, and A. J. Heeger, Macromolecules, 33, 5153 (2000).

    Article  CAS  Google Scholar 

  38. D. Wang, X. Gong, P. S. Heeger, F. Rininsland, G. C. Bazan, and A. J. Heeger, Proc. Natl. Acad. Sci. U.S.A., 99, 49 (2002).

    Article  CAS  Google Scholar 

  39. V. S. Le, B. Kim, W. Lee, J.-E. Jeong, R. Yang, and H. Y. Woo, Macromol. Rapid Commun., 34, 772 (2013).

    Article  CAS  Google Scholar 

  40. S. Tasch, E. J. W. List, C. Hochfilzer, and G. Leising, Phys. Rev. B, 56, 4479 (1997).

    Article  CAS  Google Scholar 

  41. E. Jeong, S. H. Kim, I. H. Jung, Y. Xia, K. Lee, H. Suh, H.-K. Shim, and H. Y. Woo, J. Polym. Sci. Part A: Polym. Chem., 47, 3467 (2009).

    Article  CAS  Google Scholar 

  42. G. Wang, R. Zhang, C. Xu, R. Zhou, J. Dong, H. Bai, and X. Zhan, Appl. Mater. Interfaces, 6, 11136 (2014).

    Article  CAS  Google Scholar 

  43. Q. L. Xu, L. L. An, M. H. Yu, and S. Wang, Macromol. Rapid Commun., 29, 390 (2008).

    Article  CAS  Google Scholar 

  44. A. B. Lowe and C. L. McCormick, Chem. Rev., 102, 4177 (2002).

    Article  CAS  Google Scholar 

  45. Z. E. Ibraeva, M. Hahn, W. Jaeger, L. A. Bimendina, and S. E. Kudaibergenov, Macromol. Chem. Phys., 205, 2464 (2004).

    Article  CAS  Google Scholar 

  46. K. M. Zurick and M. Bernards, J. Appl. Polym. Sci., 131, 40069 (2013).

    Google Scholar 

  47. E. Ji, D. G. Whitten and K. S. Schanze, Langmuir, 27, 1565 (2011).

    Article  CAS  Google Scholar 

  48. C. Xing, L. Liu, Z. Shi, Y. Li, and S. Wang, Adv. Funct. Mater., 20, 2175 (2010).

    Article  CAS  Google Scholar 

  49. A. V. Dobrynin, R. H. Colby, and M. Rubinstein, J. Polym. Sci. Part B: Polym. Phys., 42, 3513 (2004).

    Article  CAS  Google Scholar 

  50. A. Katchalsky and I. R. Miller, J. Polym. Sci., 13, 57 (1954).

    Article  CAS  Google Scholar 

  51. B. H. Lee, I. H. Jung, H. Y. Woo, H.-K. Shim, G. Kim, and K. Lee, Adv. Funct. Mater., 24, 1100 (2014).

    Article  CAS  Google Scholar 

  52. J.-H. Lee and D.-H. Hwang, Chem. Commun., 2836 (2003).

  53. F. Wang and G. C. Bazan, J. Am. Chem. Soc., 128, 15786 (2006).

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Han Young Woo.

Electronic supplementary material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Nag, O.K., Jeong, JE., Nguyen, T.L. et al. Synthesis and optical properties of pH-responsive conjugated polyampholytes. Macromol. Res. 23, 457–465 (2015). https://doi.org/10.1007/s13233-015-3056-7

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s13233-015-3056-7

Keywords

Navigation