화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Macromolecular Research, Vol.23, No.10, 891-897, October, 2015
DOI10.1007/s13233-015-3124-z  Export Citation
Preparation of the water-soluble fluorene-containing fluorescent polymer by one-pot method
Yuan Wang, Haijian Tan, Xiaomeng Li, Yunxia Qian, Libin Bai†, Yonggang Wu, Shufang Lv, and Hongchi Zhao†
  • College of Chemistry and Environmental Science, Hebei University, Baoding, 071002, China
E-mail:,
A water-soluble fluorescent polymer, 2,7-di}4'-[3''-(S-poly(acryloyl ethylene diamine hydrochloride)-2'''- methyl propionic acid)propionyloxy hexyloxy]phenyl{-9,9-di(n-octyl)fluorene (P3) with regular and ordered structure, was designed and synthesized with high conversion using click reaction between thiols and carbon-carbon double bonds. Because the S-H bond is relatively weak, thiol groups are subject to rapid oxidation during purification and storage and thereby result in the low conversion in the following click reaction. To circumvent this limitation, the synthesis of thiol groups and click reaction were simultaneously performed in one system (one-pot method). The intermediate products P1 (S-1-dodecyl-S'-[poly(N-Boc-acryloyl ethylene diamine)-2'-methyl propionic acid]trithiocarbonate) and M2 (2,7-di[4-(acryloyloxy hexyloxy)phenyl]-9,9-di(n-octyl)fluorene) were prepared via reversible addition fragmentation chain transfer (RAFT) polymerization and Williamson synthesis, respectively. Then, 2,7- di}4'-[3''-(S-poly(N-Boc-acryloyl ethylene diamine)-2'''-methyl propionic acid)propionyloxy hexyloxy]phenyl{-9,9-di(n-octyl)fluorene (P2) was synthesized with high conversion (83%) by employing a click reaction with P1 and M2 as starting materials. Finally, water-soluble fluorescent polymer P3 was obtained after the deprotection of P2. M2, P1, P2 and P3 were characterized by Fourier transform infrared (FTIR) spectrum, nuclear magnetic resonance (NMR), high-resolution mass spectroscopy (MS), gel permeation chromatograph (GPC), UV-Visible (UV-Vis) spectrum, and fluorescence, respectively. The results revealed that P3 displayed good solubility in water and not only exhibited a blue fluorescence emission band in water but also had a similar photoluminescent spectra to those of M2 and P2 in dichloromethane. The fluorescence quantum yield of P3 in aqueous solution could reach 0.10. In addition, the result of cell cytotoxicity indicates that P3 has low cytotoxicity and exhibits potential for biomedical applications. This work provides a new insight into the study of water-soluble fluorescent polymer.
Keywords:water-soluble fluorescent polymer;click reaction;thiol-ene reaction;reversible addition fragmentation chain transfer (RAFT);one-pot method
  1. Li K, Liu B, J. Polym. Sci. A: Polym. Chem., 1, 252 (2010)
  2. Gong WL, Zhang GF, Li C, Aldred MP, Zhu MQ, RSC Adv., 3, 9167 (2013)
  3. Relogio P, Bathfield M, Terreau ZH, Beija M, Favier A, Panis MJG, D'Agosto F, Mandrand B, Farinha JPS, Charreyre MT, Martinho JMG, J. Polym. Sci. A: Polym. Chem., 4, 2968 (2013)
  4. You J, Park T, Kim J, Heo JS, Kim HS, Kim HO, Kim E, ACS Appl. Mater. Interfaces, 6, 3305 (2014)
  5. Jiang GX, Susha AS, Lutich AA, Stefani FD, Feldmann J, Rogach AL, ACS Nano, 3, 4127 (2009)
  6. Herland A, Inganas O, Macromol. Rapid Commun., 28(17), 1703 (2007)
  7. Sun H, Feng F, Yu MH, Wang S, Macromol. Rapid Commun., 28(18-19), 1905 (2007)
  8. Qin CJ, Wong WY, Wang LX, Macromolecules, 44(3), 483 (2011)
  9. Fang Z, Pu KY, Liu B, Macromolecules, 41(22), 8380 (2008)
  10. Feng XL, Liu LB, Wang S, Zhu DB, Chem. Soc. Rev., 39, 2411 (2010)
  11. Zhu CL, Liu LB, Yang Q, Lv FT, Wang S, Chem. Rev., 112(8), 4687 (2012)
  12. Nag OK, Jeong JE, Nguyen TL, Woo HY, Macromol. Res., 23(5), 457 (2015)
  13. Thomas SW, Joly GD, Swager TM, Chem. Rev., 107(4), 1339 (2007)
  14. Miranda OR, You CC, Phillips R, Kim IB, Ghosh PS, Bunz UHF, Rotello VM, J. Am. Chem. Soc., 129(32), 9856 (2007)
  15. Traina CA, Bakus RC, Bazan GC, J. Am. Chem. Soc., 133(32), 12600 (2011)
  16. Liu B, Yu WL, Lai YH, Huang W, Macromolecules, 35(13), 4975 (2002)
  17. Tang F, He F, Cheng HC, Li LD, Langmuir, 26(14), 11774 (2010)
  18. Zhu LN, Qin JG, Yang CL, J. Phys. Chem. B, 114(46), 14884 (2010)
  19. Inal S, Kolsch JD, Sellrie F, Schenk JA, Wischerho E, Laschewsky A, Neher D, J. Mater. Chem. B, 1, 6373 (2013)
  20. Shi W, Dolai S, Averick S, Fernando SS, Saltos JA, L’Amoreaux W, Banerjee P, Raja K, Bioconjugate Chem., 20, 1595 (2009)
  21. Schillen K, Anghel DF, Miguel MD, Lindman B, Langmuir, 16(26), 10528 (2000)
  22. David RLA, Kornfield JA, Macromolecules, 41(4), 1151 (2008)
  23. Chong H, Duan XR, Yang QO, Liu LB, Wang S, Macromolecules, 43(24), 10196 (2010)
  24. Liu N, Wu YG, Bai LB, Wang Y, Huang HC, Zhao HC, Ba XW, Chem. J. Chinese U., 35, 1111 (2014)
  25. Lai JT, Filla D, Shea R, Macromolecules, 35(18), 6754 (2002)
  26. Mccormick CL, Lowe AB, Acc. Chem. Res., 37, 312 (2004)
  27. Zhu B, Han Y, Sun MH, Bo ZS, Macromolecules, 40(13), 4494 (2007)