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Multi-sensitive copolymer hydrogels of N-isopropylacrylamide with several polymerizable azobenzene-containing monomers

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Abstract

Three kinds of photosensitive and two kinds of photo/pH-sensitive polymerizable azobenzene-containing monomers were designed and synthesized. Three thermo/light dual-responsive and two thermo/light/pH triple-responsive copolymer hydrogels were prepared via copolymerization of those new azobenzene-containing monomers, N-isopropylacrylamide, and a crosslinker. The properties of those hydrogels were researched carefully by UV–Vis absorption spectrometry, differential scanning calorimetry, and gravimetry. It was found that the molecular structure, i.e., the methylene chain length, quaternary ammonium group and carboxyl group of azobenzene-containing monomers, had an important influence on the UV light response rate, phase transition and swelling ability of the copolymer hydrogel. Three hydrogels with good overall performances were screened, i.e., GelNDEP, GelNAEP0.01 and GelNAP0.01, which should be used as carriers in later studies. Analysing the influence of the molecular structure will help to fine-tune such a copolymer gel to a desired state, which is very important from an applications point of view.

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References

  1. Imran AB, Seki T, Takeoka Y (2010) Functional polymers: recent advances in hydrogels in terms of fast stimuli responsiveness and superior mechanical performance. Polym J 42:839–851

    Article  Google Scholar 

  2. Fujii S, Suzaki M, Yusa S, Muraoka M, Nakamura Y (2009) Synthesis of stimuli-responsive macroazoinitiators and their use as an inistab toward hairy polymer latex particles. J Polym Sci Part A Polym Chem 47:3431–3443

    Article  CAS  Google Scholar 

  3. Dobrynin AV, Rubinstein M (2005) Theory of polyelectrolytes in solutions and at surfaces. Prog Polym Sci 30:1049–1118

    Article  CAS  Google Scholar 

  4. Kawaguchi H (2014) Thermoresponsive microhydrogels: preparation, properties and applications. Polym Int 63:925–932

    Article  CAS  Google Scholar 

  5. Becer CR, Hahn S, Fijten MWM, Thijs HML (2008) Libraries of methacrylic acid and oligo(ethylene glycol) methacrylate copolymers with LCST behavior. J Polym Sci A Polym Chem 46:7138–7147

    Article  CAS  Google Scholar 

  6. Alexander C, Shakesheff KM (2006) Responsive polymers at the biology/materials science interface. Adv Mater 18:3321–3328

    Article  CAS  Google Scholar 

  7. Maya S, Sarmento B, Nair A, Rejinold NS, Nair SV, Jayakumar R (2013) Smart stimuli sensitive nanogels in cancer drug delivery and imaging: a review. Current pharmaceutical desin 19:7203–7218

    Article  CAS  Google Scholar 

  8. Irie M (1990) Properties and application of photoresponsive polymers. Pure Appl Chem 62:1495–1502

    Article  CAS  Google Scholar 

  9. Gong CB, Wong KL, Lam Michael HW (2008) Photoresponsive molecularly imprinted hydrogels for the photoregulated release and uptake of pharmaceuticals in the aqueous media. Chem Mater 20:1353–1358

    Article  Google Scholar 

  10. Nayak S, Lyon LA (2004) Photoinduced phase transitions in poly(N-isopropylacrylamide) microgels. Chem Mater 16:2623–2627

    Article  CAS  Google Scholar 

  11. Kameda M, Sumaru K, Kanamori T, Shinbo T (2004) Probing the dielectric environment surrounding poly(N-isopropylacrylamide) in aqueous solution with covalently attached spirobenzopyran. Langmuir 20:9315–9319

    Article  CAS  Google Scholar 

  12. Rack JJ (2009) Electron transfer triggered sulfoxide isomerization in ruthenium and osmium complexes. Coord Chem Rev 253:78–85

    Article  CAS  Google Scholar 

  13. Bandara HMD, Burdette SC (2012) Photoisomerization in different classes of azobenzene. Chem Soc Rev 41:1809–1825

    Article  CAS  Google Scholar 

  14. Guan Y, Zhao HB, Yu LX (2014) Multi-stimuli sensitive supramolecular hydrogel formed by host-guest interaction between PNIPAM-Azo and cyclodextrin dimmers. RSC Adv 4:4955–4959

    Article  CAS  Google Scholar 

  15. Klaikherd A, Nagamani C, Thayumanavan S (2009) Multi-stimuli sensitive amphiphilic block copolymer assemblies. J Am Chem Soc 131:4830–4838

    Article  CAS  Google Scholar 

  16. Ganta S, Devalapally H, Shahiwala A, Amiji M (2008) A review of stimuli-responsive nanocarriers for drug and gene delivery. J Control Release 126:187–204

    Article  CAS  Google Scholar 

  17. Qiu XY, Hu SW (2013) “Smart” materials based on cellulose: a review of the preparations, properties, and applications. Materials 6:738–781

    Article  CAS  Google Scholar 

  18. Li LX, Xing XD, Liu ZL (2013) Triply-responsive (thermo/light/pH) copolymeric hydrogel of N-isopropyl-acrylamide with an azobenzene-containing monomer. J Appl Polym Sci 124:1128–1136

    Article  Google Scholar 

  19. Li LX, Liu ZL, Xing XD, Pi JM (2012) Synthesis and properties of with temperature and light sensitivities P(NIPAm-co-DMAE-EAPB) hydrogel. J Jiangsu Univ 33:696–700

    CAS  Google Scholar 

  20. East AJ, Madison NJ (1981) Anisotropic wholly aromatic polymer derived from 4-hydroxy-4′-carboxy azobenzene and process for preparation. US Patent, 428582 A.

  21. Chen L, Li SG, Zhao YP, Wang YC, Wang QW (2005) Photoresponses and pH responses of hydrogels composed of acrylamido azobenzene and acrylic acid. J Appl Polym Sci 96:2163–2167

    Article  CAS  Google Scholar 

  22. Zhang YX, Pei SH, Wang YP, Cui ZD, Li N, Zhu Y, Zhang HB, Jiang ZH (2013) Synthesis, characterization, and photoresponsive behavior of a series of azobenzene-containing side-chain poly(ether sulfone)s with various lengths of flexible spacers. Dyes Pigments 99:1117–1123

    Article  CAS  Google Scholar 

  23. Angiolini L, Caretti D, Giorgini L, Salatelli E, Altomare A, Carlini C, Solaro R (2000) Optically active polymethacrylates with side-chain l-lactic acid residues connected to push–pull azobenzene chromophores. Polymer 41:4767–4780

    Article  CAS  Google Scholar 

  24. Janus K, Sworakowski J (2005) Photochromism of crown ethers with Incorporated azobenzene Moiety. J Phys Chem B 109:93–101

    Article  CAS  Google Scholar 

  25. Ross DL, Blanc J (1971) In: Brown GH (ed) Photochromism. Eiley-Interscience, New York, Chapter 5

    Google Scholar 

  26. Lee WF, Lin YH (2006) Swelling behavior and drug release of NIPAAm/PEGMEA copolymeric hydrogels with different crosslinkers. J Mater Sci 41:7333–7340

    Article  CAS  Google Scholar 

  27. Xiao XC, Chu LY, Chen WM, Zhu JH (2005) Monodispersed the thermoresponsive hydrogel microspheres with a volume phase transition driven by hydrogen bonding. Polymer 46:3199–3209

    Article  CAS  Google Scholar 

  28. Shin BC, Kim SS, Ko JK (2003) Gradual phase transition of poly(N-isopropylamide-co-acrylic)gel induced by electric current. Eur Polym J 39:579–584

    Article  CAS  Google Scholar 

  29. Wang XQ, Liu XY, Wang XG (2014) Hydrogel diffraction grating as sensor: a tool for studying volume phase transition of thermo-responsive hydrogel. Sensors Actuators B Chem. doi:10.1016/j.snb.2014.08.013

    Google Scholar 

  30. Feil H, Bae YH, Jan FJ, Kim SW (1993) Effect of comonomer hydrophilicity and ionization on the lower critical solution temperature of N-isopropylacrylamide copolymers. Macromolecules 26:2496–2500

    Article  CAS  Google Scholar 

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Acknowledgments

This work was supported by a grant (13JDG110) from the Scientific Research Foundation for the high-ranking talent of Jiangsu University and the Jiangsu Postdoctoral Science Foundation (1402072B).

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Authors and Affiliations

  1. School of the Environment and Safety Engineering, Jiangsu University, Zhenjiang, 212013, China

    Lixia Li, Bing Lu, Ye Zhang & Xiangyang Wu

  2. School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, China

    Xiaodong Xing & Zuliang Liu

  3. Administrative Committee of Zhenjiang New Area Green Chemical & New Material Industry Park, Zhenjian, 212013, China

    Ye Zhang

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  1. Lixia Li
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  2. Bing Lu
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  3. Ye Zhang
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  4. Xiaodong Xing
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  5. Xiangyang Wu
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Correspondence to Lixia Li.

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Li, L., Lu, B., Zhang, Y. et al. Multi-sensitive copolymer hydrogels of N-isopropylacrylamide with several polymerizable azobenzene-containing monomers. J Polym Res 22, 176 (2015). https://doi.org/10.1007/s10965-015-0787-2

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  • DOI: https://doi.org/10.1007/s10965-015-0787-2

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