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RAFT preparation and self-assembly behavior of thermosensitive triblock PNIPAAm-b-PODA-b-PNIPAAm copolymers

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Abstract

A series of well-defined thermoresponsive ABA-type triblock copolymers poly(N-isopropylacrylamide)-b-poly(n-octadecylacrylate)-b-poly(N-isopropylacrylamide) (PNIPAAm-b-PODA-b-PNIPAAm) consisting of two blocks of PNIPAAm and one block of PODA in different ratio are prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. The structures of the copolymers are characterized by 1HNMR. All block copolymers show lower critical micelle concentration (CMC) (<10 mg/L) in water, indicating the strong tendency of the triblock copolymers to self-assemble into highly stable micelles. It is interesting that the resulting micelles demonstrate double lower critical solution temperature (LCST) behavior. Dynamic light-scattering (DLS) experiments show that the micelles are well dispersed at nanoscale and have a narrow size distribution. Moreover, the drug-loading behavior of micelles is further investigated. The high drug encapsulation efficiency indicates the potential of micelles formed from PNIPAAm-b-PODA-b-PNIPAAm as drug carriers.

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References

  1. Stuart MAC, Huck WTS, Genzer J, Mueller M, Ober C, Stamm M, Sukhorukov GB, Szleifer I, Tsukruk VV, Urban M, Winnik F, Zauscher S, Luzinov I, Minko S (2010) Emerging applications of stimuli-responsive polymer materials. Nat Mater 9:101–113

    Article  Google Scholar 

  2. Ward MA, Georgiou TK (2011) Thermoresponsive polymers for biomedical applications. Polymer 3:1215–1242

    Article  CAS  Google Scholar 

  3. Licciardi M, Giammona G, Du J, Armes SP, Tang Y, Lewis AL (2006) New folate-functionalized biocompatible block copolymer micelles as potential anti-cancer drug delivery systems. Polymer 47:2946–2955

    Article  CAS  Google Scholar 

  4. Maeda Y, Higuchi T, Ikeda I (2000) Change in the hydration state during the coil-globule transition of aqueous solution of poly(N-isopropylacrylamide) as evidence by FTIR spectroscopy. Langmuir 16:7503–7509

    Article  CAS  Google Scholar 

  5. Yoo MK, Sung YK, Lee YM, Cho CS (2000) Effect of polyelectrolyte on the lower critical solution temperature of poly(N-isopropyl acrylamide) in the poly(NIPAAm-co-acrylic acid) hydrogel. Polymer 41:5713–5719

    Article  CAS  Google Scholar 

  6. Xue W, Hamley IW (2002) Thermoreversible swelling behaviour of hydrogels based on N-isopropylacrylamide with a hydrophobic comonomer. Polymer 43:3069–3077

    Article  CAS  Google Scholar 

  7. Hirvonen SP, Rossi T, Karesoja M (2015) Thermally responsive particles of poly (benzimidazobenzophenanthroline) modified with poly (N-isopropylacrylamide). Colloid Polym Sci 293(10):2957–2965

    Article  CAS  Google Scholar 

  8. Chang C, Wei H, Quan CY, Li YY, Liu J, Wang ZC (2008) Fabrication of thermosensitive PCL-PNIPAAm-PCL triblock copolymeric micelles for drug delivery. J Polym Sci Part A: Polym Chem 46:3048–3057

    Article  CAS  Google Scholar 

  9. Jiang XZ, Ge ZS, Xu J, Liu H, Liu SY (2007) Fabrication of multiresponsive shell cross-linked micelles possessing pH-controllable core swellability and thermo-tunable corona permeability. Biomacromolecules 8:3184–3192

    Article  CAS  Google Scholar 

  10. de Lambert B, Charreyre MT, Chaix C (2007) Poly (N-tert-butyl acrylamide-b-N-acryloylmorpholine) amphiphilic block copolymers via RAFT polymerization: synthesis, purification and characterization. Polymer 48(2):437–447

    Article  Google Scholar 

  11. Achilleos M, Krasia-Christoforou T, Patrickios CS (2007) Amphiphilic model conetworks based on combinations of methacrylate, acrylate, and styrenic units: synthesis by RAFT radical polymerization and characterization of the swelling behavior. Macromolecules 40(15):5575–5581

    Article  CAS  Google Scholar 

  12. Li Y, Lokitz BS, Armes SP (2006) Synthesis of reversible shell cross-linked micelles for controlled release of bioactive agents. Macromolecules 39(8):2726–2728

    Article  CAS  Google Scholar 

  13. Perrier S, Takolpuckdee P (2005) Macromolecular design via reversible addition-fragmentation chain transfer (RAFT)/xanthates (MADIX) polymerization. J Polym Sci A Polym Chem 43(22):5347–5393

    Article  CAS  Google Scholar 

  14. Stenzel MH, Davis TP, Fane AG (2003) Honeycomb structured porous films prepared from carbohydrate based polymers synthesized via the RAFT process. J Mater Chem 13(9):2090–2097

    Article  CAS  Google Scholar 

  15. Zhu JL, Zhang XZ, Cheng H, Li YY, Cheng SX, Zhuo RX (2007) Synthesis and characterization of well-defined amphiphilic poly(N-isopropylacrylamide)-b-[2-hydroxyethyl methacrylatepoly(epsilon-caprolactone)](n) graft copolymers by RAFT polymerization and macromonomer method. J Polym Sci Polym Chem 45:5354–5364

    Article  CAS  Google Scholar 

  16. Zhang YF, Luo SZ, Liu SY (2005) Fabrication of hybrid nanoparticles with thermoresponsive coronas via a self-assembling approach. Macromolecules 38:9813–9820

    Article  CAS  Google Scholar 

  17. Tang T, Castelletto V, Parras P, Hamley IW, King SM, Roy D (2006) Thermo-responsive poly(methyl methacrylate)-block-poly(Nisopropylacrylamide) block copolymers synthesized by RAFT polymerization: micellization and gelation. Macromol Chem Phys 207:1718–1726

    Article  CAS  Google Scholar 

  18. You YZ, Hong CY, Wang WP, Lu WQ, Pan CY (2004) Preparation and characterization of thermally responsive and biodegradable block copolymer comprised of PNIPAAm and PLA by combination of ROP and RAFT methods. Macromolecules 37:9761–9767

    Article  CAS  Google Scholar 

  19. **ao X, Fu YQ, Zhou JJ, Bo ZS, Li L, Chan CM (2007) Reversible thermally responsive and luminescent coil-rod-coil triblock copolymers. Macromol Rapid Commun 28:1003–1009

    Article  CAS  Google Scholar 

  20. Chung JE, Yokoyama M, Okano T (2000) Inner core segment design for drug delivery control of thermo-sensitive polymeric micelles. J Control Release 65:93–103

    Article  CAS  Google Scholar 

  21. Bivigou-Koumba AM, Görnitz E, Laschewsky A, Müller-Buschbaum P, Papadakis CM (2010) Thermoresponsive amphiphilic symmetrical triblock copolymers with a hydrophilic middle block made of poly (N-isopropylacrylamide): synthesis, self-organization, and hydrogel formation. Colloid Polym Sci 288(5):499–517

    Article  CAS  Google Scholar 

  22. Yu YQ, Hong D, Liu Z, Jia FJ, Zhou YM, Leng CF (2013) Controllable preparation and characterization of the thermosensitive block polymers. J Polymer Research 20:235

    Article  Google Scholar 

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Acknowledgments

This research was supported by the National Natural Science Foundation of China (No. 20876081), the National Key Technology Support Program of China (No. 2014BAC10B01), Key Scientific and Technological Project of China’s Shaanxi Province (No. MN2014-10) and National Training Program of Innovation and Entrepreneurship for Undergraduates (No. 201610426032) .

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  1. State Key Laboratory Base of Eco-chemical Engineering, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao, 266042, People’s Republic of China

    Jie Wu, Xuejiao Sun, Ruling Zhang, Shichao Yuan, Zongmei Wu, Qingliang Lu & Yueqin Yu

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  1. Jie Wu
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  2. Xuejiao Sun
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  3. Ruling Zhang
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Correspondence to Yueqin Yu.

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Wu, J., Sun, X., Zhang, R. et al. RAFT preparation and self-assembly behavior of thermosensitive triblock PNIPAAm-b-PODA-b-PNIPAAm copolymers. Colloid Polym Sci 294, 1989–1995 (2016). https://doi.org/10.1007/s00396-016-3958-8

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  • DOI: https://doi.org/10.1007/s00396-016-3958-8

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