• Chemoenzymatic Synthesis of H-shaped Amphiphilic Pentablock Copolymer and Its Self-assembly Behavior
  • Chen P, Li YP, Li CJ, Meng XL, Zhang B, Zhu M, Liu YJ, Wang JY
  • H-형태 양친매성 펜타블록 공중합체의 화학효소적 합성과 자기회합거동 평가
  • Chen P, Li YP, Li CJ, Meng XL, Zhang B, Zhu M, Liu YJ, Wang JY
Abstract
H-shaped amphiphilic pentablock copolymers (PSt)2-b-PCL-b-PEO-b-PCL-b-(PSt)2 was synthesized via chemoenzymatic method by combining enzyme-catalyzed ring-opening polymerization (eROP) of ε-caprolactone (ε-CL) and atom transfer radical polymerization (ATRP) of styrene. By this process, we obtained copolymers with controlled molecular weight and low polydispersity. The structure and composition of the obtained copolymers were characterized by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC) and infrared spectroscopy analysis (IR). The crystallization behavior of the copolymers was analyzed by differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The crystallization behavior of the H-shaped block copolymers demonstrated a PCL dominate crystallization. The self-assembly behavior of the copolymers was investigated in aqueous media. The hydrodynamic diameters of the copolymer micelles in aqueous solution were measured by dynamic light scattering (DLS). The morphology of the copolymer micelles was observed by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The hydrodynamic diameters of spherical micelles declined gradually with the increase of the hydrophobic chain lengths of the copolymers. The critical micelle concentration (CMC) values were determined from fluorescence emission, and it was found that the CMCs decreased with an increase of PSt hydrophobic block lengths.

Keywords: atom transfer radical polymerization (ATRP); enzymatic ring-opening polymerization (eROP); amphiphilic block copolymer.

References
  • 1. Cho CS, Jeong YI, Kim SH, Nah JW, Lee YM, Kang IK, Sung YK, Polymer(Korea)., 7, 203 (1999)
  •  
  • 2. Prabaharan M, Grailer JJ, Pilla S, Steeber DA, Gong SQ, Biomaterials., 30, 6065 (2009)
  •  
  • 3. Blanazs A, Armes SP, Ryan AJ, Macromol. Rapid Commun., 30(4-5), 267 (2009)
  •  
  • 4. Kim YJ, Sung YK, Pial AZ, Kim SW, Polymer(Korea)., 5, 214 (1997)
  •  
  • 5. Ruckenstein E, Zhang HM, Macromolecules, 31(26), 9127 (1998)
  •  
  • 6. Hirao A, Hayashi M, Haraguchi N, Macromol. Rapid Commun., 21(17), 1171 (2000)
  •  
  • 7. Hirao A, Higashihara T, Inoue K, Macromolecules, 41(10), 3579 (2008)
  •  
  • 8. Yoshida T, Seno KI, Kanaoka S, Aoshima S, J. Polym. Sci. A: Polym. Chem., 43(6), 1155 (2005)
  •  
  • 9. Aoshima S, Sugihara S, Shibayama M, Kanaoka S, Macromol. Symp., 215, 151 (2004)
  •  
  • 10. Aoshima S, Sugihara S, J. Polym. Sci. A: Polym. Chem., 38(21), 3962 (2000)
  •  
  • 11. Cunningham MF, Prog. Polym. Sci., 33, 365 (2008)
  •  
  • 12. Matyjaszewski M, Spanswick J, Materialstoday., 8, 26 (2005)
  •  
  • 13. Lee JY, Kim JH, Kim MJ, Jin MK, Polymer(Korea)., 7, 229 (1999)
  •  
  • 14. Gopalan P, Zhang YM, Li XF, Wiesner U, Ober CK, Macromolecules, 36(9), 3357 (2003)
  •  
  • 15. Pasquale AJ, Long TE, J. Polym. Sci. A: Polym. Chem., 39(1), 216 (2001)
  •  
  • 16. Coessens V, Pintauer T, Matyjaszewski K, Prog. Polym.Sci., 26, 337 (2001)
  •  
  • 17. Tsarevsky NV, Matyjaszewski K, Chem. Rev., 107(6), 2270 (2007)
  •  
  • 18. Licciardi M, Tang Y, Billingham NC, Armes SP, Biomacromolecules, 6(2), 1085 (2005)
  •  
  • 19. York AW, Kirkland SE, McCormick CL, Adv. Drug Deliver. Rev., 60, 1018 (2008)
  •  
  • 20. Li CZ, Benicewicz BC, Macromolecules, 38(14), 5929 (2005)
  •  
  • 21. Lowe AB, McCormick CL, Prog. Polym. Sci.., 3, 283 (2007)
  •  
  • 22. WellsF A, Org. Process. Res. Dev., 10, 678 (2006)
  •  
  • 23. Scarpello JT, Nair D, dos Santos LMF, White LS, Livingston AG, J. Membr. Sci., 203(1-2), 71 (2002)
  •  
  • 24. Torque C, Bricout H, Hapiot F, Monflier E, Tetrahedron., 60, 6487 (2004)
  •  
  • 25. Lopez-Gallego F, Betancor L, Hidalgo A, Mateo C, Guisan JM, Fernandez-Lafuente R, Biotechnol., 111, 219 (2004)
  •  
  • 26. Van Beilen JB, Li Z, Curr. Opin. Biotechnol., 13, 338 (2002)
  •  
  • 27. Murakami Y, Hoshi R, Hirata A, J. Mol. Catal. B: Enzym., 22, 79 (2003)
  •  
  • 28. Ivanov AE, Edink E, Kumar A, Galaev IY, Arendsen AF, Bruggink A, Mattiasson B, Biotechnol. Prog., 19(4), 1167 (2003)
  •  
  • 29. Konwarh R, Kalita D, Mahanta C, Mandal M, Karak N, Appl. Microbiol. Biotechnol., 87(6), 1983 (2010)
  •  
  • 30. Albertsson AC, Srivastava RK, Adv. Drug Deliver. Rev., 60, 1077 (2008)
  •  
  • 31. Makino A, Kobayashi S, J. Polym. Sci. A: Polym. Chem., 48(6), 1251 (2010)
  •  
  • 32. Yu XH, Zhuo RX, Feng J, Liao J, Eur. Polym. J., 40, 2445 (2004)
  •  
  • 33. Le Garrec D, Gori S, Luo L, Lessard D, Smith DC, Yessine MA, Ranger M, Leroux JC, J. Control. Release., 99, 83 (2004)
  •  
  • 34. Park EK, Kim SY, Lee SB, Lee YM, J. Control.Release., 109, 158 (2005)
  •  
  • 35. O'Reilly RK, Hawker CJ, Wooley KL, Chem. Soc. Rev., 35, 1068 (2006)
  •  
  • 36. Villarroya S, Zhou JX, Thurecht KJ, Howdle SM, Macromolecules, 39(26), 9080 (2006)
  •  
  • 37. De Geus M, Palmans ARA, Duxbury CJ, Villarroya S, Howdle SM, Heise A, Polymer Biocatalysis and Biomaterials II., 14, 216 (2008)
  •  
  • 38. Meyer U, Palmans ARA, Loontjens T, Heise A, Macromolecules, 35(8), 2873 (2002)
  •  
  • 39. Cai YL, Tang YQ, Armes SP, Macromolecules, 37(26), 9728 (2004)
  •  
  • 40. Sha K, Qin L, Li DS, Liu XT, Wang JY, Polym. Bull., 54(1-2), 1 (2005)
  •  
  • 41. Sha K, Li DS, Li YP, Zhang B, Wang JY, Macromolecules, 41(2), 361 (2008)
  •  
  • 42. Wang W, Li YP, Zhao YL, Zhang B, Wang JY, Acta Polym. Sin., 2, 199 (2010)
  •  
  • 43. Zhang B, Li YP, Sun JH, Wang SW, Zhao YL, Wu ZY, Polym. Int., 58, 752 (2009)
  •  
  • 44. Wang D, Zhang B, Li YP, Sun JH, Chem. J. Chinese. U., 29, 1479 (2008)
  •  
  • 45. Zhang B, Li YP, Ai P, Sa ZP, Zhao YL, Li M, Wang D, Sha K, J. Polym. Sci. A: Polym. Chem., 47(20), 5509 (2009)
  •  
  • Polymer(Korea) 폴리머
  • Frequency : Bimonthly(odd)
    ISSN 0379-153X(Print)
    ISSN 2234-8077(Online)
    Abbr. Polym. Korea
  • 2024 Impact Factor : 0.6
  • Indexed in SCIE

This Article

  • 2013; 37(3): 332-341

    Published online May 25, 2013

  • Received on Oct 23, 2012
  • Accepted on Jan 8, 2013