Synthesis of Stimuli-Responsive PEO-Based Triblock Copolymers and Their Applications for Preparation of Iron Oxide Nanoparticles

Joo Hyun Nam; Woo Seok Choi; Jae Hyeok Lee; Nan Hyun Kwon; Ho-Jung Kang; Jae Yeol Lee; Sehoon Kim; Jungahn Kim

Macromolecular Research, Vol.20, No.11, 1173-1180, November, 2012

DOI10.1007/s13233-012-0173-4 Export Citation

Synthesis of Stimuli-Responsive PEO-Based Triblock Copolymers and Their Applications for Preparation of Iron Oxide Nanoparticles

Joo Hyun Nam, Woo Seok Choi, Jae Hyeok Lee, Nan Hyun Kwon, Ho-Jung Kang, Jae Yeol Lee, Sehoon Kim¹, and Jungahn Kim^†

Department of Chemistry, Kyung Hee University, Seoul, 130-701, Korea
¹Biomedical Science Center, KIST, Seoul, 136-791, Korea

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In this paper, the important and useful method for manufacturing superparamagnetic iron oxide nanoparticles stabilized by water-soluble poly(ethylene oxide) (PEO)-based triblock copolymers showing stimuli-responsive phase transition is introduced. Triblock copolymers, such as poly(ethylene oxide-b-N-vinylimidazole-b-3-(methacrylamino)phenylboronic acid) (PEO-b-PVIm-b-PMAPBA), poly(ethylene oxide-b-N-vinylpyrrolidone-b-3-(methacrylamino)phenylboronic acid) (PEO-b-PVP-b-PMAPBA), and poly(ethylene oxide-b-N-vinylimidazoleb-maleic acid) (PEO-b-PVIm-b-PMAc), were synthesized using the sequential monomer addition method via reversible addition fragmentation chain transfer (RAFT) radical block copolymerizations of the corresponding monomers, using PEO-based RAFT agent. After complete polymerization of N-vinylimidazole or N-vinylpyrrolidone in dimethylformamide (DMF) at 110 ℃, 3-(methacrylamino)phenylboronic acid (MAPBA) was polymerized in DMF at 90 ℃ for 24 h, and N-phenylmaleimide was polymerized in dimethylsulfoxide (DMSO) at 110 ℃ for 28 h. All the block copolymers were water-soluble and efficient enough to stabilize the surface of nano-sized iron oxide particles in water. The nanoparticles were stable in neutral aqueous media for at least one month. The resulting products were characterized by a combination of 1H nuclear magnetic resonance spectroscopy (NMR), size exclusion chromatography, transmission electron microscopy (TEM), electron diffraction pattern, and phase transition behavior of the block copolymers using UV/visible spectrophotometer.

Keywords:water-soluble triblock copolymers;RAFT radical copolymerization;PEO-based RAFT agent;phase transition behavior;iron oxide nanoparticles.

[References]

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Lee DE, Kim AY, Saravanakumar G, Koo H, Kwon IC, Choi K, Park JH, Kim K, Macromol. Res., 19(8), 861 (2011)
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Lee S, Nam JH, Kim YJ, Cho YJ, Kwon NH, Lee JY, Kang HJ, Kim HT, Park HM, Kim S, Kim J, Macromol. Res., 19(8), 827 (2011)
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James TD, Sandanayake KR, Shinkai S, Nature, 374(6520), 345 (1995)
Springsteen G, Wang B, Chem.Commun., 1608 (2001)
Yoon J, Czarnik AW, J. Am.Chem. Soc., 114, 5874 (1992)
Wu Q, Wang L, Yu HJ, Wang JJ, Chen ZF, Chem. Rev., 111(12), 7855 (2011)
Oishi M, Sumitani S, Nagasaki Y, Bioconjug. Chem., 18, 379 (2007)
Gerweek LE, Seetharaman K, Cancer Res., 56, 1194 (1996)
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[1] Park JH, von Maltzahn G, Bhatia SN, Sailor MJ, Angew. Chem. Int. Ed., 47, 7284 (2008)

[2] Lutz JF, Stiller S, Hoth A, Kaufner L, Pison U, Cartier R, Biomacromolecules, 7(11), 3132 (2006)

[3] Kim J, Piao Y, Hyeon T, Chem. Soc. Rev., 38, 372 (2009)

[4] Mahmoudi M, Sant S, Wang B, Laurent S, Sen T, Adv. Drug Deliv. Rev., 63, 24 (2011)

[5] Xie J, Xu C, Kohler N, Hou Y, Sun S, Adv. Mater., 19(20), 3163 (2007)

[6] Hu FX, Neoh KG, Cen L, Kang ET, Biomacromolecules, 7(3), 809 (2006)

[7] Lee DE, Kim AY, Saravanakumar G, Koo H, Kwon IC, Choi K, Park JH, Kim K, Macromol. Res., 19(8), 861 (2011)

[8] Tromsdorf UI, Bruns OT, Salmen SC, Beisiegel U, Weller H, Nano Lett., 9, 4434 (2009)

[9] Tan H, Xue JM, Shuter B, Li X, Wang J, Adv. Funct. Mater., 20(5), 722 (2010)

[10] Sun C, Du K, Fang C, Bhattarai N, Veiseh O, Kievit F, Stephen Z, Lee D, Ellenbogen RG, Ratner B, Zhang M, ACS Nano., 4, 2402 (2010)

[11] Hu FQ, Wei L, Zhou Z, Ran YL, Li Z, Gao MY, Adv. Mater., 18(19), 2553 (2006)

[12] Liu DF, Wu W, Ling JJ, Wen S, Gu N, Zhang XZ, Adv. Funct. Mater., 21(8), 1498 (2011)

[13] Wang Y, Ng YW, Chen Y, Shuter B, Yi J, Ding J, Wang SC, Feng SS, Adv. Funct. Mater., 18(2), 308 (2008)

[14] Guo M, Yan Y, Zhang H, Yan H, Cao Y, Liu K, Wan S, Huang J, Yue W, J. Mater. Chem., 18, 5104 (2008)

[15] Go DH, Jeon HJ, Kim TH, Kim G, Choi JH, Lee JY, Kim J, Yoo HO, Bae YH, Macromol. Res., 16(7), 659 (2008)

[16] Kim J, Lee S, Nam JH, Cho YJ, Kim J, Lee JY, Kang HJ, Kim S, Kim HT, Park HM, Kim J, Macromol. Res., 19(7), 716 (2011)

[17] Jeon HJ, Go DH, Choi S, Kim KM, Lee JY, Choo DJ, Yoo HO, Kim JM, Kim J, Colloid Surf. A: Physicochem. Eng. Asp., 317, 496 (2008)

[18] Kim K, Kim TH, Choi JH, Lee JY, Hah SS, Yoo HO, Hwang SS, Ryu KN, Kim HJ, Kim J, J. Macromol. Chem. Phys., 211, 1127 (2010)

[19] Kim J, Choi SY, Kim KM, Go DH, Jeon HJ, Lee JY, Park HS, Lee CH, Park HM, Macromol. Res., 15(4), 337 (2007)

[20] Lee S, Nam JH, Kim YJ, Cho YJ, Kwon NH, Lee JY, Kang HJ, Kim HT, Park HM, Kim S, Kim J, Macromol. Res., 19(8), 827 (2011)

[21] Glockner G, in Polymer Characterization by Liquid Chromatography, Elsevier, Berlin, Chap. 19. (1986)

[22] James TD, Sandanayake KR, Shinkai S, Nature, 374(6520), 345 (1995)

[23] Springsteen G, Wang B, Chem.Commun., 1608 (2001)

[24] Yoon J, Czarnik AW, J. Am.Chem. Soc., 114, 5874 (1992)

[25] Wu Q, Wang L, Yu HJ, Wang JJ, Chen ZF, Chem. Rev., 111(12), 7855 (2011)

[26] Oishi M, Sumitani S, Nagasaki Y, Bioconjug. Chem., 18, 379 (2007)

[27] Gerweek LE, Seetharaman K, Cancer Res., 56, 1194 (1996)

[28] Maeng JH, Lee DH, Jung KH, Bae YH, Park IS, Jeong S, Jeon YS, Shim CK, Kim W, Kim J, Lee J, Lee YM, Kim JH, Kim WH, Hong SS, Biomaterials., 31, 4995 (2010)