Synthesis of PEO-Based Glucose-Sensitive Block Copolymers and Their Application for Preparation of Superparamagnetic Iron Oxide Nanoparticles

Sangmi Lee; Joo Hyeon Nam; Yoo Jin Kim; Young Jun Cho; Nan Hyeon Kwon; Jae Yeol Lee; Ho-Jung Kang; Hoon Tae Kim; Heung Mok Park; Sehoon Kim; Jungahn Kim

Macromolecular Research, Vol.19, No.8, 827-834, August, 2011

DOI10.1007/s13233-011-0810-3 Export Citation

Synthesis of PEO-Based Glucose-Sensitive Block Copolymers and Their Application for Preparation of Superparamagnetic Iron Oxide Nanoparticles

Sangmi Lee, Joo Hyeon Nam, Yoo Jin Kim, Young Jun Cho, Nan Hyeon Kwon, Jae Yeol Lee, Ho-Jung Kang, Hoon Tae Kim¹, Heung Mok Park¹, Sehoon Kim², and Jungahn Kim^†

Department of Chemistry, Kyung Hee University, Seoul, 130-701, Korea
¹Department of Chemical Engineering, Sogang University, Seoul, 121-742, Korea
²Biomedical Science Center, KIST, Seoul, 136-791, Korea

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Amphiphilic block copolymers were synthesized by reversible addition fragmentation chain transfer (RAFT) radical block polymerization of N-vinylimidazole and 3-(methacrylamido)phenylboronic acid using poly (ethylene oxide) (PEO)-based xanthate type of RAFT agent and 2,2′-azobisisobutyronitrile (AIBN) in dimethylformaide (DMF) at 90~110℃ for 24 h. Poly(ethylene oxide-b-3-(methacrylamido)phenylboronic acid) and poly(ethylene oxide-b-N-vinylimidazole-b-3-(methacrylamido)phenylboronic acid) were prepared successfully through the sequential monomer addition method. Both block copolymers were found to exhibit glucose-responsive behavior via the feasibility test for complex formation with Alizarin Red S (ARS). The ratio of molecular weight of the poly(N-vinyimidazole) to the poly(3-(methacrylamido)phenylboronic acid) appeared to play an important role in the pH- & glucose- responsive behavior. The resulting block copolymers were used successfully as polymeric stabilizers to prepare water-soluble Fe3O4 nanoparticles. All the materials were characterized by the combination of 1H nuclear magnetic resonance (NMR), size exclusion chromatography (SEC), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and x-ray diffraction (XRD) analyses.

Keywords:pH- and glucose-responsive block copolymer;RAFT polymerization;ring-opening polymerization;xanthate-type agent;ARS complex;water-soluble iron oxide nanoparticles.

[References]

Kwon IC, Bae YH, Kim SW, Nature, 354, 291 (1991)
Hoffmann AS, in Controlled Drug Delivery: Challenges and Strategies, Park KN, Ed., Am. Chem. Soc., Washington, D. C., 1997, Chap. 24, pp 485-498.
James TD, Sandanayake SKRA, Shinkai S, Angew. Chem.-Int. Edit., 35, 1910 (1996)
James TD, Shinkai S, Top. Curr. Chem., 218, 159 (2002)
Rzayev ZMO, Beskardes O, Coll. Czech. Chem. Commun., 72, 1591 (2007)
James TD, Sandanayake KR, Shinkai S, Nature, 374(6520), 345 (1995)
Stolowitz ML, Ahlem C, Hughes KA, Kaiser RJ, Kesicki EA, Li G, Lund KP, Torkelson SM, Wiley JP, Bioconjugate Chem., 12, 229 (2001)
DiCesare N, Lakowicz JR, J. Phys. Chem. A, 105(28), 6834 (2001)
Jin XJ, Zhang XG, Wu ZM, Teng DY, Zhang XJ, Wang YX, Wang Z, Li CX, Biomacromolecules, 10(6), 1337 (2009)
Achanta G, Modzelewska A, Feng L, Khan SR, Huang P, Mol. Pharmacol., 70, 426 (2006)
Jeon HJ, Go DH, Choi S, Kim KM, Lee JY, Choo DJ, Yoo HO, Kim JM, Kim J, Colloids Surf. A: Physicochem. Eng. Asp., 317, 496 (2008)
Kim K, Kim TH, Choi JH, Lee JY, Hah SS, Yoo HO, Hwang SS, Ryu KN, Kim HJ, Kim J, Macromol. Chem. Phys., 211, 1127 (2010)
Kim J, Choi SY, Kim KM, Go DH, Jeon HJ, Lee JY, Park HS, Lee CH, Park HM, Macromol. Res., 15(4), 337 (2007)
Chiefari J, Chong YK, Ercole F, Krstina J, Jeffery J, Le TPT, Mayadunne RTA, Meijs GF, Moad CL, Moad G, Rizzardo E, Thang SH, Macromolecules, 31(16), 5559 (1998)
Destarac M, Charmot D, Franck X, Zard SZ, Macromol. Rapid Commun., 21(15), 1035 (2000)
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Roy D, Cambre JN, Sumerlin BS, Chem. Commun., 2106 (2009)
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Yang X, Lee MC, Sartain F, Pan X, Lowe CR, Chem. Eur. J., 12, 8491 (2006)
Oishi M, Sumitani S, Nanasaki Y, Bioconjugate Chem., 18, 1379 (2007)
Roy D, Cambre JN, Sumerlin BS, Chem. Commun., 2477 (2008)
Matsumoto A, Yamamoto K, Yoshida R, Kataoka K, Aoyagi T, Miyahara Y, Chem. Commun., 46, 2203 (2010)
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Ivanov A, Yu I, Mattiasson B, J. Mol. Recognit., 19, 322 (2006)
Yoon J, Czarnik AW, J. Am. Chem. Soc., 114, 5874 (1992)
Springsteen G, Wang B, Chem. Commun., 1608 (2001)
Wang W, Gao X, Wang B, Curr. Org. Chem., 6, 1285 (2002)
Fang H, Kaur G, Wang B, J. Fluores., 14, 481 (2004)
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Chen W, Pelton R, Leung V, Macromolecules, 42(4), 1300 (2009)

[Referenced By]

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[1] Kwon IC, Bae YH, Kim SW, Nature, 354, 291 (1991)

[2] Hoffmann AS, in Controlled Drug Delivery: Challenges and Strategies, Park KN, Ed., Am. Chem. Soc., Washington, D. C., 1997, Chap. 24, pp 485-498.

[3] James TD, Sandanayake SKRA, Shinkai S, Angew. Chem.-Int. Edit., 35, 1910 (1996)

[4] James TD, Shinkai S, Top. Curr. Chem., 218, 159 (2002)

[5] Rzayev ZMO, Beskardes O, Coll. Czech. Chem. Commun., 72, 1591 (2007)

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

[7] Stolowitz ML, Ahlem C, Hughes KA, Kaiser RJ, Kesicki EA, Li G, Lund KP, Torkelson SM, Wiley JP, Bioconjugate Chem., 12, 229 (2001)

[8] DiCesare N, Lakowicz JR, J. Phys. Chem. A, 105(28), 6834 (2001)

[9] Jin XJ, Zhang XG, Wu ZM, Teng DY, Zhang XJ, Wang YX, Wang Z, Li CX, Biomacromolecules, 10(6), 1337 (2009)

[10] Achanta G, Modzelewska A, Feng L, Khan SR, Huang P, Mol. Pharmacol., 70, 426 (2006)

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

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

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

[14] Chiefari J, Chong YK, Ercole F, Krstina J, Jeffery J, Le TPT, Mayadunne RTA, Meijs GF, Moad CL, Moad G, Rizzardo E, Thang SH, Macromolecules, 31(16), 5559 (1998)

[15] Destarac M, Charmot D, Franck X, Zard SZ, Macromol. Rapid Commun., 21(15), 1035 (2000)

[16] Matyaszewski K, in Handbook of Radical Polymerization, Matyaszewski K, Davis TP, Eds., John Wiley & Sons, Inc., 2002, Chap. 8, pp 361-406.

[17] Hoare T, Pelton R, Biomacromolecules, 9(2), 733 (2008)

[18] Roy D, Cambre JN, Sumerlin BS, Chem. Commun., 2106 (2009)

[19] Sienkiewicz PA, Roberts DC, J. Inorg. Nucl. Chem., 42, 1559 (1980)

[20] Yang X, Lee MC, Sartain F, Pan X, Lowe CR, Chem. Eur. J., 12, 8491 (2006)

[21] Oishi M, Sumitani S, Nanasaki Y, Bioconjugate Chem., 18, 1379 (2007)

[22] Roy D, Cambre JN, Sumerlin BS, Chem. Commun., 2477 (2008)

[23] Matsumoto A, Yamamoto K, Yoshida R, Kataoka K, Aoyagi T, Miyahara Y, Chem. Commun., 46, 2203 (2010)

[24] Shiomori K, Ivanov AE, Yu I, Kawano Y, Mattiasson B, Macromol. Chem. Phys., 205, 27 (2004)

[25] Ivanov A, Yu I, Mattiasson B, J. Mol. Recognit., 19, 322 (2006)

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

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

[28] Wang W, Gao X, Wang B, Curr. Org. Chem., 6, 1285 (2002)

[29] Fang H, Kaur G, Wang B, J. Fluores., 14, 481 (2004)

[30] Yan J, Fang H, Wang B, Med. Res. Rev., 25, 490 (2005)

[31] Zhu L, Shabbir SH, Gray M, Lynch VM, Sorey S, Anslyn EV, J. Am. Chem. Soc., 128(4), 1222 (2006)

[32] Chen W, Pelton R, Leung V, Macromolecules, 42(4), 1300 (2009)