Abstract
The phase transition temperatures (T p) of poly(N-isopropylacrylamide-co-2-acrylamidoglycolic acid) (P(NIPAAm-co-AmGc)) and P(NIPAAm-co-AmGc)/poly(dimethylaminoethyl methacrylate) (PDMAEMA) complex were monitored to investigate the effects of pH, comonomer composition, and complex formation. P(NIPAAm-co-AmGc) was synthesized via free radical polymerization with AmGc molar fractions of 0.04, 0.08, 0.16, and 0.25; the corresponding ratios of dimethylaminoethyl methacrylate (DMAEMA) and AmGc in the P(NIPAAm-co-AmGc)-16/PDMAEMA complex were 0.3, 0.7, 1.0, 2.0, and 4.0, respectively. Our results indicated that the T p of P(NIPAAm-co-AmGc) increased as the mole fraction of AmGc increased and was higher at pH 4 than at pH 3 and pH 7. For the P(NIPAAm-co-AmGc)-16/PDMAEMA complex, the lower critical solution temperature (LCST) was observed from 23 to 48 °C, and the upper critical solution temperature (UCST) was detected above 63 °C at pH values of 3, 4, and 7. The aggregation rate of the polymer chains was determined from the slope of the turbidity change in a plot of LCST versus temperature. As the T p was lower, aggregation occurred faster in P(NIPAAm-co-AmGc)-16 but slower in the P(NIPAAm-co-AmGc)-16/PDMAEMA complex at pH 7. Aggregation was not observed during the cooling scan or, at least, was less evident than in the heating scan because the hydrophobic attractive interactions during the cooling scan were not sufficient to offset the electrostatic repulsion between ionic groups at high temperatures.
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Wei H, Cheng S, Zhang X, Zhou R (2009) Prog Polym Sci 34:893
Kawaguchi H, Fujimoto K, Mizuhara Y (1992) Colloid Polym Sci 270:53
Ruel-Gariepy E, Leroux J (2004) Eur J Pharm Biopharm 58:409
Schmaljohann D (2006) Adv Drug Deliv Rev 58:1655
Pelton R (2000) Adv Colloid Interf 85:1
Peppas NA, Huang MT, Lugo JH, Zhang J (2000) Annu Rev Biomed Eng 2:9
Savas H, Guven O (2001) Int J Pharm 224:151
Feil H, Bae YH, Feijen Y, Kim SW (1992) Macromolecules 25:5528
Lu T, Vesterinen E, Tenhu H (1998) Polymer 39:641
Qui Y, Park K (2001) Adv Drug Deliv Rev 53:321
Bates FS (1991) Science 251:898
Mok MM, Ellison CJ, Torkelson JM (2011) Macromolecules 44:6220
Georges MK, Veregin RPN, Kazmaier PM, Hamer GK (1993) Macromolecules 26:2987
Beginn U (2008) Colloid Polym Sci 286:1465
Lefebvre MD, De la Cruz MO, Shull KR (2004) Macromolecules 37:1118
Jiang R, Jin QH, Li BH, Ding DT, Wickham RA, Shi AC (2008) Macromolecules 41:5457
Lee ES, Shin HJ, Na K, Bae YH (2003) J Control Release 90:363
Hilt JZ, Gupta AK, Rashid B, Peppas NA (2003) Biomed Microdevices 5:177
Peppas LB, Peppas NA (1990) Biomaterials 11:635
Vakkalanka SK, Peppas NA (1996) Polym Bull 36:221
Zavgorodnya O, Serpe MJ (2011) Colloid Polym Sci 289:591
Zhang N, Liu M, Shen Y, Chen J, Dai L, Gao C (2011) J Mater Sci 46:1523
Schild HG, Tirrell DA (1990) J Phys Chem 94:4352
Fujishige S, Kubota K, Ando I (1989) J Phys Chem 93:3311
Djokpe E, Vogt W (2001) Macromol Chem Phys 202:750
Butun V, Armes SP, Billingham NC (2001) Macromolecules 34:1148
Han X, Zhang X, Yin Q, Hu J, Liu H, Hu Y (2013) Macromol Rapid Commun 34:574
Lowe AB, McCormick CL (2002) Chem Rev 102:4177
Plamper FA, Ruppel M, Schmalz A, Borisov O, Ballauff M, Muller AHE (2007) Macromolecules 40:8361
Plamper FA, Schmalz A, Ballauff M, Muller AHE (2007) J Am Chem Soc 129:14538
Plamper FA, McKee JR, Laukkanen A, Nykanen A, Walther A, Ruokolainen J, Aseyev V, Tenhu H (2009) Soft Matter 5:1812
Yuan W, Zou H, Guo W, Wang A, Ren J (2012) J Mater Chem 22:24783
Yancheva E, Paneva D, Maximova V, Mespouille L, Dubois P, Manolova N, Rashkov I (2007) Biomacromolecules 8:976
Rivas BL, Quilodran B, Quiroz E (2003) J Appl Polym Sci 88:2614
Arotcarena M, Heise B, Ishaya S, Laschewsky A (2002) J Am Chem Soc 124:3787
He J, Yan B, Tremblay L, Zhao Y (2011) Langmuir 27:436
Wu G, Chen S, Zhan Q, Wang Y (2011) Macromolecules 44:999
Bruice TC, Bradbury WC (1965) J Am Chem Soc 5:4852
Nagasawa M, Murase M, Kondo K (1965) J Phys Chem 69:4005
Kim B, Hong D, Chang WV (2014) J Appl Polym Sci 131:41026
Sudre G, Tran Y, Creton C, Hourdet D (2012) Polymer 53:379
Pozo-Gonzalo C, Virgillo C, Yan Y, Howlett PC, Byrne N, MacFarlane DR, Forsyth M (2014) Electrochem Commun 38:24
Hofmeister F (1888) Arch Exp Pathol Pharmakol 24:246
Robinson DR, Jencks WP (1965) J Am Chem Soc 87:2470
Yamauchi H, Maeda Y (2007) J Phys Chem 111:12964
Casolaro M (1995) Macromolecules 28:2351
Casolaro M (1997) Polymer 38:4215
Xiong Z, Peng B, Han X, Peng C, Liu H, Hu Y (2011) J Colloid Interface Sci 356:557
Costa ROR, Freitas RFS (2002) Polymer 43:5879
Franks F (1968) Effects of solutes on the hydrogen bonding in water. In: Covington AK, Jones P (eds) Hydrogen-bonded solvent systems. Taylor & Francis, London, p 31
Lopez-Perez PM, da Silva RMP, Pashkuleva I, Parra F, Reis RL, San Roman J (2010) Langmuir 26:5934
Cho SH, Jhon MS, Yuk SH, Lee HB (1997) J Polym Sci B Polym Phys 35:595
Yoo MK, Sung YK, Cho CS, Lee YM (1997) Polymer 38:2759
Bhargava P, Tu YF, Zheng JX, Xiong HM, Quirk RP, Cheng SZD (2007) J Am Chem Soc 129:1113
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Kim, B., Hong, D. & Chang, W.V. LCST and UCST double-phase transitions of poly(N-isopropylacrylamide-co-2-acrylamidoglycolic acid)/poly(dimethylaminoethyl methacrylate) complex. Colloid Polym Sci 293, 699–708 (2015). https://doi.org/10.1007/s00396-014-3452-0
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DOI: https://doi.org/10.1007/s00396-014-3452-0