Abstract
The phase transition behavior of poly(2-ethyl-2-oxazoline) (PEtOx) under complexation with star-shaped poly(acrylic acid) (PAA) having various arm numbers (two, three, four, and six) has been studied by turbidity and laser light scattering measurements. The change in cloud point temperature (T cp) of PEtOx was monitored as a function of pH, ionic strength, and arm number of the star polyelectrolyte. The shift in T cp to a lower value than that of pure PEtOx was more pronounced at pH 4.2 (pH < pKa), when the carboxylic acid groups are protonated as compared to pH 7.0 (pH > pKa ), when the acid moieties are partially ionized. Dynamic light scattering showed that these complexes may have micellar core-shell type structure with a mean hydrodynamic radius (R h) ranging from 12 nm to ∼200 nm depending upon the temperature. Significant shift in T cp was observed for six-arm star poly(acrylic acid) complexes at both pH values. This change in the T cp is accredited to the differences in the driving forces of phase transition, including hydrogen bonding between carboxylic acid groups of PAA and the carbonyl moiety of PEtOx as well as the hydrophobic interactions.
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Chen HL, Morawetz H (1982) Macromolecules 15:1445–1447
Bokias G, Staikos G, Iliopoulos I, Audebert R (1994) Macromolecules 27:427–431
Osada YJ (1979) Polym Sci Part A Polym Chem 17:3485–3498
Bian FL, Liu MZ (2003) Eur Polym J 39:1867–1874
Nurkeeva ZS, Mun GA, Khutoryanskiy VV, Bitekenova AB, Dubolazov AV, Esirkegenova SZ (2003) Eur Polym J 10:65–68
Dubolazov AV, Nurkeeva ZS, Mun GA, Khutoryanskiy VV (2006) Biomacromolecules 7:1637–1643
Dou H, Tang M, Sun K (2005) Macromol Chem Phys 206:2177–2181
Mun GA, Khutoryanskiy VV, Nurkeeva ZS, Urkimbaeva PI, Zhunuspaev D (2004) J Polym Sci Part B: Polym Phys 42:2625–2632
Xu FJ, Zhang ZX, Ping Y, Li J, Kang ET, Neoh KG (2009) Biomacromolecules 10:285–293
Nemoto Y, Borovkov A, Zhou Y-M, Talewa Y, Tatsumi E, Nakayama Y (2009) Bioconjug Chem 20:2293–2299
Synatschke CV, Schallon A, Jerome V, Freitag R, Muller AHE (2011) Biomacromolecules 12:4247–4255
Kim BS, Gao H, Argun AA, Matyjaszewski K, Hammond PT (2009) Macromolecules 42:368–375
Choi I, Suntivich R, Plamper FA, Synatschke CV, Muller AHE, Tsukruk VVJ (2011) Am Chem Soc 133:9592–9606
Zhizhang G, Xingyu C, Jianyu X, Duo W, Jianshu L, Chenlong X (2010) Macromolecules 21:9087–9093
Li Y, Dubin PL, Spindler R, Tomalia DA (1995) Macromolecules 28:8426–8428
Miura N, Dubin PL, Moorefield CN, Newkome GR (1999) Langmuir 15:4245–4250
Storkle D, Duschner S, Heimann N, Maskos M, Schmidt M (2007) Macromolecules 40:7998–8006
Froehlich E, Mandeville JS, Weinert CM, Kreplak L, Tajmir-Riahi HA (2011) Biomacromolecules 12:511–517
Ishizu K, Toyoda K, Furukawa T, Sogabe A (2004) Macromolecules 37:3954–3957
Pergushov DV, Babin IA, Plamper FA, Zezin AB, Müller AHE (2008) Langmuir 24:6414–6419
Pergushov DV, Babin IA, Plamper FA, Schmalz H, Muller AHE, Zezin AB (2009) Dokl Phys Chem 425:57–61
Pergushov DV, Borisov OV, Zezin AB, Müller AHE (2011) Adv Polym Sci 241:131–161
Babin IA, Pergushov DV, Wolf A, Plamper FA, Schmalz H, Müller AHE, Zezin AB (2011) Dokl Phys Chem 44:219–223
Khutoryanskiy VV, Nurkeeva ZS, Mun GA, Dubolazov AVJ (2004) Appl Polym Sci 93:1946–1950
Dubolazov AV, Nurkeeva ZS, Mun GA, Lukmanova DM, Khutoryanskiy VV (2004) Euras Chem Technol J 6:299–303
Staikos G, Karayanni K, Mylonas Y (1997) Macromol Chem Phys 198:2905–2915
Koussathana M, Lianos G, Staikos G (1997) Macromolecules 30:7798–7802
Nurkeeva ZS, Mun GA, Khutoryanskiy VV (2003) Macromol Biosci 3:283–295
Lin PY, Clash C, Pearce EM, Kwei TK, Aponte MA (1988) J Polym Sci Part B: Polym Phys 26:603–619
Haruna M (2010) Bajopas 3:250–254
Hoogenboom R, Thijs HML, Jochem MJHC, Van Lankvelt BM, Fijten MWM, Schubert US (2008) Chem Commun 44:5758–5760
Kwon IC, Bae YH, Kim SW (1991) Nature 354:291–293
Chen FL, Pearce EM, Kwei TK (1988) Polymer 29:2285–2289
Lichkus AM, Painter PC, Coleman MM (1988) Macromolecules 21:2636–2641
Ambreen J, Yang J, Ye X, Siddiq M (2013) Colloid Polym Sci 291:919–925
Lee SC, Chang Y, Yoon JS, Kim C, Kwon IC, Kim YH, Jeong SY (1999) Macromolecules 32:1847–1852
Kim C, Lee SC, Shin JH, Yoon JS, Kwon IC, Jeong SY (2000) Macromolecules 33:7448–7452
Kim C, Lee SC, Kwon IC, Chung H, Jeong SY (2002) Macromolecules 35:193–200
Mendrek B, Trzebicka B (2009) Eur Polym J 45:1979–1993
Chen F, Liu G, Zhang GJ (2012) Phys Chem B 116:10941–10950
Feng X, Pan C (2001) J Polym Sci: Polym Chem 39:2233–2243
Zimm BHJ (1948) Chem Phys 16:1093–1099
Chu B (1991) Laser Light Scattering, Basic Principles and Practice, 2nd edn. Academic Press, New York, pp 2–8
Wu C, Xia KQ (1994) Rev Sci Instrum 65:587–590
Bijsterbosch HD, Cohen SMA, Fleer GJ, van Caeter P, Goethals EJ (1998) Macromolecules 31:7436–7444
Berne B, Pecora R (1976) Dynamic Light Scattering. Plenum Press, New York
Wu C, Niu AZ (1999) Sci China B 42:520–524
Diab C, Akiyama Y, Kataoka K, Winnik FM (2004) Macromolecules 37:2556–2562
Park JS, Akiyama Y, Winnik FM, Kataoka K (2004) Macromolecules 37:6786–6792
Wiesbrock F, Hoogenboom R, Abeln CH, Schubert US (2004) Macromol Rapid Commun 25:1895–1899
Christova D, Velichkova R, Loos W, Goethals EJ, Du Prez F (2003) Polymer 44:2255–2261
Zhou S, Fan S, Au-yeung SCF, Wu C (1995) Polymer 36:1341–1346
Gebhardt JE, Furstenau DW (1983) Colloids Surf 7:221–231
Jones MS (1999) Eur Polym J 35:795–801
Lu X, Hu Z, Schwartz J (2002) Macromolecules 35:9164–9168
Hofmann AS et al (2000) J Biomed Mater Res 52:577–586
Saeed A, Dominique MRG, Andrew GM (2012) React Funct Polym 72:77–82
Nurkeeva ZS, Mun GA, Khutoryanskiy VV, Sergaziev AD (2001) Eur Polym J 37:1233–1237
Belnikevich NG, Budtova TV, Ivanova NP, Panarin YF, Panov YP, Frenkel SY (1989) Vysokomol Soedin Ser A 31:1691–1696
Budtova TV, Belnikevich NG, Belyaev VM, Panov YN, Frenkel SY (1991) Vysokomol Soedin Ser B 33:520–525
Sivadasan K, Somasundaran P, Turro NJ (1991) Colloid Polym Sci 269:131–137
Garay MT, Alava C, Rodriguez M (2000) Polymer 41:5799–5807
Ye J, Xu J, Hu J, Wang X, Zhang G, Liu S, Wu C (2008) Macromolecules 41:4416–4422
Bekturov EA, Bimendina LA (1981) Adv Polym Sci 41:99–147
Iliopoulos I, Halary JL, Audebert RJ (1988) Polym Sci Part A Polym Chem 26:275–284
Huang Y, Cheng H, Han, Charles C (2010) Macromolecules 43:10031–10037
Acknowledgments
Ms. Jaweria Ambreen is thankful to Higher Education Commission of Pakistan for indigenous scholarship and IPFP fellowship program. We are also thankful to Dr. Xiaodong Ye, University of Science and Technology of China (USTC) for his thought provoking ideas and helpful discussions as well as Chen Fenggui, USTC in the synthesis of star-shaped polymers.
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Ambreen, J., Siddiq, M. Effect of arm number of poly(acrylic acid) on cloud point temperature of poly(2-ethyl-2-oxazoline). J Polym Res 21, 608 (2014). https://doi.org/10.1007/s10965-014-0608-z
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DOI: https://doi.org/10.1007/s10965-014-0608-z