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Thermoresponsive behavior of poly(N-isopropylacrylamide)s with dodecyl and carboxyl terminal groups in aqueous solution: pH-dependent cloud point temperature

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Abstract

It was recently reported that poly(N-isopropyl acrylamide) (PNIPAm) polymers synthesized by RAFT polymerization using S-1-dodecyl-S′-(α,α′-dimethyl-α′′-acetic acid)trithiocarbonate as a chain transfer agent form micelles in aqueous solutions with the core of hydrophobic terminal dodecyl groups and the corona of PNIPAm chains with carboxylic groups at the periphery, the ionization of which prevents the micelles from phase separation above the lower critical solution temperature of PNIPAm in water (Langmuir 30:7986–7992). In this paper, we study the pH- and ionic strength-dependence of the aggregation behavior of two HOOC-PNIPAm-C12 polymers, differing in the degree of polymerization, in aqueous solutions. We show that the cloud point temperature (CPT) of HOOC-PNIPAm-C12 can be shifted up to several tens of K by changing pH of the solution. The aggregation of the PNIPAms above the CPT can be efficiently accelerated by screening electrostatic repulsion between PNIPAm micelles by changing ionic strength of the solution.

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References

  1. Dai ZJ, Ngai T (2013) Microgel particles: the structure-property relationships and their biomedical applications. J Polym Sci A Polym Chem 51:2995–3003. doi:10.1002/pola.26698

    Article  CAS  Google Scholar 

  2. Hu L, Sarker AK, Islam MR, Li X, Lu ZZ, Serpe MJ (2013) Poly(N-isopropylacrylamide) microgel-based assemblies. J Polym Sci A Polym Chem 51:3004–3020. doi:10.1002/pola.26702

    Article  CAS  Google Scholar 

  3. Hocine S, Li MH (2013) Thermoresponsive self-assembled polymer colloids in water. Soft Matter 9:5839–5861. doi:10.1039/c3sm50428j

    Article  CAS  Google Scholar 

  4. Chan K, Pelton R, Zhang J (1999) On the formation of colloidally dispersed phase-separated poly(N-isopropylacrylamide). Langmuir 15:4018–4020. doi:10.1021/la9812673

    Article  CAS  Google Scholar 

  5. Cao ZQ, Liu WG, Gao P, Yao KD, Li HX, Wang GC (2005) Toward an understanding of thermoresponsive transition behavior of hydrophobically modified N-isopropylacrylamide copolymer solution. Polymer 46:5268–5277. doi:10.1016/j.polymer.2005.04.050

    Article  CAS  Google Scholar 

  6. Xia Y, Burke NAD, Stöver HDH (2006) End group effect on the thermal response of narrow-disperse poly(N-isopropylacrylamide) prepared by atom transfer radical polymerization. Macromolecules 39:2275–2283. doi:10.1021/ma0519617

    Article  CAS  Google Scholar 

  7. Xue N, Qiu XP, Chen YG, Satoh T, Kakuchi T, Winnik FM (2016) Effect of chain architecture on the phase transition of star and cyclic poly(N-isopropylacrylamide) in water. J Polym Sci B Polym Phys 54:2059–2068. doi:10.1002/polb.24114

    Article  CAS  Google Scholar 

  8. Luo SZ, Xu J, Zhu ZY, Wu C, Liu SY (2006) Phase transition behavior of Unimolecular micelles with Thermoresponsive poly(N-isopropylacrylamide) coronas. J Phys Chem B 110:9132–9139. doi:10.1021/jp061055b

    Article  CAS  PubMed  Google Scholar 

  9. Nuopponen M, Ojala J, Tenhu H (2004) Aggregation behaviour of well defined amphiphilic diblock copolymers with poly (N-isopropylacrylamide) and hydrophobic blocks. Polymer 45:3643–3650. doi:10.1016/j.polymer.2004.03.083

    Article  CAS  Google Scholar 

  10. Zhang WA, Zhou XC, Li H, Fang Y, Zhang GZ (2005a) Conformational transition of tethered poly(N-isopropylacrylamide) chains in coronas of micelles and vesicles. Macromolecules 38:909–914. doi:10.1021/ma048227s

    Article  CAS  Google Scholar 

  11. Ye XD, Fei JY, Guan J, Zhou XC, Zhang GZ (2010) Dispersion of polystyrene inside polystyrene-b-poly(N-isopropylacrylamide) micelles in water. J Polym Sci B Polym Phys 48:749–755. doi:10.1002/polb.21948

    Article  CAS  Google Scholar 

  12. Blackman LD, Wright DB, Robin MP, Gibson MI, O'Reilly RK (2015) Effect of micellization on the thermoresponsive behavior of polymeric assemblies. ACS Macro Lett 4:1210–1214. doi:10.1021/acsmacrolett.5b00551

    Article  CAS  Google Scholar 

  13. Kyriakos K, Philipp M, Adelsberger J, Jaksch S, Berezkin AV, Lugo DM, Richtering W, Grillo I, Miasnikova A, Laschewsky AP, Müller-Buschbaum P, Papadakis CM (2014) Cononsolvency of water/methanol mixtures for PNIPAM and PS-b-PNIPAM: pathway of aggregate formation investigated using time-resolved SANS. Macromolecules 47:6867–6879

    Article  CAS  Google Scholar 

  14. Adelsberger J, Kulkarni A, Jain A, Wang WN, Bivigou-Koumba AM, Busch P, Pipich V, Holderer O, Hellweg T, Laschewsky A, Müller-Buschbaum P, Papadakis CM (2010) Thermoresponsive PS-b-PNIPAM-b-PS micelles: aggregation behavior, segmental dynamics, and thermal response. Macromolecules 43:2490–2501. doi:10.1021/ma902714p

    Article  CAS  Google Scholar 

  15. Papagiannopoulos A, Zhao JP, Zhang GZ, Pispas S, Radulescu A (2014) Thermoresponsive aggregation of PS-PNIPAM-PS triblock copolymer: a combined study of light scattering and small angle neutron scattering. Eur Polym J 56:59–68. doi:10.1016/j.eurpolymj.2014.04.013

    Article  CAS  Google Scholar 

  16. FitzGerald PA, Gupta S, Wood K, Perrier S (2014) Warr GG (2014) temperature- and pH-responsive micelles with collapsible poly(N-isopropylacrylamide) Headgroups. Langmuir 30:7986–7992. doi:10.1021/la501861t

    Article  CAS  PubMed  Google Scholar 

  17. Mylonas E, Svergun DI (2007) Accuracy of molecular mass determination of proteins in solution by small-angle X-ray scattering. J Appl Crystallogr 40:S245–S249. doi:10.1107/S002188980700252X

    Article  CAS  Google Scholar 

  18. Bressler I, Kohlbrecher J, Thünemann AF (2015) SASfit: a tool for small-angle scattering data analysis using a library of analytical expressions. J Appl Crystallogr 48:1587–1598

    Article  CAS  Google Scholar 

  19. Keller S, Vargas C, Zhao HY, Piszczek G, Brautigam CA, Schuck P (2012) High-precision isothermal titration calorimetry with automated peak-shape analysis. Anal Chem 84:5066–5073. doi:10.1021/ac3007522

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  20. Yong P, Yang YJ, Wang ZY, Yang LM, Chen J (2016) Diverse nanostructures and gel behaviours contained in a thermo- and dual-pH-sensitive ABC (PNIPAM-PAA-P4VP) terpolymer in an aqueous solution. RSC Adv 6:88306–88314. doi:10.1039/c6ra14682a

    Article  CAS  Google Scholar 

  21. Iatridi Z, Lencina MMS, Tsitsilianis C (2015) PNIPAM-based heteroarm star-graft quarterpolymers: synthesis, characterization and pH-dependent thermoresponsiveness in aqueous media. Polym Chem 6:3942–3955. doi:10.1039/c5py00393h

    Article  CAS  Google Scholar 

  22. Zhang YJ, Furyk S, Bergbreiter DE, Cremer PS (2005b) Specific ion effects on the water solubility of macromolecules: PNIPAM and the Hofmeister series. J Am Chem Soc 127:14505–14510. doi:10.1021/ja0546424

    Article  CAS  PubMed  Google Scholar 

  23. Brey JJ, Prados A (2001) Slow logarithmic relaxation in models with hierarchically constrained dynamics. Phys Rev E 63:021108. doi:10.1103/PhysRevE.63.021108

    Article  CAS  Google Scholar 

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Acknowledgments

M. Š. acknowledges the support from the Czech Science Foundation (Grant No. 14-11516S) and from the Ministry of Education, Youth and Sports of the Czech Republic (Operational Programme Research, Development and Education: “Excellent Research Teams”, Project No. CZ.02.1.01/0.0/0.0/15_003/0000417 – CUCAM). The support of Clement Blanchet (EMBL) is kindly acknowledged.

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Authors and Affiliations

  1. Department of Physical and Macromolecular Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 12840, Prague 2, Czech Republic

    Juraj Škvarla, Rahul K. Raya, Mariusz Uchman, Jiří Zedník, Karel Procházka & Miroslav Štěpánek

  2. Helmholtz-Zentrum Geesthacht, Centre for Materials and Coastal Research, 21502, Geesthacht, Germany

    Vasil M. Garamus

  3. Theoretical & Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vassileos Constantinou Ave, 11635, Athens, Greece

    Anastasia Meristoudi & Stergios Pispas

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  1. Juraj Škvarla
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  2. Rahul K. Raya
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  9. Miroslav Štěpánek
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Correspondence to Miroslav Štěpánek.

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Škvarla, J., Raya, R.K., Uchman, M. et al. Thermoresponsive behavior of poly(N-isopropylacrylamide)s with dodecyl and carboxyl terminal groups in aqueous solution: pH-dependent cloud point temperature. Colloid Polym Sci 295, 1343–1349 (2017). https://doi.org/10.1007/s00396-017-4067-z

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  • DOI: https://doi.org/10.1007/s00396-017-4067-z

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