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Synthesis and physicochemical properties of cationic microgels based on poly(N-isopropylmethacrylamide)

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Abstract

Surfactant-free, radical precipitation copolymerization of N-isopropylmethacrylamide and the cationic co-monomer N-(3-aminopropyl) methacrylamide hydrochloride (APMH) was carried out to prepare microgels functionalized with primary amines. The morphology and hydrodynamic diameter of the microgels were characterized by atomic force microscopy and photon correlation spectroscopy, with the effect of NaCl concentration and initiator type on the microgel size and yield being investigated. When a 2,2′-azobis (2-amidinopropane) dihydrochloride (V50)-initiated reaction was carried out in pure water, relatively small microgels (∼160 nm in diameter) were obtained in low yield (∼20%). However, both the yield and size increased if the reaction was carried out in saline or by using ammonium persulfate as initiator instead of V50. Stable amine-laden microgels in the range from 160 to 950 nm in diameter with narrow size distributions were thus produced using reaction media with controlled salinity. Microgel swelling and electrophoretic mobility values as a function of pH, ionic strength, and temperature were also studied, illustrating the presence of cationic sidechains and their influence on microgel properties. Finally, the availability of the primary amine groups for post-polymerization modification was confirmed via modification with fluorescein-N-hydroxysuccinamide.

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References

  1. Pelton RH, Chibante P (1986) Preparation of aqueous lattices with N-isopropylacrylamide. Colloids Surf 20:247–256

    Article  CAS  Google Scholar 

  2. Lee CF, Lin CC, Chi WY (2008) Thermosensitive and control release behavior of poly (N-isopropylacrylamide-co-acrylic acid) latex particles. J Polym Sci A Polym Chem 46:5734–5741

    Article  CAS  Google Scholar 

  3. Choi SH, Yoon JJ, Park TG (2002) Galactosylated poly(N-isopropylacrylamide) hydrogel submicrometer particles for specific cellular uptake within hepatocytes. J Colloid Interface Sci 251:57–63

    Article  CAS  Google Scholar 

  4. Blackburn WH, Dickerson EB, Smith MH, McDonald JF, Lyon LA (2009) Peptide-functionalized nanogels for targeted siRNA delivery. Bioconjug Chem 20:960–968

    Article  CAS  Google Scholar 

  5. Kim J, Nayak S, Lyon LA (2005) Bioresponsive hydrogel microlenses. J Am Chem Soc 127:9588–9592

    Article  CAS  Google Scholar 

  6. Kim JS, Singh N, Lyon LA (2007) Displacement-induced switching rates of bioresponsive hydrogel microlenses. Chem Mater 19:2527–2532

    Article  CAS  Google Scholar 

  7. Zhang YJ, Guan Y, Zhou SQ (2006) Synthesis and volume phase transitions of glucose-sensitive microgels. Biomacromolecules 7:3196–3201

    Article  CAS  Google Scholar 

  8. Jia XQ, Yeo Y, Clifton RJ, Jiao T, Kohane DS, Kobler JB, Zeitels SM, Langer R (2006) Hyaluronic acid-based microgels and microgel networks for vocal fold regeneration. Biomacromolecules 7:3336–3344

    Article  CAS  Google Scholar 

  9. Freemont TJ, Saunders BR (2008) PH-responsive microgel dispersions for repairing damaged load-bearing soft tissue. Soft Matter 4:919–924

    Article  CAS  Google Scholar 

  10. Grabstain V, Bianco-Peled H (2003) Mechanisms controlling the temperature-dependent binding of proteins to poly(N-isopropylacrylamide) microgels. Biotechnol Prog 19:1728–1733

    Article  CAS  Google Scholar 

  11. Snowden MJ, Chowdhry BZ, Vincent B, Morris GE (1996) Colloidal copolymer microgels of N-isopropylacrylamide and acrylic acid: pH, ionic strength and temperature effects. J Chem Soc, Faraday Trans 92:5013–5016

    Article  CAS  Google Scholar 

  12. Meng ZY, Hendrickson GR, Lyon LA (2009) Simultaneous orthogonal chemoligations on multiresponsive microgels. Macromolecules 42:7664–7669

    Article  CAS  Google Scholar 

  13. Suzuki D, Kawaguchi H (2006) Hybrid microgels with reversibly changeable multiple brilliant color. Langmuir 22:3818–3822

    Article  CAS  Google Scholar 

  14. Hermanson GT (1995) Bioconjugate Techniques. Academic, San Diego

    Google Scholar 

  15. Dyer MA, Ainslie KM, Pishko MV (2007) Protein adhesion on silicon-supported hyperbranched poly(ethylene glycol) and poly(allylamine) thin films. Langmuir 23:7018–7023

    Article  CAS  Google Scholar 

  16. Ramos J, Martin-Molina A, Sanz-Izquierdo MP, Rus A, Borque L, Hidalgo-Alvarez R, Galisteo-Gonzalez F, Forcada J (2003) Amino-functionalized latex particles obtained by a multistep method: Development of a new immunoreagent. J Polym Sci A Polym Chem 41:2404–2411

    Article  CAS  Google Scholar 

  17. Xu JJ, Timmons AB, Pelton R (2004) N-Vinylformamide as a route to amine-containing latexes and microgels. Colloid Polym Sci 282:256–263

    Article  CAS  Google Scholar 

  18. Leung MF, Zhu JM, Harris FW, Li P (2004) New route to smart core-shell polymeric microgels: Synthesis and properties. Macromol Rapid Commun 25:1819–1823

    Article  CAS  Google Scholar 

  19. Meunier F, Elaissari A, Pichot C (1995) Preparation and characterization of cationic poly(N-isopropylacrylamide) copolymer latexes. Polym Adv Technol 6:489–496

    Article  CAS  Google Scholar 

  20. Meng Z, Cho JK, Breedveld V, Lyon LA (2009) Physical aging and phase behavior of multiresponsive microgel colloidal dispersions. J Phys Chem B 113:4590–4599

    Article  CAS  Google Scholar 

  21. South AB, Whitmire RE, Garcia AJ, Lyon LA (2009) Centrifugal deposition of microgels for the rapid assembly of nonfouling thin films. ACS Appl Mater Interfaces 1:2747–2754

    Article  CAS  Google Scholar 

  22. Bao LY, Zha LS (2006) Preparation of poly(N-isopropylacrylamide) microgels using different initiators under various pH values. J Macromol Sci Part A Pure Appl Chem 43:1765–1771

    Article  CAS  Google Scholar 

  23. Mai-ngam K, Boonkitpattarakul K, Sakulsombat M, Chumningan P, Mai-ngam B (2009) Synthesis and phase separation of amine-functional temperature responsive copolymers based on poly(N-isopropylacrylamide). Eur Polym J 45:1260–1269

    Article  CAS  Google Scholar 

  24. Bokias G, Hourdet D (2001) Synthesis and characterization of positively charged amphiphilic water soluble polymers based on poly(N-isopropylacrylamide). Polymer 42:6329–6337

    Article  CAS  Google Scholar 

  25. Lopez-Leon T, Ortega-Vinuesa JL, Bastos-Gonzalez D, Elaissari A (2006) Cationic and anionic poly(N-isopropylacrylamide) based submicron gel particles: Electrokinetic properties and colloidal stability. J Phys Chem B 110:4629–4636

    Article  CAS  Google Scholar 

  26. Zhao JP, Zhang GZ, Pispas S (2009) Morphological transitions in aggregates of thermosensitive poly(ethylene oxide)-b-poly(N-isopropylacrylamide) block copolymers prepared via RAFT polymerization. J Polym Sci A Polym Chem 47:4099–4110

    Article  CAS  Google Scholar 

  27. Gao J, Frisken BJ (2003) Cross-linker-free N-isopropylacrylamide gel nanospheres. Langmuir 19:5212–5216

    Article  CAS  Google Scholar 

  28. Gao J, Frisken BJ (2005) Influence of secondary components on the synthesis of self-cross-linked N-isopropylacrylamide microgels. Langmuir 21:545–551

    Article  CAS  Google Scholar 

  29. Huang X, Misra GP, Vaish A, Flanagan JM, Sutermaster B, Lowe TL (2008) Novel nanogels with both thermoresponsive and hydrolytically degradable properties. Macromolecules 41:8339–8345

    Article  CAS  Google Scholar 

  30. Ma XM, Xi JY, Xian Z, Tang XZ (2005) Deswelling comparison of temperature-sensitive poly(N-isopropylacrylamide) microgels containing functional-OH groups with different hydrophilic long side chains. J Polym Sci, B: Polym Phys 43:3575–3583

    Article  CAS  Google Scholar 

  31. Debord JD, Lyon LA (2003) Synthesis and characterization of pH-responsive copolymer microgels with tunable volume phase transition temperatures. Langmuir 19:7662–7664

    Article  CAS  Google Scholar 

  32. Daly E, Saunders BR (2000) A study of the effect of electrolyte on the swelling and stability of poly(N-isopropylacrylamide) microgel dispersions. Langmuir 16:5546–5552

    Article  CAS  Google Scholar 

  33. Fernandez-Nieves A, Fernandez-Barbero A, de las Nieves FJ (2001) Salt effects over the swelling of ionized mesoscopic gels. J Chem Phys 115:7644–7649

    Article  CAS  Google Scholar 

  34. van de Wetering P, Zuidam NJ, van Steenbergen MJ, van der Houwen OAGJ, Underberg WJM, Hennink WE (1998) A mechanistic study of the hydrolytic stability of poly(2-(dimethylamino)ethyl methacrylate). Macromolecules 31:8063–8068

    Article  Google Scholar 

  35. Thompson KL, Read ES, Armes SP (2008) Chemical degradation of poly(2-aminoethyl methacrylate). Polym Degrad Stab 93:1460–1466

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was partially supported by the National Institutes of Health (1 R01 GM088291-01). XH thanks China Scholarship Council (CSC) for the fellowship support. We thank the Kröger group at GT for the use of their zeta-potential equipment.

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Authors and Affiliations

  1. School of Chemistry and Biochemistry and the Petit Institute for Bioengineering and Bioscience, Georgia Institute of Technology, Atlanta, GA, 30332, USA

    Xiaobo Hu & L. Andrew Lyon

  2. Research Institute of Materials Science, South China University of Technology, Guangzhou, 510640, People’s Republic of China

    Xiaobo Hu & Zhen Tong

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  1. Xiaobo Hu
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  2. Zhen Tong
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  3. L. Andrew Lyon
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Correspondence to L. Andrew Lyon.

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Hu, X., Tong, Z. & Lyon, L.A. Synthesis and physicochemical properties of cationic microgels based on poly(N-isopropylmethacrylamide). Colloid Polym Sci 289, 333–339 (2011). https://doi.org/10.1007/s00396-010-2347-y

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  • DOI: https://doi.org/10.1007/s00396-010-2347-y

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