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Temperature-responsive copolymer brush constructed on a silica microparticle by atom transfer radical polymerization

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Abstract

A polymer, poly(2-(2-methoxyethoxy)ethyl methacrylate) (PMDM), was accumulated on a silica microparticle by surface-initiated atom transfer radical polymerization (ATRP). The hydrodynamic diameter of the polymer-grafted silica particle (PMDM-SiP) dispersed in water was observed to decrease above 24 °C, which could be ascribed to a coil-globule transition of PMDM chains. This is in accordance with the increase in turbidity of an aqueous solution of free PMDM, which was produced parallel in liquid phase at the ATRP, above 23 °C. The lower critical solution temperature (LCST), defined as the temperature at which the absorbance reached the optical density of 0.30, was 27.6 °C for free PMDM. An introduction of zwitterionic vinyl monomer, carboxymethylbetaine (CMB), into both a polymer brush and a free polymer (P(MDM-r-CMB)) raised the LCST. In addition, the hydrodynamic diameter (D h) of the polymer-modified particles was not affected by the presence of NaBr nor lysozyme at 15 °C, whereas it was largely affected at 35 °C due to the decrease in hydrophilicity of the polymer graft chain above the LCST. In contrast, bovine serum albumin did not affect the D h value of the polymer-modified particles both below and above the LCST. The usefulness of the PMDM brush having CMB as a comonomer in the biomedical field was suggested.

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References

  1. Kitano H, Maehara Y, Matano M, Sugimura M, Shigemori K (1997) Interfacial recognition of sugar residues in block copolymers by lectin as studied by the multiple internal reflection fluorescence method. Langmuir 13:5041–5048

    Article  CAS  Google Scholar 

  2. Kitano H, Fukui N, Ohhori K, Maehara Y, Kokado N, Yoshizumi A (1999) Temperature-responsiveness of A-B-A block telomers at solid-liquid interfaces. J Colloid Interf Sci 212:58–64

    Article  CAS  Google Scholar 

  3. Chang Y, Chen S, Zheng Z, Jiang S (2006) Highly protein-resistant coatings from well-defined diblock copolymers containing sulfobetaines. Langmuir 22:2222–2226

    Article  CAS  Google Scholar 

  4. Decher G (1997) Fuzzy nanoassemblies: toward layered polymeric multicomposites. Science 277:1232–1237

    Article  CAS  Google Scholar 

  5. Ohno K, Koh K, Tsujii Y, Fukuda T (2002) Synthesis of gold nanoparticles coated with well-defined, high-density polymer brushes by surface-initiated living radical polymerization. Macromol 35:8989–8993

    Article  CAS  Google Scholar 

  6. Ohno K, Koh K, Tsujii Y, Fukuda T (2003) Fabrication of ordered arrays of gold nanoparticles coated with high-density polymer brushes. Angew Chem Int Ed 42:2751–2754

    Article  CAS  Google Scholar 

  7. Edmondson S, Osborne VL, Huck WTS (2004) Polymer brushes via surface-initiated polymerizations. Chem Soc Rev 33:14–22

    Article  CAS  Google Scholar 

  8. Kitano H, Kawasaki A, Kawasaki H, Morokoshi S (2005) Resistance of zwitterionic telomers accumulated on metal surfaces against nonspecific adsorption of proteins. J Colloid Interf Sci 282:340–348

    Article  CAS  Google Scholar 

  9. Kitano H, Tachimoto K, Shinohara H (2004) Wrapping of single-walled carbon nanotubes with A-B-A block telomers. Macromol Chem Phys 205:2064–2071

    Article  CAS  Google Scholar 

  10. Matsuura K, Ohno K, Kagaya S, Kitano H (2007) Carboxybetaine polymer-protected nanoparticles: high dispersion stability and resistance against non-specific adsorption of proteins. Macromol Chem Phys 208:862–873

    Article  CAS  Google Scholar 

  11. Morokoshi S, Ohhori K, Mizukami K, Kitano H (2004) Sensing capabilities of colloidal gold modified with self-assembled monolayer of a glucose-carrying chain on a glass substrate. Langmuir 20:8897–8902

    Article  CAS  Google Scholar 

  12. Kitano H, Anraku Y, Shinohara H (2006) Sensing capabilities of colloidal gold monolayer modified with a phenylboronic acid-carrying polymer brush. Biomacromolecules 7:1065–1071

    Article  CAS  Google Scholar 

  13. Kitano H, Takahashi Y, Mizukami K, Matsuura K (2009) Kinetic study on the binding of lectin to mannose residues in a polymer brush. Colloids Surf B 70:91–97

    Article  CAS  Google Scholar 

  14. Zhang Z, Chao T, Chen S, Jiang S (2006) Superlow fouling sulfobetaine and carboxybetaine polymers on glass slides. Langmuir 22:10072–10077

    Article  CAS  Google Scholar 

  15. Kitano H, Suzuki H, Kondo T, Sasaki K, Iwanaga S, Nakamura M, Ohno K, Saruwatari Y (2011) Image printing on the surface of anti-biofouling zwitterionic polymer brushes by ion beam irradiation. Macromol Biosci 11:557–564

    Article  CAS  Google Scholar 

  16. Liong M, Lu J, Kovochich M, Xia T, Ruehm SG, Nel AE, Tamanoi F, Zink JI (2008) Multifunctional inorganic nanoparticles for imaging, targeting, and drug delivery. ACS Nano 2:889–896

    Article  CAS  Google Scholar 

  17. Lee CS, Chang HH, Bae PK, Jung J, Chung BH (2013) Bifunctional nanoparticles constructed using one-pot encapsulation of a fluorescent polymer and magnetic (Fe3O4) nanoparticles in a silica shell. Macromol Biosci 13:321–331

    Article  CAS  Google Scholar 

  18. Mignot A, Truillet C, Lux F, Sancey L, Louis C, Denat F, Boschetti F, Bocher L, Gloter A, Stephan O, Antoine R, Dugourd P, Luneau D, Novitchi G, Figueiredo LC, de Morais PC, Bonneviot L, Albela B, Ribot F, Van Lokeren L, Dechamps-Olivier I, Chuburu F, Lemercier G, Villiers C, Marche PN, Le Duc G, Roux S, Tillement O, Perriat P (2013) A top-down synthesis route to ultrasmall multifunctional Gd-based silica nanoparticles for theranostic applications. Chem A Eur J 19:6122–6136

    Article  CAS  Google Scholar 

  19. Kitano H, Nakaji-Hirabayashi T, Gemmei-Ide M, Kyogoku M (2004) Effect of macrocycles on the temperature-responsiveness of poly(methoxydiethylene glycol methacrylate)-graft-PEG. Macromol Chem Phys 205:1651–1659

    Article  CAS  Google Scholar 

  20. Maeda Y, Kubota T, Yamauchi H, Nakaji T, Kitano H (2007) Hydration changes of poly(2-(2-methoxyethoxy)ethyl methacrylate) during thermosensitive phase separation in water. Langmuir 23:11259–11265

    Article  CAS  Google Scholar 

  21. Kitano H, Kago H, Matsuura K (2009) Temperature-responsive polymer brush constructed on a colloidal gold monolayer. J Colloid Interf Sci 331:343–350

    Article  CAS  Google Scholar 

  22. Kitano H, Kondo T, Suzuki H, Ohno K (2010) Temperature-responsive polymer-brush constructed on a glass substrate by atom transfer radical polymerization. J Colloid Interf Sci 345:325–331

    Article  CAS  Google Scholar 

  23. Ye J, Narin R (2009) Water-assisted atom transfer radical polymerization of N-isopropylacrylamide: nature of solvent and temperature. J Phys Chem B 113:676–681

    Article  CAS  Google Scholar 

  24. Alli S, Alli A, Hazer B (2012) Hyperbranched homo and thermoresponsive graft copolymers by using ATRP-macromonomer initiators. J Appl Polym Sci 124:536–548

    Article  CAS  Google Scholar 

  25. Cai Y, Liu Y-Y (2013) Amphiphilic unimolecular nanoparticles based on a hyperbranched polyacrylate and a PNIPAm shell: synthesis via ATRP and properties. Macromol Chem Phys 214:892–891

    Article  Google Scholar 

  26. Okuda Y (2000) Japan Patent 3032155

  27. Uchiyama Y, Okuda Y, Ninoi T, Mukaiyama T (2007) Japan Patent 3878315

  28. Ohno K, Akashi T, Huang Y, Tsujii Y (2010) Surface-initiated living radical polymerization from narrowly size-distributed silica nanoparticles of diameters less than 100 nm. Macromol 43:8805–8812

    Article  CAS  Google Scholar 

  29. Suzuki H, Murou M, Kitano H, Ohno K, Saruwatari Y (2011) Silica particles coated with zwitterionic polymer brush: formation of colloidal crystals and anti-biofouling properties in aqueous medium. Colloids Surf B 84:111–116

    Article  CAS  Google Scholar 

  30. Ohno K, Morinaga T, Koh K, Tsujii Y, Fukda T (2005) Synthesis of monodisperse silica particles coated with well-defined, high-density polymer brushes by surface-initiated atom transfer radical polymerization. Macromol 38:2137–2142

    Article  CAS  Google Scholar 

  31. Takeuchi S, Omodaka I, Hasegawa K, Maeda Y, Kitano H (1993) Temperature-responsive graft copolymers for immobilization of enzymes. Makromol Chem 194:1991–1999

    Article  CAS  Google Scholar 

  32. Kitano H, Yan C, Nakamura K (1991) Microspheres prepared from temperature-sensitive graft polymers. Makromol Chem 192:2915–2923

    Article  CAS  Google Scholar 

  33. Tsujii Y, Ejaz M, Sato K, Goto A, Fukuda T (2001) Mechanism and kinetics of RAFT-mediated graft polymerization of styrene on a solid surface. 1. Experimental evidence of surface radical migration. Macromolecules 34:8872–8878

    Article  CAS  Google Scholar 

  34. Brandrup J, Immergut EH, Grulke EA, Grulke EA, Abe A, Bloch D (2003) Polymer handbook, 4th Ed; Wiley-Interscience

  35. Kitano H, Kondo T, Kamada T, Iwanaga S, Nakamura M, Ohno K (2011) Anti-biofouling properties an amphoteric polymer brush constructed on a glass substrate. Colloids Surf B 88:455–462

    Article  CAS  Google Scholar 

  36. Ohshima H (2010) Biophysical chemistry of biointerfaces. Wiley, Hoboken

    Book  Google Scholar 

  37. Ohshima H, Makino K, Kato T, Fujimoto K, Kondo T, Kawaguchi H (1993) Electrophoretic mobility of latex particles covered with temperature-sensitive hydrogel layers. J Colloid Interface Sci 159:512–514

    Article  CAS  Google Scholar 

  38. Yamakawa T, Imahori K (1979) Biochemistry data book, vol I. Tokyo Kagaku-Dojin, Tokyo

    Google Scholar 

  39. Obiweluozor FO, GhavamiNejad A, Hashmi S, Vatankhah-Varnoosfaderani M, Stadler FJ (2014) A NIPAM–zwitterion copolymer: rheological interpretation of the specific ion effect on the LCST. Macromol Chem Phys 215:1077–1091

    Article  CAS  Google Scholar 

  40. von der Ehe C, Weber C, Wagner M, Czaplewska JA, Gottschaldt M, Schubert US (2014) Synthesis of thermoresponsive glycopolymers combining RAFT polymerization, thiol-ene reaction, and subsequent immobilization onto solid supports. Macromol Chem Phys 215:1306–1318

    Article  Google Scholar 

Download references

Acknowledgments

This research was supported by a Grant-in-Aid for Scientific Research (22350101 and 26188100) from the Japan Society for the Promotion of Science (JSPS) and a Grant-in-Aid for Innovative Areas (20106007) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Tokyo, Japan. T. N.-H. is grateful to the Japan Science & Technology Promotion Foundation (JST) for the tenure track program. The authors are indebted to Osaka Organic Chemical Industry for the kind gift of CMB.

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Authors and Affiliations

  1. Department of Applied Chemistry, Graduate School of Science and Engineering, University of Toyama, Toyama, 930-8555, Japan

    Kouji Nomura, Hirokazu Makino & Hiromi Kitano

  2. Frontier Research Core for Life Sciences, University of Toyama, Toyama, 930-8555, Japan

    Tadashi Nakaji-Hirabayashi

  3. Institute for Chemical Research, Kyoto University, Uji, 611-0011, Japan

    Kohji Ohno

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  1. Kouji Nomura
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  2. Hirokazu Makino
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  3. Tadashi Nakaji-Hirabayashi
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  4. Hiromi Kitano
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  5. Kohji Ohno
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Correspondence to Hiromi Kitano.

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Nomura, K., Makino, H., Nakaji-Hirabayashi, T. et al. Temperature-responsive copolymer brush constructed on a silica microparticle by atom transfer radical polymerization. Colloid Polym Sci 293, 851–859 (2015). https://doi.org/10.1007/s00396-014-3476-5

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  • DOI: https://doi.org/10.1007/s00396-014-3476-5

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