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Journal for Biophysical Chemistry

Micro- and Nanostructured Poly[oligo(ethylene glycol)methacrylate] Brushes Grown From Photopatterned Halogen Initiators by Atom Transfer Radical Polymerization

Abstract

Photolithographic techniques have been used to fabricate polymer brush micro- and nanostructures. On exposure to UV light with a wavelength of 244 nm, halogens were selectively removed from films of chloromethylphenyltrichlorosilane and 3-(2-bromoisobutyramido)propyl-triethoxysilane on silicon dioxide. Patterning was achieved at the micrometer scale, by using a mask in conjunction with the incident laser beam, and at the nanometer scale, by utilizing interferometric lithography (IL). Friction force microscopy images of patterned surfaces exhibited frictional contrast due to removal of the halogen but no topographical contrast. In both cases the halogenated surface was used as an initiator for surface atom-transfer radical polymerization. Patterning of the surface by UV lithography enabled the definition of patterns of initiator from which micro- and nanostructured poly[oligo(ethylene glycol)methacrylate] bottle brushes were grown. Micropatterned brushes formed on both surfaces exhibited excellent resistance to protein adsorption, enabling the formation of protein patterns. Using IL, brush structures were formed that covered macroscopic areas (approximately 0.5 cm2) but exhibited a full width at half maximum height as small as 78 nm, with a period of 225 nm. Spatially selective photolytic removal of halogens that are immobilized on a surface thus appears to be a simple, rapid, and versatile method for the formation of micro- and nanostructured polymer brushes and for the control of protein adsorption.

References

  1. S. Lee, M. Müller, M. Ratoi-Salagean, J. Vörös, S. Pasche, S. M. D. Paul, H. A. Spikes, M. Textor, and N. D. Spencer, Tribol. Lett. 15, 231 (2003).

    Article  CAS  Google Scholar 

  2. M. Müller, S. Lee, H. A. Spikes, and N. D. Spencer, Tribol. Lett. 15, 395 (2003).

    Article  Google Scholar 

  3. T. Drobek and N. D. Spencer, Langmuir 24, 1484 (2008).

    Article  CAS  Google Scholar 

  4. M. Chen, W. H. Briscoe, S. P. Armes, and J. Klein, Science 323, 1698 (2009).

    Article  CAS  Google Scholar 

  5. K. Kitano, Y. Inoue, R. Matsuno, M. Takai, and K. Ishihara, Colloids Surf., B 74, 350 (2009).

    Article  CAS  Google Scholar 

  6. A. J. Morse, S. Edmondson, D. Dupina, S. P. Armes, Z. Zhang, G. J. Leggett, R. L. Thompson, and A. L. Lewis, Soft Matter 6, 1571 (2010).

    Article  CAS  Google Scholar 

  7. F. Zhou and W. T. S. Huck, Phys. Chem. Chem. Phys. 8, 3815 (2006).

    Article  CAS  Google Scholar 

  8. J. M. Harris, Poly(Ethylene Glycol) Chemistry: Biochemical and Biomedical Applications (Plenum, New York, 1992).

    Google Scholar 

  9. G. P. Löpez, B. D. Ratner, C. D. Tidwell, C. L. Haycox, R. J. Rapoza, and T. A. Horbett, J. Biomed. Mater. Res. 26, 415 (1992).

    Article  Google Scholar 

  10. C. Pale-Grosdemange, E. S. Simon, K. L. Prime, and G. M. Whitesides, J. Am. Chem. Soc. 113, 12 (1991).

    Article  CAS  Google Scholar 

  11. E. Ostuni, R. G. Chapman, E. R. Holmlin, S. Takayama, and G. M. Whitesides, Langmuir 17, 5605 (2001).

    Article  CAS  Google Scholar 

  12. P. Harder, M. Grunze, R. Dahint, G. M. Whitesides, and P. E. Laibinis, J. Phys. Chem. B 102, 426 (1998).

    Article  CAS  Google Scholar 

  13. R. D. Piner, J. Zhu, F. Xu, S. Hong, and C. A. Mirkin, Science 283, 661 (1999).

    Article  CAS  Google Scholar 

  14. S. Hong, J. Zhu, and C. A. Mirkin, Science 286, 523 (1999).

    Article  CAS  Google Scholar 

  15. K.-B. Lee, S.-J. Park, C. A. Mirkin, J. C. Smith, and M. Mrksich, Science 295, 1702 (2002).

    Article  CAS  Google Scholar 

  16. K. Salaita, Y. Wang, J. Fragala, R. A. Vega, C. Liu, and C. A. Mirkin, Angew. Chem., Int. Ed. 45, 7220 (2006).

    Article  CAS  Google Scholar 

  17. S. Sun, K. S. L. Chong, and G. J. Leggett, J. Am. Chem. Soc. 124, 2414 (2002).

    Article  CAS  Google Scholar 

  18. S. Sun and G. J. Leggett, Nano Lett. 4, 1381 (2004).

    Article  CAS  Google Scholar 

  19. M. Montague, R. E. Ducker, K. S. L. Chong, R. J. Manning, F. J. M. Rutten, M. C. Davies, and G. J. Leggett, Langmuir 23, 7328 (2007).

    Article  CAS  Google Scholar 

  20. R. Maoz, E. Frydman, S. R. Cohen, and J. Sagiv, Adv. Mater. 12, 725 (2000).

    Article  CAS  Google Scholar 

  21. R. Maoz, E. Frydman, S. R. Cohen, and J. Sagiv, Adv. Mater. 12, 424 (2000).

    Article  CAS  Google Scholar 

  22. S. Hoeppener, R. Maoz, and J. Sagiv, Nano Lett. 3, 761 (2003).

    Article  CAS  Google Scholar 

  23. R. S. Dibbell, G. S. Soja, R. M. Hoth, and D. F. Watson, Langmuir 23, 3432 (2007).

    Article  CAS  Google Scholar 

  24. G. R. Soja, J. R. Mann, and D. F. Watson, Langmuir 24, 5249 (2008).

    Article  CAS  Google Scholar 

  25. G. R. Soja and D. F. Watson, Langmuir 25, 5398 (2009).

    Article  CAS  Google Scholar 

  26. G. Tizazu, A. Adawi, G. J. Leggett, and D. G. Lidzey, Langmuir 25, 10746 (2009).

    Article  CAS  Google Scholar 

  27. H. Ma, D. Li, X. Sheng, B. Zhao, and A. Chilkoti, Langmuir 22, 3751 (2006).

    Article  CAS  Google Scholar 

  28. H. Ma, M. Wells, T. P. Beebe, Jr., and A. Chilkoti, Adv. Funct. Mater. 16, 640 (2006).

    Article  CAS  Google Scholar 

  29. A. Hucknall, S. Rangarajan, and A. Chilkoti, Adv. Mater. 21, 2441 (2009).

    Article  CAS  Google Scholar 

  30. M. Husemann, M. Morrison, D. Benoit, J. Frommer, C. M. Mate, W. D. Hinsberg, J. L. Hedrick, and C. J. Hawker, J. Am. Chem. Soc. 122, 1844 (2000).

    Article  CAS  Google Scholar 

  31. S. Alang Ahmad, A. Hucknall, A. Chilkoti, and G. J. Leggett, Langmuir 26, 9937 (2010).

    Article  CAS  Google Scholar 

  32. F. Zhou, Z. Zheng, B. Yu, W. Liu, and W. T. S. Huck, J. Am. Chem. Soc. 128, 16253 (2006).

    Article  CAS  Google Scholar 

  33. Y. Zou, P.-Y. J. Yeh, N. A. A. Rossi, D. E. Brooks, and J. N. Kizakkedathu, Biomacromolecules 11, 284 (2010).

    Article  CAS  Google Scholar 

  34. M. Mathieu, A. Friebe, S. Franzka, M. Ulbricht, and N. Hartmann, Langmuir 25, 12393 (2009).

    Article  CAS  Google Scholar 

  35. Y. Liu, V. Klep, and I. Luzinov, J. Am. Chem. Soc. 128, 8106 (2006).

    Article  CAS  Google Scholar 

  36. C. Schuh, S. Santer, O. Prucker, and J. Ruhe, Adv. Mater. 21, 4706 (2009).

    CAS  Google Scholar 

  37. X. Jia, X. Jiang, R. Liu, and J. Yin, ACS Appl. Mater. Interfaces 2, 1200 (2010).

    Article  CAS  Google Scholar 

  38. M. Kaholek, W.-K. Lee, B. LaMattina, K. C. Caster, and S. Zauscher, Nano Lett. 4, 373 (2004).

    Article  CAS  Google Scholar 

  39. M. Kaholek, W.-K. Lee, J. Feng, B. LaMattina, D. J. Dyer, and S. Zauscher, Chem. Mater. 18, 3660 (2006).

    Article  CAS  Google Scholar 

  40. S. Sun, M. Montague, K. Critchley, M.-S. Chen, W. J. Dressick, S. D. Evans, and G. J. Leggett, Nano Lett. 6, 29 (2006).

    Article  Google Scholar 

  41. R. Iwata, P. Suk-In, V. P. Hoven, A. Takahara, K. Akiyoshi, and Y. Iwasaki, Biomacromolecules 5, 2308 (2004).

    Article  CAS  Google Scholar 

  42. S. R. J. Brueck, Proc. IEEE 93, 1704 (2005).

    Article  CAS  Google Scholar 

  43. C. Lu and R. H. Lipson, Laser Photonics Rev. 1, 568 (2009).

    Article  Google Scholar 

  44. S. Alang Ahmad, L. S. Wong, E. Ul-Haq, J. K. Hobbs, G. J. Leggett, and J. Micklefield, J. Am. Chem. Soc. 131, 1513 (2009).

    Article  CAS  Google Scholar 

  45. H. Ma, M. Textor, R. L. Clark, and A. Chilkoti, BioInterphases 1, 35 (2006).

    Article  CAS  Google Scholar 

  46. A. Hucknall, A. J. Simnick, R. T. Hill, A. Chilkoti, A. Garcia, M. S. Johannes, R. L. Clark, S. Zauscher, and B. D. Ratner, BioInterphases 4, FA50 (2009).

    Article  CAS  Google Scholar 

  47. R. E. Ducker and G. J. Leggett, J. Am. Chem. Soc. 128, 392 (2006).

    Article  CAS  Google Scholar 

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Ahmad, S.A., Leggett, G.J., Hucknall, A. et al. Micro- and Nanostructured Poly[oligo(ethylene glycol)methacrylate] Brushes Grown From Photopatterned Halogen Initiators by Atom Transfer Radical Polymerization. Biointerphases 6, 8–15 (2011). https://doi.org/10.1116/1.3553579

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  • DOI: https://doi.org/10.1116/1.3553579