Chapter 20. Size-Exclusion Effect and Protein Repellency of Concentrated Polymer Brushes Prepared by Surface-Initiated Living Radical Polymerization

  1. Prof. Dr. Michael Buback5 and
  2. A. M. van Herk6
  1. Chiaki Yoshikawa1,
  2. Atsushi Goto1,
  3. Norio Ishizuka2,
  4. Kazuki Nakanishi3,
  5. Akio Kishida4,
  6. Yoshinobu Tsujii1 and
  7. Takeshi Fukuda1

Published Online: 31 MAY 2007

DOI: 10.1002/9783527610860.ch20

Radical Polymerization: Kinetics and Mechanism, Volume 248

Radical Polymerization: Kinetics and Mechanism, Volume 248

How to Cite

Yoshikawa, C., Goto, A., Ishizuka, N., Nakanishi, K., Kishida, A., Tsujii, Y. and Fukuda, T. (2007) Size-Exclusion Effect and Protein Repellency of Concentrated Polymer Brushes Prepared by Surface-Initiated Living Radical Polymerization, in Radical Polymerization: Kinetics and Mechanism, Volume 248 (eds M. Buback and A. M. van Herk), Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany. doi: 10.1002/9783527610860.ch20

Editor Information

  1. 5

    Institute of Physical Chemistry, Georg-August-University Göttingen, Tammannstrasse 6, D-37077 Göttingen, Germany

  2. 6

    Laboratory for Polymer Chemistry, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven, The Netherlands

Author Information

  1. 1

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

  2. 2

    Emaus Kyoto, Shimotsubayashi, Nishikyo-ku, Kyoto 615-8035, Japan

  3. 3

    Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan

  4. 4

    Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University, Chiyoda, Tokyo 101-0062, Japan

Publication History

  1. Published Online: 31 MAY 2007
  2. Published Print: 13 APR 2007

ISBN Information

Print ISBN: 9783527320561

Online ISBN: 9783527610860

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Keywords:

  • radical polymerization;
  • kinetics;
  • mechanism;
  • polymer reaction engineering;
  • polymer materials;
  • biocompatibility;
  • biointerface;
  • living radical polymerization;
  • polymer brush;
  • protein;
  • size exclusion;
  • PHEMA-grafted column

Summary

The adsorption of proteins on poly(2-hydroxyethyl methacrylate) (PHEMA) brushes was systematically investigated from the viewpoint of the size-exclusion effect of the concentrated brushes. By use of surface-initiated atom transfer radical polymerization, well-defined, concentrated PHEMA brushes were successfully grafted on the inner surface of the silica monolithic column with meso pores of ca. 80 nm as well as a silicon wafer and a quartz crystal microbalance (QCM) chip. By eluting low-polydispersity pullulans with different molecular weight through the modified monolithic column, the concentrated PHEMA brush was characterized and demonstrated to sharply exclude solute molecules with the critical molecular size (size-exclusion limit) comparable to the distance between the nearest-neighbouring graft points d. The elution behaviours of proteins with different sizes were studied with this PHEMA-grafted column: the protein sufficiently larger than the critical size was perfectly excluded from the brush layer and separated only in the size-exclusion mode by the meso pores without affinity interaction with the brush surface. Then, the irreversible adsorption of proteins on PHEMA brushes was investigated using QCM by varying graft densities (σ=0.007, 0.06, and 0.7 chains/nm2) and protein sizes (effective diameter=2–13 nm). A good correlation between the protein size and the graft density was observed: proteins larger than d caused no significant irreversible adsorption on the PHEMA brushes. Thus, we experimentally substantiated the postulated size-exclusion effect of the concentrated brushes and confirmed that this effect plays an important role for suppressing protein adsorption.