Strongly Stretched Protein Resistant Poly(ethylene glycol) Brushes Prepared by Grafting-To

Publication year: 2015
Authors: Gustav Emilsson †, Rafael L. Schoch ‡, Laurent Feuz , Fredrik Höök †, Roderick Y. H. Lim ‡, and Andreas B. Dahlin *†
Affiliations:
 Department of Applied Physics, Chalmers University of Technology, 41296 Göteborg, Sweden
 Biozentrum and the Swiss Nanoscience Institute, University of Basel, 4056 Basel, Switzerland
Published in: ACS Applied Materials & Interfaces, 2015, 7 (14), pp 7505–7515
doi: 10.1021/acsami.5b01590

We present a new grafting-to method for resistant “non-fouling” poly(ethylene glycol) brushes, which is based on grafting of polymers with reactive end groups in 0.9 M Na2SO4 at room temperature. The grafting process, the resulting brushes, and the resistance toward biomolecular adsorption are investigated by surface plasmon resonance, quartz crystal microbalance, and atomic force microscopy. We determine both grafting density and thickness independently and use narrow molecular weight distributions which result in well-defined brushes. High density (e.g., 0.4 coils per nm2 for 10 kDa) and thick (40 nm for 20 kDa) brushes are readily achieved that suppress adsorption from complete serum (10× dilution, exposure for 50 min) by up to 99% on gold (down to 4 ng/cm2 protein coverage). The brushes outperform oligo(ethylene glycol) monolayers prepared on the same surfaces and analyzed in the same manner. The brush heights are in agreement with calculations based on a simple model similar to the de Gennes “strongly stretched” brush, where the height is proportional to molecular weight. This result has so far generally been considered to be possible only for brushes prepared by grafting-from. Our results are consistent with the theory that the brushes act as kinetic barriers rather than efficient prevention of adsorption at equilibrium. We suggest that the free energy barrier for passing the brush depends on both monomer concentration and thickness. The extraordinary simplicity of the method and good inert properties of the brushes should make our results widely applicable in biointerface science.


MP-SPR keywords: grafting density, interaction, PEG, polymer brushes, protein resistance, stretching, thickness