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Chemisorbed poly(propylene sulphide)-based copolymers resist biomolecular interactions

Abstract

Alkanethiolates have been widely used as chemisorbates to modify gold surfaces, in spite of their relatively poor oxidative stability. We introduce gold-chemisorbing block copolymers bearing an anchoring block of poly(propylene sulphide) (PPS), selected in the expectation of greater stability. These materials offer a more robust approach to surface modification of gold. As an example, a triblock copolymer with poly(ethylene glycol) (PEG) was selected, with the goal of minimizing biological adsorption and adhesion. The copolymer PEG17-bl-PPS25-bl-PEG9 chemisorbed to form a dense monolayer of 226 ± 26 ng cm−2, 2.2 nm thick. The copolymeric adlayer was much more stable to oxidation than commonly used alkanethiolates. Its presence greatly reduced protein adsorption (>95%), even after exposure to whole blood serum (>55 mg ml−1), as well as cell adhesion over long culture durations (>97%). PPS-containing copolymers are an attractive alternative to alkanethiolates, and PEG-bl-PPS-bl-PEG presents a powerful example for use in biodiagnostic and bioanalytical devices.

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Figure 1: High-resolution S2p X-ray photoelectron spectra (in counts per second).
Figure 2: Surface plasmon resonance measurements.
Figure 3: Rat dermal fibroblasts cultured on gold surfaces coated with lines of the copolymer.

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Acknowledgements

This work was supported in part by a grant from the Swiss Commission for Technology and Innovation to M.T. and J.A.H. and a grant from the Swiss Top Nano21 program (project Nanocontainers) to H.V. Part of this work was performed under the auspices of the US Department of Energy by Lawrence Livermore National Laboratory under contract W-7405-Eng.48. We thank C. Orme, C. Evans and A. Nelson for assistance with the XPS acquisition, A. Christian and J. Montgomery for the rat fibroblasts, and B. Cheung for the PDMS microfluidic channels.

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Correspondence to J.A. Hubbell.

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Chemisorbed Poly(propylene sulfide)-based Copolymers for chemisorption on gold surfaces to resist biomolecular interactions (PDF 21 kb)

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Bearinger, J., Terrettaz, S., Michel, R. et al. Chemisorbed poly(propylene sulphide)-based copolymers resist biomolecular interactions. Nature Mater 2, 259–264 (2003). https://doi.org/10.1038/nmat851

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