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Chemisorption of thiolated poly(ethylene oxide) to gold: surface chain densities measured by ellipsometry and neutron reflectometry

Larry D. Unsworth, Zin Tun, Heather Sheardown, John L. Brash
Journal of Colloid and Interface Science 281 (2005) 112-121

Uns2005.htm

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Journal
Abstract
Introduction
Notes by Dr. Zin Tun

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The Journal

 

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Abstract

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Introduction

   Poly (ethylene oxide) (PEO)-modified surfaces have attracted much attention due to their excellent anti-biofouling properties [1-4]. In particular they have been shown to be resistant to nonspecific protein adsorption. An important class of such materials are formed by grafting, i.e., attachment of PEO to the surface via the polymer chain ends. Although the mechanism of protein resistance on these surfaces is not entirely clear, it is believed that the PEO chain length, surface chain density, and chain conformation are important factors [3,5]. -- (Uns2005intro01.gif)

   Alexander [6] has pointed out that the conformation of end-tethered chains on a surface depends on the chain density (Fig. 1). A random coil conformation (mushroom regime) occurs when the graft spacing (S) is greater than 2 RF (RF is the Flory radius), and a more extended conformation (brush regime) occurs when S < 2 RF . It is also well understood that stretching-entropy and excluded-volume interactions influence the chain density in the brush regime, in both cases as a result of lateral confinement. Thus by varying chain density, chain conformation ranging from unperturbed random coil to fully extended can, in principle, be obtained. -- (Uns2005intro02.gif)

   The focus of the present work is to produce well-characterized PEO-grafted surfaces of variable chain density and chain length to allow a detailed study of the influence of these parameters on protein resistance. In this article the preparation and characterization of a series of surfaces prepared by chemisorption of chain-end thiolated PEO (molecular weight range 750-5000) to gold is reported . Such a system should in principle allow variation of chain density up to high values, with an absolute upper limit corresponding to the density of thiol binding sites on gold. (Uns2005intro03.gif)

   The coupling of polymers and other molecules to gold by reaction with thiol groups has been widely reported [7-10]. A system that has been investigated extensively consists of intermediate-length alkanes (e.g., C-11), thiol-terminated at one end and "tipped" or not with an oligoethylene oxide (OEO) moiety at the other end. In these systems the ratio of OEO-terminated  to non-OEO-terminated chains was used to control the effective PEO chain density on the surface [8-10]. The PEO chain length was in the range of three to six ethylene oxide units. (Uns2005intro04.gif)

 

 

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Notes by Dr. Zin Tun

 

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End of TIL file