Self‐assembled monolayers of alkylsiloxanes supported on polydimethyl siloxane (PDMS) rubber were used as model systems to study the relation between blood compatibility and surface chemistry. The inner lumen of PDMS tubes was first treated with an oxygen plasma. The resultant oxidized surfaces were postderivatized by reacting them with alkyltrichlorosilanes to form the monolayer films. The chemical properties of the monolayers were controlled by varying the head‐group chemical compositions. Surface derivatization was verified using variable‐angle X‐ray photoelectron spectroscopy (XPS or ESCA). Blood compatibility was evaluated using a canine ex vivo arteriovenous series shunt model. Surfaces grafted with hydrophobic head‐groups as ‐CH3 and ‐CF3 had significantly lower platelet and fibrinogen deposition than the surfaces composed of hydrophilic groups such as ‐CO2CH3, ‐(CH2CH2O)3COCH3, and ‐(OCH2CH2)3OH. © 1995 John Wiley & Sons, Inc.
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