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Patterned and switchable surfaces for biomaterial applications

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Andrew Hook – <strong>Patterned</strong> <strong>and</strong> <strong>switchable</strong> <strong>surfaces</strong> <strong>for</strong> <strong>biomaterial</strong> <strong>applications</strong>The absence of a Si signal on the Si-ALAPP <strong>surfaces</strong> (Table 2.1) stronglysuggests that pinhole-free films with a thickness of more than 10 nm (theapproximate penetration depth of XPS <strong>for</strong> polymers) were <strong>for</strong>med. The oxygencontent of this film is due to the uptake of oxygen once it is re-exposed to air byreaction with long-lived reactive species in the polymer film such as free radicals[183, 184]. Upon subsequent grafting of PEG to the amino groups of the ALAPPcoating, a significant decrease in the nitrogen content (11.0% to 5.7%) <strong>and</strong> anaccompanying rise in the oxygen content (9.0% to 21.0%) was observed.Furthermore, the C 1s spectrum in Figure 2.4B shows a large increase in the C-O/C-N component <strong>and</strong> a relative decrease in the aliphatic carbon peak <strong>and</strong> higher oxidisedcarbon components as compared with the ALAPP film (Figure 2.4A; Table 2.2).These results suggest not only that PEG was successfully grafted to the ALAPP, butalso that amino groups were indeed present on the ALAPP surface. The presence of anitrogen signal <strong>for</strong> the PEG grafted surface suggests that this layer is less than 10 nmthick. The theoretical length of a fully extended PEG chain with a molecular weightof 5000 is approximately 42 nm [65]. The large difference between this theoreticalvalue <strong>and</strong> the observed value is due both to the low persistence length of PEGr<strong>and</strong>om coils <strong>and</strong> to the fact that the XPS measurements were taken in the dry statewhere the grafted polymer is collapsed. A recent study by Zdryko et al., 2003 [65]reports a greater than 3 fold swelling of the PEG layer in an aqueous environment ascompared to a dry sample.2-77

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