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We note that absorbances in reflectance FTIR spectra depend on the orientation of the transition dipole with respect to the surface normal (see: Allara, D.L.; Nuzzo, R.G. Langmuir 1985, 1, 52.). Because partial desorption of the SAM may result in orientation changes of the remaining carbonyl groups attached to the surface, estimates of surface coverage from IR spectra are only approximate.
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note
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Thickness data for initiator layers suggest that coverage by initiator A on Au may be less than that of initiator C on aluminum, whereas initiator B on Au has a similar coverage to that of initiator C on aluminum. All of the initiator layers on gold should still be dense enough to initiate polymerization.
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29
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0011318532
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note
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It must be pointed out that the amount of AIBN in solution is 104 times larger than the amount of azo-initiator in the monolayer. Therefore, the effect of radicals from initiator monolayers could be less than the effect of radicals from AIBN. However, radicals formed from immobilized initiators will be concentrated at the surface.
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30
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0011331208
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note
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Direct detection of the formation of cyclic or linear sulfides would not be possible because of the very small number of molecules in a SAM.
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