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| - Orientation Modulation of a Synthetic Polypeptide inSelf-Assembled Monolayers: A TOF-SIMS Study
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| - Structure and orientation of molecules are key properties of functionalized surfaces. Using time-of-flight secondary ion mass spectrometry (TOF-SIMS), here we investigate how to modulate theseparameters upon the immobilization process varying the conditions of self-assembly. The molecule ofinterest, a template-assembled synthetic protein (TASP), consists of a central peptide ring with orthogonallyarranged residues. Thioalkane chains allow the directed self-assembly of the molecule on a gold surface;four serine residues on the opposite side of the ring can be used as anchoring sites for various functionalsensing molecules. The TASP conformation and its orientation in self-assembled monolayers (SAMs) playa central role for the accessibility of these serine residues. To study the influence of the self-assemblyconditions, two series of samples were prepared. Pure TASP monolayers of different surface densities arecompared to mixed TASP/alkanethiol monolayers prepared by sequential adsorption varying sequenceand particular incubation times as well as by coadsorption modifying incubation times and TASP/alkanethiolmass ratios. Switching the TASP orientation from a state where the molecules are lying flat on the surfaceto an upright orientation turned out to be possible by inserting the TASP into a preformed alkanethiolmonolayer of an appropriate surface density. This study demonstrates that TOF-SIMS is an excellent toolnot only to investigate the surface composition, but also the molecular structure of functionalized surfaces.
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