Abstract: | We prepared two new linkers, S‐functionalized adamantane derivatives 2 and 3 , which bind as monolayers on polycrystalline gold. From these surface anchors, both L ‐ and D ‐isomers of alanine can be grown as thin films of α‐helical polypeptides directed from the gold surface by using the appropriate N‐carboxyalanine anhydride. FT‐IR Studies show that these layers are roughly 1000‐Å thick and that, under the same growth conditions, the L ‐polypeptide layers grow at a rate ca. 30% greater than that of the non‐natural D ‐amino acid. X‐Ray photoelectron spectroscopy studies show that, upon equilibration, all three S‐atoms of the sulfide moieties of 2 are bound to the gold surface, and that, on average, three of the four thiols of 3 are chemoadsorbed. The essential role of H2O on the surface of these films as a necessary component in these gas‐phase polymerization reactions is demonstrated. |