Controlled decoration of the surface with macromolecules: polymerization on a self-assembled monolayer (SAM).

Polymer functionalized surfaces are important components of various sensors, solar cells and molecular electronic devices. In this context, the use of self-assembled monolayer (SAM) formation and subsequent reactions on the surface have attracted a lot of interest due to its stability, reliability and excellent control over orientation of functional groups. The chemical reactions to be employed on a SAM must ensure an effective functional group conversion while the reaction conditions must be mild enough to retain the structural integrity. This synthetic constraint has no universal solution; specific strategies such as "graft from", "graft to", "graft through" or "direct" immobilization approaches are employed depending on the nature of the substrate, polymer and its area of applications. We have reviewed current developments in the methodology of immobilization of a polymer in the first part of the article. Special emphasis has been given to the merits and demerits of certain methods. Another issue concerns the utility - demonstrated or perceived - of conjugated or non-conjugated macromolecules anchored on a functionally decorated SAM in the areas of material science and biotechnology. In the last part of the review article, we looked at the collective research efforts towards SAM-based polymer devices and identified major pointers of progress (236 references).