This article reviews recent progress in the development of ferrocene (Fc)-modified thin films and nanoparticles in relation to their biosensor applications. Redox-active materials in enzyme biosensors commonly use Fc derivatives, which mediate electron transfer between the electrode and enzyme active site. Either voltammetric or amperometric signals originating from redox reactions of Fc are detected or modulated by the binding of analytes on the electrode. Fc-modified thin films have been prepared by a variety of protocols, including in situ
polymerization, layer-by-layer (LbL) deposition, host-guest complexation and molecular recognitions. In situ
polymerization provides a facile way to form Fc thin films, because the Fc polymers are directly deposited onto the electrode surface. LbL deposition, which can modulate the film thickness and Fc content, is suitable for preparing well-organized thin films. Other techniques, such as host-guest complexation and protein-based molecular recognition, are useful for preparing Fc thin films. Fc-modified Au nanoparticles have been widely used as redox-active materials to fabricate electrochemical biosensors. Fc derivatives are often attached to Au nanoparticles through a thiol-Au linkage. Nanoparticles consisting of inorganic porous materials, such as zeolites and iron oxide, and nanoparticle-based composite materials have also been used to prepare Fc-modified nanoparticles. To construct biosensors, Fc-modified nanoparticles are immobilized on the electrode surface together with enzymes.