This article reviews recent progress in the development of nanomaterial-based electrochemical biosensors for cancer biomarkers. Because of their high electrical conductivity, high affinity to biomolecules, and high surface area-to-weight ratios, nanomaterials, including metal nanoparticles, carbon nanotubes, and graphene, have been used for fabricating electrochemical biosensors. Electrodes are often coated with nanomaterials to increase the effective surface area of the electrodes and immobilize a large number of biomolecules such as enzymes and antibodies. Alternatively, nanomaterials are used as signaling labels for increasing the output signals of cancer biomarker sensors, in which nanomaterials are conjugated with secondary antibodies and redox compounds. According to this strategy, a variety of biosensors have been developed for detecting cancer biomarkers. Recent studies show that using nanomaterials is highly advantageous in preparing high-performance biosensors for detecting lower levels of cancer biomarkers. This review focuses mainly on the protocols for using nanomaterials to construct cancer biomarker sensors and the performance characteristics of the sensors. Recent trends in the development of cancer biomarker sensors are discussed according to the nanomaterials used.

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.

We review the synthesis of dendrimer-containing layer-by-layer (LbL) assemblies and their applications, including biosensing, controlled drug release, and bio-imaging. Dendrimers can be built into LbL films and microcapsules by alternating deposition of dendrimers and counter polymers on the surface of flat substrates and colloidal microparticles through electrostatic bonding, hydrogen bonding, covalent bonding, and biological affinity. Dendrimer-containing LbL assemblies have been used to construct biosensors, in which electron transfer mediators and metal nanoparticles are often coupled with dendrimers. Enzymes have been successfully immobilized on the surface of electrochemical and optical transducers by forming enzyme/dendrimer LbL multilayers. In this way, high-performance enzyme sensors are fabricated. In addition, dendrimer LbL films and microcapsules are useful for constructing drug delivery systems because dendrimers bind drugs to form inclusion complexes or the dendrimer surface is covalently modified with drugs. Magnetic resonance imaging of cancer cells by iron oxide nanoparticles coated with dendrimer LbL film is also discussed.