Electrochemical immunosensors are affinity-based biosensors characterized by several useful features such as specificity, miniaturizability, low cost and simplicity, making them very interesting for many applications in several scientific fields. One of the significant issues in the design of electrochemical immunosensors is to increase the system’s sensitivity. Different strategies have been developed, one of the most common is the use of nanostructured materials as electrode materials, nanocarriers, electroactive or electrocatalytic nanotracers because of their abilities in signal amplification and biocompatibility. In this review, we will consider some of the most used nanostructures employed in the development of electrochemical immunosensors (e.g., metallic nanoparticles, graphene, carbon nanotubes) and many other still uncommon nanomaterials. Furthermore, their diagnostic applications in the last decade will be discussed, referring to two relevant issues of present-day: the detection of tumor markers and viruses.
One of the main problems in the development of immunosensors is to overcome the complexity of binding antibody to the sensor surface. Most of immobilizing methods lead to a random orientation of antibodies with a lower binding site density and immunoaffinity. In order to control the orientation of antibody immobilization, several resorc[4]arene derivatives were designed and synthesized. After the spectroscopic characterization of resorc[4]arene self-assembled monolayers (SAMs) onto gold films, the surface coverage and the orientation of insulin antibody (Ab-Ins) were assessed by Surface Plasmon Resonance (SPR) technique and compared with a random immobilization method. Experimental results combined with theoretical studies confirmed the dipole-dipole interaction as an important factor in antibody orientation and demonstrated the importance of the upper rim functionalization of resorcarenes. Accordingly, resorcarene 5 showed a major binding force towards Ab-Ins thanks to the H-bond interactions with the amine protein groups. Based on these findings, the resorcarene-based immunosensor is a powerful system with improved sensitivity providing new insight into sensors development.
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