Silicon-based field-effect devices have been widely studied for label-free DNA detection in recent years. These devices rely on the detection of changes in the electrical surface potential during the DNA recognition event and thus require a reliable and selective immobilization of charged biomolecules on the device surface [1]. The preparation of self-assembled monolayers of phosphonic acids (SAMPs) on metal oxide surfaces is an efficient approach to generate well-defined organic interfaces with a high density of receptor binding sites close to the sensing surface [2,3]. In this work, we report the functionalization and characterization of silicon/silicon nitride surfaces with different types of peptide nucleic acid (PNA), a synthetic analogue to DNA [4]. Differently modified PNA molecules are covalently immobilized on the underlying SAMPs either in a multidentate or monodentate fashion to investigate the effect of different binding modes on receptor density and morphology important for PNA-DNA hybridization (Scheme 1). Multidentate immobilization of the bioreceptors via C6-SH attachment groups at the γ-points along the PNA backbone provides a rigid, lying configuration on the device surface (PNA 1), whereas a monodentate immobilization by Cys-capped PNA molecules (PNA 2) results in more flexible and more accessible receptor binding sites. Our results indicate that the presented functionalization scheme can be successfully applied to produce morphologically and electrochemically different PNA bioreceptor binding sites on silicon/silicon nitride surfaces. Consequently, a well-chosen modification of the PNA backbone is a valid approach to influence the sensing properties of surface-immobilized PNA bioreceptors, which might provide an additional parameter to further tune and tailor the sensing capabilities of PNA-based biosensing devices.
«