Electrode surface nanostructuring via nanoparticle electronucleation for signal enhancement in electrochemical genosensors.

Biosensor read out signals can be enhanced by carefully designing the transducer surfaces to achieve an optimal interaction between the recognition elements immobilised and the targeted analyte. This is particularly evident in the case of genosensors, where spacing and orientation of immobilised DNA capture probes need to be controlled to maximise subsequent surface hybridisation with the target sequence and achieve high binding signals. Addressing this goal, we present a novel approach based on the surface nanostructuring of glassy carbon electrodes (GCEs) towards the development of highly sensitive electrochemical genosensors. Gold nanoparticles were sequentially electrochemically nucleated on glassy carbon electrodes to form dense arrays of randomly distributed gold nanodomains. The number density of the electronucleated nanoparticles could be increased by repeatedly alternating between a short electronucleation step and the subsequent insulation of the nucleated nanoparticles with thiolated DNA probes. This approach allowed for the creation of highly structured surfaces whilst preventing aggregation of nanoparticles. The performances of planar gold electrodes and that of the nanopatterned surfaces prepared following several rounds of deposition were compared for the amperometric detection of DNA. Three rounds of deposition exhibited the highest sensitivity (44.89 nA × nM(-1)), with a dynamic detection range spanning from 0.53 nM to 25 nM of the targeted sequence, i.e. one order of magnitude lower than that obtained for the planar gold electrodes. The use of the nanostructured surface we report here may find application not only in DNA biosensors but also for any sensing application requiring highly sensitive measurements.

Electrochemical surface structuring with palladium nanoparticles for signal enhancement.

Surface nanostructuring with metal nanoparticles has gained importance because of the unique physicochemical properties of the nanoparticles. We have fabricated nanostructured surfaces on the basis of the sequential electrochemical deposition of palladium nanoparticles (Pd NPs) onto glassy carbon electrodes (GCEs). To increase the number density of the Pd NPs at the GC electrode surface, successive rounds of deposition/protection cycles were realized. Freshly deposited Pd NPs were immediately capped with 6-ferrocenylhexanethiol (Fc-C(6)SH) to prevent secondary nucleation processes from occurring during subsequent deposition rounds. This approach allowed us to maintain a narrow size distribution and, as such, the inherent properties of the deposited Pd NPs. Scanning electron microscopy (SEM) was used to confirm the successful deposition as well as to measure the size and spatial distribution of the deposited Pd NPs. SEM image analysis results showed that the number density of Pd NPs increased in each sequential deposition stage. The anodic peak current signal recorded for the electroactive SAM of Fc-C(6)SH following six consecutive deposition/protection cycles was found to be 75 times higher than that formed on a bulk palladium electrode. Finally, for comparison, gold NPs were deposited on GCEs following the same approach and exhibited considerably reduced signal enhancement properties as compared to the Pd NPs. The work presented here should find wide applicability for enhancing sensor signals by specifically structuring transducer surfaces on the nanoscale.

Electrochemically deposited palladium as a substrate for self-assembled monolayers.

The vast majority of reports of self-assembled monolayers (SAMs) on metals focus on the use of gold. However, other metals, such as palladium, platinum, and silver offer advantages over gold as a substrate. In this work, palladium is electrochemically deposited from PdCl2 solutions on glassy carbon electrodes to form a substrate for alkanethiol SAMs. The conditions for deposition are optimized with respect to the electrolyte, pH, and electrochemical parameters. The palladium surfaces have been characterized by scanning electron microscopy (SEM) and the surface roughness has been estimated by chronocoulometry. SAMs of alkane thiols have been formed on the palladium surfaces, and their ability to suppress a Faradaic process is used as an indication for palladium coverage on the glassy carbon. The morphology of the Pd deposit as characterized by SEM and the blocking behavior of the SAM formed on deposited Pd delivers a consistent picture of the Pd surface. It has been clearly demonstrated that, via selection of experimental conditions for the electrochemical deposition, the morphology of the palladium surface and its ability to support SAMs can be controlled. The work will be applied to create a mixed monolayer of metals, which can subsequently be used to create a mixed SAM of a biocomponent and an alkanethiol for biosensing applications.