Investigation of Ion Transport in Polypyrrole Modified Ultra-Microelectrodes During Scanning Electrochemical Microscopy

Scanning electrochemical microscopy (SECM) is an electrochemical technique used to measure faradaic current changes local to the surface of a sample. The incorporation of shear force (SF) feedback in SECM enables the concurrent acquisition of topographical data of substrates along with electrochemical measurements. Contemporary SECM measurements require a redox mediator such as ferrocene methanol (FcMeOH) for electrochemical measurements; however, this could prove detrimental in the imaging of biological cells. In this article, nanoscale polypyrrole membranes doped with dodecylbenzene sulfonate (PPy(DBS)) are deposited at the tip of an ultra-microelectrode (UME) to demonstrate a novel modification of the contemporary SECM-SF imaging technique that operates in the absence of a redox mediator. The effect of distance from an insulating substrate and bulk electrolyte concentration on sensor response are examined to validate this technique as a tool for correlated topographical imaging and cation flux mapping. Varying the distance of the PPy(DBS) tipped probe from the substrate in a solution containing NaCl causes a localized change in cation concentration within the vicinity of the membrane due to hindered diffusion of ions from the bulk solution to the diffusion field. The cation transport into the membrane in close proximity to the substrate is low as compared to that in the electrolyte bulk and asymptotically approaches the bulk value at the sense length. At a constant height from the base, changing the bulk NaCl concentration from 5 mM to 10 mM increases the filling efficiency from 35% to 70%. Further, the sense length of this modified electrode in NaCl is about 440 nm which is significantly lower as compared to that of a bare electrode in ferrocene methanol (5–20 μm). It is postulated that this novel technique will be capable of producing high resolution maps of surface cation concentrations, thus having a significant impact in the field of biological imaging.

Adsorption isotherms for coadsorption studies from solution

The mixed adsorption of k adsorbates from solution on energetically homogeneous surfaces is studied by means of lattice statistical thermodynamics. The adsorption layer is considered to behave as a non-electrolyte bulk solution composed from k adsorbates and solvent. On the basis of this assumption the adsorption isotherms and their state equations are determined by means of the lattice theory of strictly regular solutions and Flory–Huggins statistics. The thermodynamic restrictions imposed when these models have to be applied to real systems are also determined and discussed.