Abstract
Electrokinetic modelling and experimental studies are conducted on an adsorption system, with a model redox-active adsorbate 3,3′,5,5′-tetramethylbenzidine (TMB), strongly adsorbed to a platinum nanoparticle (PtNP)-modified porous laser induced graphene (LIG) surface. The adsorption-assisted system defined here involves an electrochemical reaction coupled to a preceding, surface-bound, chemical oxidation of the adsorbate. TMB is also known to undergo intermediate reversible dimerization during oxidation. A shift in the general expressions governing the voltammetric trends due to this reversible dimerization step, and the associated impact on the electrokinetic parameters is presented here for the first time. Impedance analysis reveals a modified Randles circuit, with the faradaic contribution of the adsorbate represented by a CPE circuit component. The adsorption-associated phasance, Qads, is expressed as a function of the surface concentrations, ΓO and ΓR, of the oxidised and reduced forms. Changes in the total surface concentration of the adsorbate, Γm, as a result of the presence of localised non-conductive entities, such as proteins, can be correlated to Qads, and subsequently, this capacitive change can be utilised for affinity sensing of an antigen on a specific immunosurface. Proof of concept is carried out with the immunosensing of a model protein, rheumatoid factor, on a PtNP-modified LIG surface biofunctionalised with the specific capture probe, the Fc fragment of IgG. The relationship between the antigenic concentration CRF, Qads and Γm is established. This label-free, adsorption-assisted, capacitive biosensing mechanism has not be reported previously, to the best of our knowledge, with a linear range of 0–300 U mL−1 and an LOD of 0.515 U mL−1 in spiked serum samples, comparable to the gold standard, ELISA.
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