Optimisation of the conditions for stripping voltammetric analysis at liquid-liquid interfaces supported at micropore arrays: a computational simulation

Micropore membranes have been used to form arrays of micro interfaces between immiscible electroly tesolutions (μITIES) as a basis for the sensing of non-redoxactiveions. Implementation of stripping voltammetry as asensing method at these arrays of μITIES was applied recently to detect drugs and biomolecules at low concentrations. The present study uses computational simulation to investigate the optimum conditions for stripping voltammetricsensing at the μITIES array. In this scenario, thediffusion of ions in both the aqueous and the organic phasescontributes to the sensing response. The influence of the preconcentration time, the micropore aspect ratio, the location of the micro interface within the pore, the ratio of the diffusion coefficients of the analyte ion in the organic and aqueous phases, and the pore wall angle were investigated. The simulations reveal that the accessibility of the microinterfaces during the preconcentration period should not be hampered by a recessed interface and that diffusional transport in the phase where the analyte ions are preconcentrated should be minimized. This will ensure that the ions are accumulated within the micropores close to the interface and thus be readily available for back transferduring the stripping process. On the basis of the results, an optimal combination of the examined parameters is proposed,which together improve the stripping voltammetric signal and provide an improvement in the detection limit

Ion-Transfer Voltammetric Behavior of Propranolol at Nanoscale Liquid-Liquid Interface Arrays

In this work, the ion-transfer voltammetric detection of the protonated β-blocker propranolol was explored at arrays of nanoscale interfaces between two immiscible electrolyte solutions (ITIES). Silicon nitride nanoporous membranes with 400 pores in a hexagonal arrangement, with either 50 or 17 nm radius pores, were used to form regular arrays of nanoITIES. It was found that the aqueous-to-organic ion-transfer current continuously increased steadily rather than reaching a limiting current plateau after the ion-transfer wave; the slope of this limiting current region was concentration dependent and associated with the high ion flux at the nanointerfaces. Electrochemical data were examined in terms of an independent nanointerface approach and an equivalent microdisc approach, supported by finite element simulation. In comparison to the larger interface configuration (50 nm radius), the array of 17 nm radius nanoITIES exhibited a 6.5-times higher current density for propranolol detection due to the enhanced ion flux arising from the convergent diffusion to smaller electrochemical interfaces. Both nanoITIES arrays achieved the equivalent limits of detection, 0.8 μM, using cyclic voltammetry. Additionally, the effect of scan rate on the charging and faradaic currents at these nanoITIES arrays, as well as their stability over time, was investigated. The results demonstrate that arrays of nanoscale liquid–liquid interfaces can be applied to study electrochemical drug transfer, and provide the basis for the development of miniaturized and integrated detection platforms for drug analysis

Ion-Transfer Voltammetric Behavior of Protein Digests at Liquid|Liquid Interfaces

The development of new methods for the detection of proteins and peptides is of widespread importance. In this work, the electrochemical behavior of peptide mixtures resulting from proteolytic digestion of proteins was investigated at the polarized liquid|liquid interface (or the interface between two immiscible electrolyte solutions, ITIES). The influence of pepsin digestion on three proteins (hemoglobin, lysozyme, and cytochrome c) was studied, and it was revealed that resulting cyclic voltammograms of the three protein digests were different due to the unique peptide mixtures for a given protein. Differential pulse stripping voltammetry of protein digests enabled the detection of digested proteins at concentrations ranging between 0.55 and 4.22 M. A limit of detection of 0.55 M of the initial concentration of protein was achieved, demonstrating the analytical possibilities of such an electrochemical method. These results show that ion transfer voltammetry offers the opportunity to study and develop label-free detection of peptides resulting from enzymatic digestions of proteins and may thus have a role in development of new proteomic technologies