Ultrasensitive multiwall carbon nanotube-mesoporous MCM-41 hybrid-based platform for the electrochemical detection of ascorbic acid.

This work presents for the first time the systematic preparation of a novel carbon nanotube-MCM-41 hybrid employing the mesoporous material MCM-41 as a successful dispersant for multiwall carbon nanotubes (MWCNTs). Relevant dispersion variables such as the amount of MWCNTs, MCM-41 concentration, and sonication time were optimized through a central composite design (CDD)/response surface methodology (RSM). Several solvents were evaluated and N,N-dimethylformamide (DMF) was selected because it allowed reaching stable dispersions with very good electrochemical response. The electrochemical performance of glassy carbon electrodes (GCE) modified with different hybrids was evaluated by cyclic voltammetry (CV) using ascorbic acid (AA) as redox marker, while their surface morphology was characterized by SEM microscopy. The optimal MWCNT-MCM-41 dispersion condition was 0.75 mg mL-1 MWCNTs, 0.25 mg mL-1 MCM-41, and 30 min sonication. Both, electrochemical results and SEM images correlate with a percolation behavior from MWCNT-MCM-41 hybrid. Electrooxidation of AA at GCE modified with the optimal hybrid occurred under diffusion control and exhibited an enhanced current response (65 µA) and a lower overvoltage (-0.005 V) compared to bare GCE (ip = 22 µA, Ep = 0.255 V). The amperometric response of AA at GCE/MWCNT-MCM-41 exhibited remarkable figures of merit, including an ultralow detection limit (1.5 nM), high sensitivity (45.4 × 103 µA M-1), excellent short- and long-term stability, and very good anti-interference ability for AA detection. The analytical applicability of the developed electrochemical sensor was evaluated by sensing AA in several real samples, showing excellent correlation with the values reported by manufacturers in both pharmaceutical and food samples.

Detection of perfluorooctane sulfonate by ion-transfer stripping voltammetry at an array of microinterfaces between two immiscible electrolyte solutions.

Per- and polyfluoroalkyl substances (PFAS) are a category of persistent environmental contaminants that have been linked to health issues in humans. In this work, we investigate the detection of perfluorooctanesulfonate (PFOS-), one such PFAS, by ion-transfer voltammetry at an array of microinterfaces between two immiscible electrolyte solutions (µITIES). Cyclic voltammetry, differential pulse voltammetry and differential pulse stripping voltammetry (DPSV) indicated the ion-transfer behaviour and detection of PFOS-, with the latter enabling detection at picomolar concentrations. Using a 5 min preconcentration time, during which PFOS- was preconcentrated into the organic phase of the µITIES array, a limit of detection (LOD) of 0.03 nM (0.015 µg L-1) in aqueous electrolyte was achieved. This performance is attributed to the enhanced mass transport (radial diffusion) to the µITIES that occurs during preconcentration. To investigate the potentiality for applications of this analytical approach to environmental samples, measurements in a range of water matrices were investigated. Drinking water, laboratory tap water and seawater matrices were assessed by spiking with PFOS- over the 0.1-1 nM range. A matrix effect was observed, with changes in sensitivity and LOD relative to those in pure aqueous electrolyte solutions. Such matrix effects need to be considered in designing applications of these PFOS- measurements to environmental samples. The results presented here indicate that DPSV at a µITIES array can form the basis for a fast and sensitive screening method for PFOS- contamination that is suited to portable and on-site applications.