β-cyclodextrin-functionalized acetylene black nanocomposite electrode with enhanced host-guest enrichment for...

Accurate electrochemical quantification of niclosamide (NA) remains challenging due to its limited aqueous solubility, sluggish electron-transfer kinetics, and the inherently complex multi-electron nitro-reduction pathway. In this work, a β-cyclodextrin/acetylene black composite electrode (β-CD@AB/GCE) is developed to overcome these limitations through the combined benefits of a highly conductive porous carbon network and the strong host-guest inclusion capability of β-cyclodextrin. The composite architecture enhances interfacial preconcentration of NA, promotes favorable molecular orientation for electron transfer, and improves the efficiency of mass and charge transport throughout the porous film. To elucidate the mechanistic origins of these enhancements, a fully coupled multiphysics framework was constructed in COMSOL, integrating charge conservation, mass transport of diluted species, Butler-Volmer kinetics, and Langmuir adsorption dynamics. The model accurately captures experimentally observed behaviors (including potential gradients, ohmic polarization, concentration depletion, and the transition between diffusion-controlled and adsorption-controlled regimes) with excellent agreement between simulations and voltammetric measurements (RMSE = 0.078). Both modeling and experiments reveal that β-CD-mediated enrichment increases interfacial NA concentration by more than an order of magnitude, while the optimized porous microstructure ensures uniform overpotential distribution and efficient charge transfer. The resulting β-CD@AB/GCE sensor exhibits high sensitivity (3.675 µA µM^-1), a broad linear range, and an ultralow detection limit of 0.019 µM. The proposed electrochemical sensing platform, investigated entirely through COMSOL Multiphysics simulations, demonstrates a linear electrochemical response toward the target analyte within the concentration range of 0.05-10 µM. The simulated calibration curve yields the equation I _p = 0.192C + 0.015 (R ² = 0.996), corresponding to a detection limit of 0.02 µM. This broad and well-defined linear range confirms the strong quantitative capability of the simulated sensor design. These findings establish a mechanistic foundation for the rational design of β-cyclodextrin-functionalized carbon electrodes and provide a broadly applicable strategy for next-generation electrochemical sensors targeting hydrophobic nitroaromatic pharmaceuticals and related bioactive species.