Unlocking the electrochemical performance of glassy carbon electrodes by surface engineered, sustainable chitosan membranes

Chitosan coatings, derived from crustacean shell waste, possess inherent biocompatibility and biodegradability, rendering them suitable for various biomedical and environmental applications, including electrochemical biosensing. Its amine and hydroxyl functional groups offer abundant sites for chemical modifications to boost the charge transfer kinetics and provide excellent adhesion, enabling the construction of robust electrode-coating interfaces for electroanalysis. This study explores the role of electrostatically-driven chemical interactions and crosslinking density originating from different chitosan (Cs) and glutaraldehyde (Ga) concentrations in this aspect. Studying anionic ([Fe(CN)₆]^3-/4-), neutral (FcDM^0/+), and cationic ([Ru(NH₃)₆]^2+/3+) redox probes highlights the influence of Coulombic interactions with chitosan chains containing positively-charged pathways, calculated by DFT analysis. Our study reveals how a proper Ch-to-Ga ratio has a superior influence on the cross-linking efficacy and resultant charge transfer kinetics, which is primarily boosted by up to 20× analyte preconcentration increase, due to electrostatically-driven migration of negatively charged ferrocyanide ions toward positively charged chitosan hydrogel. Notably the surface engineering approach allows for a two-orders of magnitude enhancement in [Fe(CN)₆]^4- limit of detection, from 0.1 µM for bare GCE down to even 0.2 nM upon an adequate hydrogel modification.