Enhanced Solubility and Electron Transfer of Osmium-Based Mediators via Quaternized Poly(4-Vinylpyridine) for Electrochemical Glucose Detection.

Hydrophilic polymer-osmium complexes enhance electron transfer between enzymes and electrodes in biosensors. In this study, hydrophobic poly(4-vinylpyridine) (PVP) was quaternized with 2-bromoethanol to synthesize water-soluble PVP(Q)-C2H4OH polymers (MW 60,000 and 160,000). The resulting PVP(Q)-C2H4OH-Os(dmo-bpy)2Cl complexes were verified by UV-Vis, FT-IR, 1H NMR, SEM-EDS, and zeta potential analyses, confirming successful quaternization and osmium coordination with good dispersion stability. Electrochemical tests (cyclic voltammetry, multi-potential step, amperometry) demonstrated that electrodes with quaternized mediators showed greatly enhanced catalytic currents for glucose (0-20 mM), with sensitivities of 6.9791 (MW 60,000) and 6.6279 μA·mM-1·cm-2 (MW 160,000), respectively, which were 6.6-10.3 times higher than those of non-quaternized polymers. Selectivity tests showed negligible interference from common species such as ascorbic acid, dopamine, uric acid, and serotonin. Continuous glucose monitoring (CGM) electrodes were fabricated by immobilizing the mediator and glucose dehydrogenase on silanized Au electrodes. SEM, scan rate, and impedance analyses confirmed stable binding. The modified electrodes showed strong linearity (R2 = 0.992) and high sensitivity (2.56 μA·mM-1·cm-2), and good stability, maintaining ~82% activity for seven days. Human plasma testing validated accurate glucose detection (6.05 mM), consistent with physiological levels. Overall, quaternized PVP(Q) mediators significantly improved solubility and electron transfer, enabling the development of a stable, selective glucose sensor suitable for CGM applications.