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Peroxidase-mimetic, electrochemically active, Co3O4-decorated pectic acid-based polyacrylate derivatives for rapid
1Polymers and Pigments Department, National Research Centre Dokki, P.O. Box. 12622 Giza Egypt ms.hashem@nrc.sci.eg.
Abstract:
In this work, a nanocomposite of a pectic acid (PcA)-based copolymer composed of acrylamide (Am) and acrylic acid (AcA) embedding cobalt oxide nanoparticles (Co3O4 NPs), PcA-g-poly(Am-co-AcA)/Co3O4, was fabricated as an enzyme-free electrochemical sensing platform for the sensitive detection of hydrogen peroxide (H2O2). This Co3O4 NP-based nanocomposite was developed through free radical-initiated grafting copolymerization and then characterized by Fourier-transform infrared (FT-IR) spectroscopy and transmission electron microscopy (TEM). Pectic acid-based polyacrylate derivatives decorated with Co3O4 NPs formed a larger nanocomposite aggregate with an average size of approximately 67 nm, as observed by TEM. Electrochemical techniques including cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) confirmed the superior charge-transfer capability and enlarged electrochemically active surface area of the nanocomposite-modified electrode compared with those of the bare electrode. Under the optimized experimental conditions, the fabricated sensor exhibited a rapid amperometric response, excellent sensitivity, a broad linear working range from 0.01 to 800 µM, an ultralow limit of detection (LOD) of 3 nM, a limit of quantification (LOQ) of 9 nM and high selectivity toward H2O2 in the presence of common interfering species. The Co3O4-based nanocomposite sensor demonstrated good repeatability with reproducibility besides long-term storage stability, highlighting its analytical reliability. The practical applicability of the sensing platform was successfully validated by determining H2O2 in commercial apple juice samples using the standard addition method, providing satisfactory recoveries and low relative standard deviations. The combination of a simple fabrication procedure, low-cost materials, and outstanding electrochemical performance makes the PcA-g-poly(Am-co-AcA)/Co3O4 nanocomposite a promising candidate for routine food safety monitoring and the development of advanced polymer-based nanozyme sensors, alongside its electroactivity exploitation in catalytic systems and other advanced bioelectronic technologies.