Synergistic effect of silver, reduced graphene oxide and metal-organic framework-5 nanocomposite for the simultaneous voltammetric sensing of darunavir and naproxen pharmaceutical analytes using chemometric methods

Abstract

Darunavir (DRV), a protease inhibitor widely prescribed for antiretroviral therapy, and naproxen (NAP), a nonsteroidal anti-inflammatory drug, are frequently co-administered in patients with HIV-related inflammatory conditions, necessitating their accurate and simultaneous quantification in biological matrices. This study addresses the critical need for a sensitive and reliable analytical platform for the concurrent detection of DRV and NAP in complex biological samples. Conventional methods often suffer from poor selectivity due to overlapping oxidation peaks and limited sensitivity. To overcome these challenges, we developed a novel electrochemical nanosensor based on a silver-decorated reduced graphene oxide/metal–organic framework-5 nanocomposite–modified carbon paste electrode (Ag@RGO@MOF-5/CPE). The hybrid nanomaterial synergistically combines the high electrical conductivity of RGO, the large surface area of MOF-5, and the strong electrocatalytic activity of silver nanoparticles. Under optimized conditions via response surface methodology, the Ag@RGO@MOF-5/CPE exhibited enhanced current response and reduced oxidation overpotential for DRV, and NAP. However, due to overlapping oxidation potentials of drugs, partial least squares-1 (PLS-1) regression was implemented to enable accurate simultaneous determination, yielding detection limits of 0.20 μM for DRV and 0.40 μM for NAP in Britton-Robinson buffer (pH 7.0). The overlapping peaks were efficiently resolved via PLS-1 regression, and this approach was applied for detection of DRV, and NAP in human plasma and urine samples with satisfactory recovery. Overall, the integration of PLS-1 effectively eliminates signal overlap and offering a rapid, cost-effective, and robust alternative to chromatographic techniques for therapeutic drug monitoring in HIV/inflammation co-treatments, ultimately enhancing clinical safety and pharmacological efficiency.