Synthesis of homogeneously distributed gold nanoparticles built-in metal free organic framework: Electrochemical detection of riboflavin in pharmaceutical and human fluids samples

This study describes the synthesis of gold nanoparticles (AuNPs) incorporated melamine based covalent organic framework (MCOF) and their modification on glassy carbon electrode (GCE) for the sensitive and selective detection of riboflavin (RF). The MCOF was synthesized by refluxing melamine and terephthalaldehyde followed by AuNPs were incorporated into MCOF. The synthesized nanocomposite (MCOF-AuNPs) was confirmed by different spectral, microscopic and electrochemical methods. The TEM images show spherical AuNPs with an average diameter of 8 nm on the sheet-like structure of MCOF. The heterogeneous electron transfer rate constant (k_et) was calculated for 1 mM K₃/K₄[Fe(CN)₆] containing 0.1 M KCl at bare GC, MCOF and MCOF-AuNPs/GCEs was found to be 1.14, 1.72 and 4.31 × 10^-4 cm² s⁻¹, respectively. The higher k_et value achieved at MCOF-AuNPs/GCE indicates that the electron transfer rate reaction was faster at this electrode than others. The MCOF-AuNPs modified electrode was then utilized for the reduction of RF in 0.2 M phosphate-buffered saline (PBS) (pH 7.0). The MCOF-AuNPs/GCE showed 3.0 and 1.7-fold higher reduction current with 40 and 60 mV less positive potential shift against RF than bare GCE and MCOF/GCE. Under the optimized sensing parameters, the linear range concentration was achieved from 5 nM to 0.2 mM with the LOD of 2.0 nM. Finally, the present sensor was applied for the quantitative determination of RF in human biological fluids samples (human blood, urine, and saliva). Besides, the practical application was also demonstrated by determining RF in vitamin B-complex tablets and satisfactory results were obtained.