The Release of Non-Extractable Ferulic Acid from Cereal By-Products by Enzyme-Assisted Hydrolysis for Possible Utilization in Green Synthesis of Silver Nanoparticles.

The present work was undertaken to elucidate the potential contribution of biosynthetically produced ferulic acid (FA) via enzymatic hydrolysis (EH) of rye bran (RB) to the formation of silver nanoparticles (AgNPs) during green synthesis. An analytical approach accomplished by multiple reaction monitoring (MRM) using triple quadrupole mass selective detection (HPLC-ESI-TQ-MS/MS) of the obtained hydrolysate revealed a relative abundance of two isomeric forms of FA, i.e., trans -FA ( t -FA) and trans - iso -FA ( t - iso -FA). Further analysis utilizing high-performance liquid chromatography with refractive index (HPLC-RID) detection confirmed the effectiveness of RB EH, indicating the presence of cellulose and hemicellulose degradation products in the hydrolysate, i.e., xylose, arabinose, and glucose. The purification process by solid-phase extraction with styrene-divinylbenzene-based reversed-phase sorbent ensured up to 116.02 and 126.21 mg g -1 of t -FA and t - iso -FA in the final eluate fraction, respectively. In the green synthesis of AgNPs using synthetic t -FA, the formation of NPs with an average size of 56.8 nm was confirmed by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) techniques. The inclusion of polyvinylpyrrolidone (PVP-40) in the composition of NPs during synthesis favorably affected the morphological features, i.e., the size and shape of AgNPs, in which as big as 22.4 nm NPs were engineered. Meanwhile, nearly homogeneous round-shaped AgNPs with an average size of 16.5 nm were engineered using biosynthetically produced a mixture of t -FA and t - iso -FA and PVP-40 as a capping agent. The antimicrobial activity of AgNPs against Gram-positive and Gram-negative bacteria, including Pseudomonas aeruginosa , E. coli , Enterococcus faecalis , Bacillus subtilis , and Staphylococcus aureus was confirmed by the disk diffusion method and additionally supported by values of minimum inhibitory (MIC) and bactericidal (MBC) concentrations. Given the need to reduce problems of environmental pollution with cereal processing by-products, this study demonstrated a technological solution of RB rational use in the sustainable production of AgNPs during green synthesis. The AgNPs can be considered as active pharmaceutical ingredients (APIs) to be used for developing new antimicrobial agents and modifying therapies in treating multi-drug resistant (MDR) pathogens.