Polymer-capped gold nanoparticles as nanozymes with improved catalytic activity for the monitoring of serum ciprofloxacin

Abstract

More recently, gold nanoparticle (AuNP)-based nanozymes have become one of the burgeoning research hot topics. However, few studies have focused on these AuNP-nanozymes with polymers as ligands. A significant challenge is to reveal their catalytic mechanism and to improve their catalytic activity by changing the structures of the polymers. In this study, polyacrylamide (PAM) with different chain lengths was synthesized and used as the ligand to prepare PAM@AuNPs. The resultant nanozymes exhibited good peroxidase-like activity for catalyzing the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) in the presence of hydrogen peroxide (H₂O₂). In particular, due to the electrostatic interaction between the negatively charged PAM@AuNPs and the positively charged drug, the addition of ciprofloxacin in the oxidation system induced the aggregation of PAM@AuNPs and produced more amount of reactive oxygen species, which greatly promoted the catalytic activity of PAM@AuNPs. Inspired by the attractive property, a highly selective and sensitive colorimetric assay for the monitoring of ciprofloxacin was created. A good linear relationship between the UV-Vis absorption intensity of PAM@AuNPs-TMB-H₂O₂ at 650 nm wavelength and the ciprofloxacin concentration was observed ranging from 1.0 μM to 12.0 μM (R² = 0.998), providing the detection limit of 0.5 μM. The ciprofloxacin metabolism was further studied in rats. It reveals great potential of polymer protected AuNP-nanozymes in practical drug analysis.