SERS Sensor for Acetylcholine Detection Based on Covalent Organic Framework Hybridized Gold Nanoparticles As Nanozymes

An innovative and potent nanozyme with reductase-like activity was developed by integrating the in situ synthesis of gold nanoparticles (Au NPs) onto the surface of a covalent organic framework (COF). Based on the reductase-like activity of the COF-hybridized Au NPs, this nanozyme could efficiently catalyze the reduction of 4-nitrophenol (4-NPH). Moreover, the prepared nanohybrid was utilized as an excellent surface-enhanced Raman scattering (SERS) substrate for highly sensitive SERS detection by combining the excellent adsorption properties of COFs and the large number of Raman hotspots between the high-density Au NPs. For the first time, 4-NPH was used as an SERS marker to detect the electron receptor acetylcholine (Ach), with high sensitivity; Ach acted as an inhibitor in this catalytic reaction. The linear range of Ach was 1.0 pM to 10 nM, the correlation coefficient was 0.993, the detection limit was approximately 0.3 pM with a signal-to-noise ratio (s/n) of 3, and the acceptable recovery in the serum was 97.2% to 104.5%. The results from this study show that the nanozyme-SERS system has great potential for chemical and bioassay applications.