Positively Charged Gold Quantum Dots: An Nanozymatic “Off-On” Sensor for Thiocyanate Detection

The concentration of thiocyanate (SCN^-) in bodily fluids is a good indicator of potential and severe health issues such as nasal bleeding, goiters, vertigo, unconsciousness, several inflammatory diseases, and cystic fibrosis. Herein, a visual SCN^- sensing method has been developed using the enzyme-like nature of positively charged gold quantum dots (Au QDs) mixed with 3,3',5,5'-tetramethylbenzidine (TMB) and hydrogen peroxide (H₂O₂₎. This research also reports a new method of synthesizing positively charged Au QDs directly from gold nanoparticles through a hydrothermal process. Microscopic imaging has showed that the Au QDs were 3-5 nm in size, and the emission wavelength was at 438 nm. Au QDs did not display any enzyme-like nature while mixed up with TMB and H₂O₂. However, the nanozymatic activity of Au QDs appeared when SCN^- was included, leading to a very low detection limit (LOD) of 8 nM and 99-105% recovery in complex media. The steady-state kinetic reaction of Au QDs showed that Au QDs had a lower Michaelis-Menten constant (Km) toward H₂O₂ and TMB, which indicates that the Au QDs had a higher affinity for H₂O₂ and TMB than horseradish peroxidase (HRP). A mechanism study has revealed that the scavenging ability of hydroxyl (•OH) radicals by the SCN^- group plays an important role in enhancing the sensitivity in this study. The proposed nanozymatic "Off-On" SCN^- sensor was also successfully validated in commercial milk samples.