Spindle-shaped Cu-Ru mesoporous nanospheres with enhanced enzyme-like activity for visual differentiation of toxic o-/m-aminophenol and recognition mechanisms.

To effectively differentiate toxic aminophenol isomers, a kind of spindle-shaped Cu-Ru bimetal mesoporous nanozyme (Cu-Ru MPNZ) with high specific surface was developed by one-pot homogeneous reduction method, directed by hexadecyl trimethyl ammonium bromide (CTAB) in this work. By virtue of the distinctive microstructure, Cu-Ru MPNZ expressed superior bi-functional oxidase- and peroxidase-mimic activity to catalyze the oxidation of 3,3',5,5,'-tetramethylbenzidine (TMB) and 2,2'-azinobis (3-ethylbenzothiazoline-6- sulfonic acid) ammonium salt (ABTS) with low Michaelis-Menten constants and quick reaction rates. Especially, toxic aminophenol isomers could exclusively react with the oxydates of TMB or ABTS to express differentiable signals in color. Under the optimal conditions, Cu-Ru MPNZ was successfully applied for visual differentiation of toxic aminophenol isomers in real aqueous, juices and medicinal samples with low detection limits (1.60 × 10-8 mol/L for o-aminophenol and 3.25 × 10-8 mol/L for m-aminophenol) and satisfactory recoveries (96.6-103.5%). The different recognition mechanisms of Cu-Ru MPNZ to toxic o- and m-aminophenol isomers were proposed for the first time as far as we known. This work will provide a potential way to monitor different organic isomer pollution in future.

Folic acid capping Bi3+-doped Ag quantum dots for enzyme-like dual-mode recognition of toxic S2- and visual sensing of NO2.

BACKGROUND: NO2- and S2- are two kinds of common toxic anions widely distributed in environmental water, soil and food products. Human beings have suffered a lot of diseases from intake of excessive NO2- or S2-, i.e., infantile methemoglobin, cancer and even to death. Although tremendous efforts have been afforded to monitor NO2- and S2-, most were high instrument-depended with complex processing procedures. To keep food safety and to protect human health, it will be a huge challenge to develop a convenient and efficient way to monitor S2- and NO2- in practice. RESULTS: A kind of folic acid capping Bi3+-doped Ag quantum dots (FA@Bi3+-Ag QDs) was developed for the first time by one-pot homogeneous reduced self-assembly. Not only did FA@Bi3+-Ag QDs possess intrinsic fluorescent property, it expressed synergistic peroxidase-like activity to catalyze the redox of 3,3',5,5'-tetramethylbenzidine (TMB) and H2O2 with Km/vmax of 0.087 mM/6.61 × 10-8 M s-1 and 6.42 mM/6.25 × 10-7 M s-1 respectively. Interestingly, trace S2- could exclusively alter its fluorescent property and peroxidase-like activity, exhibiting significant hypochromic and "turn-on" fluorescent effects. While trace NO2- could make FA@Bi3+-Ag QDs-TMB-H2O2 system hyperchromic. Under the optimized conditions, FA@Bi3+-Ag QDs were applied for dual-mode recognition of S2- and visual sensing of NO2- in real food samples with satisfactory recoveries, i.e., 100.7-107.9 %/95.8-104.7 % and 97.2-104.8 % respectively. The synergistic enzyme-mimic mechanism of FA@Bi3+-Ag QDs and its selective response mechanisms to S2- and NO2- were also proposed. SIGNIFICANCE: This represents the first nanozyme-based FA@Bi3+-Ag QDs system for dual-mode recognition of S2- and visual sensing of NO2-, well meeting the basic requirement in drinking water set by WHO. It will offer a promising way for multi-mode monitoring of different pollution using the same nanozyme-based sensor.