Coordinatively unsaturated cobalt single-atom nanozymes for visual pesticides detection by smartphone-based platform

By adjusting the coordination environment of single-atom catalysts,the enzyme-like activity can be finely tuned for highly sensitive biosensing.Herein,we demonstrated that coordinatively unsaturated cobalt-nitrogen sites doped within porous carbon(SA-CoN_(3))could serve as highly efficient oxidase mimic.Compared with the typical planar four-coordination structure(SA-CoN_(4)),the as-obtained single-atom Co nanozymes anchored by three nitrogen atoms are found to display much higher oxidase-like catalytic efficiency.Combined theoretical and experimental analysis revealed that the coordinatively unsaturated Co sites could facilitate adsorption and activation of O_(2) molecule and thus improve their oxidase-like activity.Based on the enhanced oxidase-like activity of SA-CoN_(3),a paper/smartphone sensor for organophosphorus pesticides(OPs)was successfully constructed and used to quantify glyphosate in environmental and food samples with a low detection limit of 0.66μM.This work not only highlights the important role of coordination unsaturation of SA nanozymes for promoting oxidase-like activity,but also provides an easy and cost-effective way to conduct effective quantification of OPs in the field.

Highly exposed Cu active sites as efficient peroxidase mimics for colorimetric analysis

Nanozymes are nanomaterials with intrinsic enzyme-mimic activity,but their large-scale application is generally limited by their low catalytic activity.Herein,we demonstrated that highly exposed Cu active sites on two-dimensional(2D)nitrogen-doped carbon(Cu_(x)/NC)can serve as efficient peroxidase-like(POD)catalysts with high atomic utilization.Specially,the uniformly distributed Cu active sites could react with H_(2)O_(2)to produce singlet oxygen(^(1)O_(2))under acidic conditions,which can efficiently oxidizes colorless 3,3',5,5'-tetramethylbenzidine(TMB)to blue oxidized TMB(oxTMB).Among various Cu_(x)/NC nanozymes studied,the Cuo.14/NC exhibited smaller maximum catalytic velocities(V_(max))and Menten constant(K_(m))for TMB and H_(2)O_(2).Benefiting from the highly active peroxidase-like activity,the Cu_(0.14)/NC nanozyme could be successfully applied for the hydroquinone(HQ)and ascorbic acid(AA)detection applications through the inhibitory effect of HQ and AA.More interestingly,α-glucosidase(α-Glu)detection sensing platform could be constructed based on HQ as a signal transmitter,with the detection range ranging from O to 12 U/L and the minimum detection limit being 0.68 U/L.This work provides not only an idea for the rational design of highly exposed Cu active sites but also fabricate an effective detection sensing platform forHQ,AA,andα-Glu detection.