Modulation of the enzyme-like activity of CuAsp nanozyme by gallic acid and the selective detection of bisphenol A in infant food packaging.

The activity modulation of nanozymes with multi-enzymatic activities has both opportunities and challenges in practical applications. In this study, we found firstly that gallic acid erosion had a significant inhibitory effect on the peroxidase-catalyzed colorimetric reaction process of copper aspartate nanozyme prepared based on aspartic acid and copper (CuAsp), and the laccase-like catalytic activity remained almost unchanged. A sensing strategy for bisphenol A was then developed based on the laccase-like activity of GA-CuAsp synthesized by gallic acid (GA) acid erosion of CuAsp, which may have less interference due to the peroxidase-like activity. The developed sensing strategy had good selectivity and interference resistant ability, with a detection limit of 0.75 µmol L-1. In addition, the method was successfully applied to detecting BPA in plastic bottled drinking water samples and infant food packaging.

A novel strategy for identification of pesticides in different categories by concentration-independent model based on a nanozyme with multienzyme-like activities.

Conventional rapid detection methods are difficult to identify or distinguish various pesticide residues at the same time. And sensor arrays are also limited by the complexity of preparing multiple receptors and high cost. To address this challenge, a single material with multiple properties is considered. Herein, we first found that different categories of pesticides have diverse regulatory behaviors on the multiple catalytic activities of Asp-Cu nanozyme. Thus, a three-channel sensor array based on the laccase-like, peroxidase-like, and superoxide dismutase-like activities of Asp-Cu nanozyme was constructed and successfully used for the discrimination of eight kinds of pesticides (glyphosate, phosmet, isocarbophos, carbaryl, pentachloronitrobenzene, metsulfuron-methyl, etoxazole, and 2-methyl-4-chlorophenoxyacetic acid). In addition, a concentration-independent model for qualitative identification of pesticides has been established, and 100% correctness was achieved in the recognition of unknown samples. Then, the sensor array also exhibited excellent interference immunity and was reliable for real sample analysis. It provided a reference for pesticide efficient detection and food quality supervision.

An efficient differential sensing strategy for phenolic pollutants based on a nanozyme with polyphenol oxidase activity.

To realize the efficient differential sensing of phenolic pollutants in sewage, a novel sensing strategy was successfully developed based on a nanozyme (GMP-Cu) with polyphenol oxidase activity. Phenolic pollutants can be oxidized using GMP-Cu, and the oxidation products reacts subsequently with 4-aminoantipyrine to produce a quinone-imine compound. The absorption spectra of final quinone-imine products that resulted from different phenolic pollutants showed obvious differences, which were due to the interaction difference between GMP-Cu and phenolic pollutants, as well as the different molecular structures of the quinone-imine products from different phenolic pollutants. Based on the difference in the absorption spectra, a novel differential sensing strategy was developed. A genetic algorithm was used to select the characteristic wavelengths at different enzymatic reaction times. Hierarchical cluster analysis and PLS-DA algorithms were utilized for the discriminant sensing of seven representative phenolic pollutants, including hydroquinone, resorcinol, catechol, resorcinol, phenol, p-chlorophenol, and 2,4-dichlorophenol. A scientific wavelength selection algorithm and a recognition algorithm resulted in the successful identification of phenolic pollutants in sewage with a discriminant accuracy of 100%, and differentiation of the phenolic pollutants regardless of their concentration. These results indicated that a sensing strategy can be used as an effective tool for the efficient identification and differentiation of phenolic pollutants in sewage.

Determination of catechin and glutathione using copper aspartate nanofibers with multiple enzyme-like activities.

Copper aspartate nanofibers were facilely prepared based on aspartic acid and copper (CuAsp nanofibers). It is found that the prepared CuAsp nanofibers have catalytic activities of five enzymes, including peroxidase, laccase, catalase, ascorbate oxidase, and superoxide dismutase mimetic activities. The kinetic and catalytic properties of CuAsp nanofibers were systematically investigated, showing their high catalytic activity, excellent stability, and reusability. The laccase mimetic activity of nanofibers could be used to detect catechin in the range 20-1200 µM with a detection limit of 5.88 µM. In addition, a sensing platform for glutathione with a detection limit of 0.25 µM and a detection range of 1-50 µM was established based on CuAsp nanofibers which have the peroxidase-mimicking activity. The sensor had good selectivity and could detect glutathione in actual samples of human serum. Therefore, CuAsp nanofibers with multi-enzyme activity have broad application prospects such as biosensing, environmental management, and disease diagnosis.

Fluorescence detection of dopamine based on the polyphenol oxidase-mimicking enzyme.

In this work, a novel fluorescent method for the detection of dopamine (DA) was developed based on a fluorescent nanocomposite (Pdots@AMP-Cu) with polyphenol oxidase activity. Pdots@AMP-Cu was first prepared by the composite of fluorescent polymer dots and coordination nanostructures of adenosine monophosphate (AMP) and Cu2+. The Pdots@AMP-Cu exhibited obvious red fluorescence emission (668 nm), as well as polyphenol oxidase activity by catalyzing the substrate 2,4-DP and 4-AP, and resulted in obvious changes of the solution color from colorless to red. A novel detection method for DA was then developed based on Pdots@AMP-Cu. It is observed that DA can be oxidized by Pdots@AMP-Cu to form eumelanin, and at the same time, the fluorescence of Pdots@AMP-Cu is efficiently quenched by eumelanin due to electron transfer. A good linear relationship was observed between the fluorescent intensity and DA concentration from 10 to 400 µM, and the limit of detection for DA was 4 µM. Moreover, the proposed method exhibited high selectivity toward common amino acids, ascorbic acid, uric acid, etc. And it could also be utilized for DA sensing in human serum samples with satisfactory recoveries. Graphical abstract.

A colorimetric sensor array based on natural pigments for the discrimination of saccharides.

A colorimetric sensor array based on natural pigments was developed to discriminate between various saccharides. Anthocyanins, pH-sensitive natural pigments, were extracted from fruits and flowers and used as components of the sensor array. Variation in pH, due to the reaction between saccharides and boronic acids, caused obvious colour changes in the natural pigments. Only by observing the difference map with the naked eye could 11 common saccharides be divided into independent individuals. In conjunction with pattern recognition, the sensor array clearly differentiated between sugar and sugar alcohol with highly accuracy and allowed rapid quantification of different concentrations of maltitol and fructose. This sensor array for saccharides is expected to become a promising alternative tool for food monitoring. The link between anthocyanin and saccharide detection opened a new guiding direction for the application of anthocyanins in foods.

Fluorometric and colorimetric analysis of alkaline phosphatase activity based on a nucleotide coordinated copper ion mimicking polyphenol oxidase.

In this work, a fluorometric and colorimetric analysis of alkaline phosphatase (ALP) activity was developed based on nanozymes. The nanozymes were composed of nucleotides (ATP, ADP and AMP) coordinated with copper ions. All three kinds of nanozymes (ATP-Cu, ADP-Cu and AMP-Cu) exhibited polyphenol oxidase (PPO)-mimic activity by catalyzing a chromogenic reaction of 2,4-dichlorophenol (2,4-DP) and 4-aminoantipyrine (4-AP). However, there were obvious differences in the PPO-like activity and the fluorescence of the three nanozymes produced from the same concentration of nucleotides (keeping the concentration of Cu2+ unchanged at 5 mM). The catalytic activities of produced ADP-Cu and AMP-Cu were obviously higher than that of ATP-Cu at a certain nucleotide concentration of 3 mM. In addition, when ATP was hydrolyzed into ADP and AMP by ALP, more nanozymes were produced and the catalytic activity of the system was enhanced, which resulted in an obvious increase of the colorimetric signal. The signal intensity was proportional to ALP concentration in the range of 0-30 U L-1, and the detection limit for ALP was 0.3 U L-1 from the colorimetric detection. Moreover, the fluorescence intensity of the produced nanozymes was also proportional to the ALP concentration in the range of 1-30 U L-1 and the detection limit was 0.45 U L-1 from the fluorescence detection. A fluorometric and colorimetric sensing ALP method was thus established. The method showed a high selectivity for ALP activity compared with proteins, amino acids and other interference components. Furthermore, the proposed method was also used to detect ALP activity in human serum samples, which showed great potential for diagnostic and practical purposes.