Smartphone-assisted portable swabs for blood glucose management: A point-of-use assay for dual-mode visual detection based on bifunctional carbon dots.

Controlling glucose (Glu) intake is a "required course" for diabetics, thus quickly and precisely measuring the amount of Glu in food is crucial. For this purpose, a novel smartphone-assisted portable swab for the dual-mode visual detection of Glu was constructed combined the selectivity of natural enzymes with the controllable catalytic activity of nanozymes. Glu was specifically decomposed by glucose oxidase (natural enzyme) to produce H2O2, which was catalyzed by carbon dots (FeMn/N-CDs, nanozyme) to accelerate the reaction of o-phenylenediamine (OPD, colorless) to produce 2,3-diaminophenazine (DAP, yellow). As a result, the absorbance at 450 nm gradually increased with the increasing concentration of Glu, leading to a color change in the system from colorless to yellow. Meanwhile, the fluorescence of FeMn/N-CDs gradually decreased at 450 nm, while the fluorescence of DAP gradually increased at 550 nm, allowing for both ratiometric fluorescence and colorimetric dual-mode detection. Furthermore, natural enzyme and nanozyme together with OPD were co-loaded on the swabs to achieve cascade catalysis of Glu. The assembled portable swabs have detection ranges of 1-600 µM (LOD = 0.37 µM) and 4-1200 µM (LOD = 1.19 µM) for the colorimetric and fluorometric detection, respectively. The field test results on real samples demonstrated that the portable swabs have great promise for use in efficiently and accurately guiding the dietary intake of diabetics.

Calcium Fluoride/Manganese Dioxide Nanocomposite with Dual Enzyme-like Activities for Uric Acid Sensing: A Comparative Study of Enzyme and Nonenzyme Methods.

The debate over enzyme methods versus nonenzyme methods in the field of nanosensing has lasted for decades despite hundreds of published studies on this topic. In this study, we first present a comparative analysis of these methods using a reaction based on the CaF2/MnO2 nanocomposite (CM Nc) with dual-enzyme activity, presenting oxidase- and peroxidase-like activities. Uric acid (UA) is a byproduct of purine metabolism in the body, and abnormal levels can cause many diseases; hence, tracking the amount of UA in human serum is crucial. The enzyme method was established using uricase and CM Nc: UA produced H2O2 when catalyzed by uricase; H2O2 was then catalyzed into reactive oxygen species (ROS) by the peroxidase activity of the CM Nc; this ROS oxidized 3,3',5,5'-tetramethylbenzidine (TMB), which was oxidized into blue oxidized TMB (oxTMB). The nonenzyme method was built on the scavenging effect of UA on the ROS, which prevented the catalytic capability of CM Nc toward TMB and induced blue oxTMB fading. The results of further tests revealed the good selectivity of the enzyme method compared to the fast response of the nonenzyme method. Additionally, both methods were effective in determining the UA concentration in human serum. The two separate methods can also independently verify each other, increasing the accuracy of the detection results in accordance with the relatively independent detection principles. This research provided theoretical backing for the practical design of multienzyme nanozyme catalysts, which can facilitate the precise detection of UA in biochemical products.

Ratiometric colorimetric detection of nitrite using CoMnO3 nanofibers as an oxidase-like enzyme to induce diazotization reaction.

Nitrite is a typical food additive and preservative used in the food industry, which has attracted considerable attention due to its severe adverse effects on human health. Herein, a sensitive and highly selective ratiometric colorimetric sensing platform for the detection of nitrite was created based on a polymetallic oxide nanozyme, CoMnO3 nanofibers (CMO) catalysis integrated with the particular diazotization reaction. The nanozyme has superior oxidase-like activity (Km was 0.105 mM and Vmax was 63.7 × 10-8 M S-1) and could catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) to oxidized TMB (oxTMB), as CMO could achieve the conversion of oxygen in the solution to superoxide anion (O2˙-). In addition, it is interesting to note that oxTMB can be diazotized in the presence of nitrite under acidic conditions, causing a shift in the ratio of nitrite concentration to the absorbance peaks at 450 and 652 nm (A450/A652). The ratio of A450/A652 exhibited a positive linear relationship with the concentration of nitrite within the concentration range of 0.2-200 µM, with a detection limit of 0.094 µM. Simultaneously, this method was also successful in quantifying the nitrite produced by brined and pickled foods and the dynamic tracking of the nitrite levels in various types of dishes. The analysis method not only offers dual-signal ratio sensing with high sensitivity but also holds the benefit of outstanding selectivity for the use of the particular reaction, which has a wide range of application prospects in food safety management.

Simplifying the complexity: Single enzyme (choline oxidase) inhibition-based biosensor with dual-readout method for organophosphorus pesticide detection.

Organophosphorus pesticides (OPs) are widely used in agricultural production, but their residues could cause pollution to the environment and living organisms. In this paper, a simple dual-readout method for OPs detection was proposed based on ChOx single enzyme inhibition. Firstly, ChOx can catalyze the production of H2O2 from choline chloride (Ch-Cl). Bifunctional iron-doped carbon dots (Fe-CDs) with good peroxidase-like activity and superior fluorescence properties can catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) to blue oxidized TMB (oxTMB) by H2O2 formed, and oxTMB could quench the fluorescence of Fe-CDs. In light of the fact that OPs exhibited activity in inhibiting ChOx, less H2O2 and the decreasing oxTMB led to a result that the fluorescence of the system recovered and the solution became lighter in blue color. Moreover, the process of ChOx inhibition by OPs was analyzed by molecular docking technique and it was found that OPs interact with key amino acid residues catalyzed by ChOx (Asn510, His466, Ser101, His351, Phe357, Trp331, Glu312). Finally, a dual-mode (colorimetry and fluorescence) sensor was created for the detection of OPs with the detection limit of 6 ng/L, and was successfully used in the quantitative determination of OPs in actual samples with satisfactory results.

Enhancing catalytic performance of Fe and Mo co-doped dual single-atom catalysts with dual-enzyme activities for sensitive detection of hydrogen peroxide and uric acid.

Single-atom catalysts (SACs) have attracted much attention due to their excellent catalytic activity, but the improvement of atomic loading which means that weight fraction (wt%) of metal atom was still facing great challenges. In this work, iron and molybdenum co-doped dual single-atom catalysts (Fe/Mo DSACs) was prepared for the first time by using the soft template sacrifice strategy, which improved significantly the atomic load and exhibited both the oxidase-like (OXD) activity and the dominant peroxidase-like (POD) activity. Further experiments reveal that Fe/Mo DSACs can not only catalyze O2 to generate O2•- and 1O2, but also catalyze H2O2 to generate a large number of •OH, which caused 3, 3', 5, 5'-tetramethylbenzidine (TMB) to be oxidized to oxTMB, accompanied by the color changing from colorless to blue. The steady-state kinetic test showed that Michaelis-Menten constant (Km) values and the maximum initial velocity values (Vmax) of the POD activity of Fe/Mo DSACs were 0.0018 mM and 12.6 × 10-8 M s-1, respectively. The corresponding catalytic efficiency was tens of times higher than Fe SACs and Mo SACs, which proves that the synergistic effect between Fe and Mo has significantly improved the catalytic ability. Based on the excellent POD activity of Fe/Mo DSACs, a colorimetric sensing platform combined with TMB was proposed to realize the sensitive detection of H2O2 and uric acid (UA) in a wide range, with limits of detection as low as 0.13 and 0.18 µM, respectively. Finally, accurate and reliable results were obtained in the detection of H2O2 in cells, and of UA in human serum and urine.

Development of a pH-Responsive, SO42--loaded Fe and N co-doped carbon quantum dots-based fluorescent method for highly sensitive detection of glyphosate.

A novel sulfate-loaded iron-nitrogen co-doped carbon quantum dots (SO42--CQDs)-based fluorescent method was synthesized by the facile and environmentally friendly pyrolysis of persimmon frost (carbon source) and (NH4)2Fe(SO4)2·6H2O. After SMMC-7721 cells were incubated with the SO42--CQDs for 24 h, more than 95% of the cells remained viable, even at a high concentration of the SO42--CQDs, indicating excellent biocompatibility and low toxicity. In addition, it was able to be taken up by the cells to emit their bright blue fluorescence after excitation at 365 nm, indicating suitable cell permeability. The SO42--CQDs also exhibited a unique response to changes in pH, which was applied in the detection of OPs by relying on the production of acetic acid from the hydrolysis of acetylcholine (ACh) by acetylcholinesterase (AChE), which decreased the pH and engendered an increase in the fluorescence of the SO42--CQDs; however, the inhibition of AChE by glyphosate resulted in little influence on fluorescence intensity due to the lack of acetic acid produced. This mechanism was the basis for the development of a sensitive assay for the detection of glyphosate. The resulting assay had a limit of detection of 0.066 ng/mL. Furthermore, the method was successfully applied for the precise and accurate monitoring of the concentration, distribution, and variation of glyphosate residues in chives and cultivated soil. Therefore, the proposed method was anticipated to provide a promising alternative for other detection methods to enable the reliable analysis of OPs in food products.

Graphitic-phase C3N4 nanosheets combined with MnO2 nanosheets for sensitive fluorescence quenching detection of organophosphorus pesticides.

In this study, we have developed a sensitive approach to measure organophosphorus pesticides (OPs) using graphitic-phase C3N4 nanosheets (g-C3N4) combined with a nanomaterial-based quencher, MnO2 nanosheets (MnO2 NS). Since MnO2 NS can quench the fluorescence of g-C3N4 via the inner-filter effect (IFE), enzymatic hydrolysate (thiocholine, TCh) can efficiently trigger the decomposition of MnO2 nanosheets in the presence of acetylcholinesterase (AChE) and acetylthiocholine (ATCh), resulting in the fluorescence recovery of g-C3N4. OPs, as inhibitors to AChE activity, can prevent the generation of TCh and decomposition of MnO2 nanosheets while exhibiting fluorescence quenching. Therefore, the AChE-ATCh-MnO2-g-C3N4 system can be utilized to quantitatively detect OPs based on g-C3N4 fluorescence. Under optimal conditions, the linear ranges for the determination of parathion-methyl (PM) and 2,2-dichlorovinyl dimethyl phosphate (DDVP) were found to be 0.1-2.1 ng/mL and 0.5-16 ng/mL, respectively, with limits of detection of 0.069 ng/mL and 0.20 ng/mL, respectively. The advantages of this assay are user-friendliness, ease of use, and cost effectiveness compared to other more sophisticated analytical instruments.

Monitoring of parathion methyl using a colorimetric gold nanoparticle-based acetylcholinesterase assay.

A colorimetric gold nanoparticles (AuNPs)-based acetylcholinesterase (AChE) assay was designed for the first time to measure the concentration of parathion-methyl (PM) in lake water samples. In this assay, the analyte PM inhibited the hydrolysis of acetylthiocholine (ATCh) by AChE, preventing the formation of thiocholine (TCh) that would otherwise react with the AuNPs catalyst and deactivate the catalyst. Therefore, in the presence of PM, the AuNPs catalyzed the oxidation of the 3,3',5,5'-tetramethylbenzidine (TMB) colorimetric indicator to oxTMB, inducing a visual color change from colorless to blue. However, in the absence of PM, AChE hydrolyzed ATCh to TCh, which then reacted with the AuNPs, preventing the oxidation of TMB to oxTMB and rendering the solution colorless. Therefore, the change in the color of the analyte solution indicated the presence of PM, and the absorbance of the resulting solution was measured by UV-Vis spectroscopy to calculate the concentration of PM after generation of a calibration curve. This method was then employed using the smartphone app Color Picker, which converted the color information from the photos of the solution into digital red (R), green (G), and blue (B) values. The ratio of green (G) to blue (B) (G/B) was then plotted against the corresponding concentration to calculate the standard curve, whose regression equation was expressed by y = -0.012x + 1.02 (ng/mL), and the coefficient of determination (R2) was 0.97. In addition, this method was also used to determine the amount of PM in real lake water samples with recovery of 90.2-133.3%.

A sensitive fluorescent assay for the determination of parathion-methyl using AHNSA probe with MnO2 nanosheets.

In this paper, a novel fluorescence assay has been constructed for the determination of parathion-methyl (PM) by using 4-amino-3-hydroxy-1-naphthalenesulfonic acid (AHNSA) as probe. MnO2 nanosheets (MnO2 NS) could quench the fluorescence of AHNSA, while Mn2+, the reduction product of MnO2 NS, has no influence on it, resulting in fluorescence recovery. This is because that MnO2 NS have oxidized characteristic, and they can react with choline (TCh), which is the product of acetylthiocholine (ATCh) catalyzed by acetylcholinesterase (AChE). In the presence of OPs, the activity of AChE was inhibited, accompanied by the restraint of the redox reaction of MnO2 NS, therefore the fluorescence of AHNSA was quenched. Under the optimized experimental conditions, a linear range of PM was determined to be 0.4-40 ng/mL (R2 = 0.997) by the proposed method with the limit of detection for 0.18 ng/mL (S/N = 3). The assay was successfully applied to the determination of PM in lake water, which average recoveries were between 86.5% and 114.4%.