Modified Metal-Organic Framework (MOF-818) inspired by natural enzymes for intelligent detection of total antioxidants and bisphenol A in infant beverages.

BACKGROUND: Accurate and quick judgement of the food quality can protect the legitimate rights of consumers. Currently, nanozymes are widely employed in the rapid detection of food due to their stability and economy. The contents of bisphenol A and antioxidant can be used to measure the quality of beverages. However, due to the complexity of the actual samples, it is still challenging to achieve the sensitive detection of both at the same time. The development of nanozyme with high enzyme activity is essential for sensitive detection of targets in complex foods. RESULTS: In this work, a novel nanomaterial (ZrTGA) was synthesized based on thioglycolic acid-modified Metal-Organic Framework (MOF-818). The interaction between Cu-S bonds and increase in the proportion of Cu1+ resulted in ZrTGA exhibiting higher peroxidase-like and polyphenol oxidase-like activities. These enzyme activities were 317 % and 200 % of the original values, respectively. With high enzyme activity can sensitively detect two important indicators of bisphenol A and antioxidants in beverages. The increased enzyme activity of ZrTGA enabled the content of both substances to be detected by smartphone extraction of RGB. Finally, through the output of the ''0″ and ''1″ signals of the logic gates, it is possible to quickly determine the level of the two substances and thus directly assess the quality of the beverages. SIGNIFICANCE: The modification of nanozyme enables the detection of substances at low concentrations based on enhancing dual-enzyme activity. The combination of mobile phone photography and logic gate technology enables the continuous detection of two important indicators in beverages, overcoming the limitations of traditional large-scale instruments. It also provides an alternative strategy for food quality detection.

Smartphone-assisted hydrogel platform based on BSA-CeO2 nanoclusters for dual-mode determination of acetylcholinesterase and organophosphorus pesticides.

A dual-mode sensor was developed for detecting acetylcholinesterase (AChE) and organophosphorus pesticides (OPs) via bifunctional BSA-CeO2 nanoclusters (NCs) with oxidase-mimetic activity and fluorescence property. The dual-mode sensor has the characteristics of self-calibration and self-verification, meeting the needs of different detection conditions and provide more accurate results. The colorimetric sensor and fluorescence sensor have been successfully used for detecting AChE with limit of detection (LOD) of 0.081 mU/mL and 0.056 mU/mL, respectively, while the LOD for OPs were 0.9 ng/mL and 0.78 ng/mL, respectively. The recovery of AChE was 93.9-107.2% and of OPs was 95.8-105.0% in actual samples. A novel strategy was developed to monitor pesticide residues and detect AChE level, which will motivate future work to explore the potential applications of multifunctional nanozymes.

Achieving smartphone-based colorimetric assay for Hg2+ with a bimetallic site strategy based on Hg2+-triggered oxidase-like catalytic activity of NSC/Co6Ni3S8 nanocomposite.

Modulation of the nanozyme's catalytic activity is crucial for its real applications in detecting target analytes. Herein, we fabricated the nanocomposite (NSC/Co6Ni3S8) of N, S co-doped carbon and Co6Ni3S8 by a facile sol-gel approach. Compared to NSC/Ni9S8, NSC/Co6Ni3S8 with bimetallic active sites displayed better enzyme-mimetic activity. This nanocomposite could catalyze O2 to form ·O2- and oxidize colorless 3, 3', 5, 5'-tetramethylbenzidine (TMB) into blue oxTMB. The other two free radicals (h+ and ·OH) played minor roles during the catalytic reaction. Hg2+ could integrate with S2- to form HgS and the surface charges of O2 were transferred to Hg2+ to promote O2 adsorption. DFT theoretical calculations highlight that the main reasons for the enhancing effect of Hg2+ on color development results from electron transfer and increased adsorption energy of O2 molecules onto the surface of NSC/Co6Ni3S8. By employing the oxidase-like activity of NSC/Co6Ni3S8 and Hg2+-triggered promoting effect, a colorimetric sensing platform was established for Hg2+ assay with a linear range of 10-200 µg/L and detection limit of 3 µg/L. Through integration with a smartphone-based APP "Thing Identify" software, a visual colorimetric assay for Hg2+ was constructed with a detection limit of 5 µg/L. Compared to the data detected by the mercury vapor meter, the relative recoveries of 92.4-108.1% evidenced the higher accuracy of this smartphone-based visual detection. Overall, the NSC/Co6Ni3S8-based colorimetric assay is convenient, rapid, and visual, and can be applied for routine monitoring of Hg2+ in real-world waters under outdoor conditions.

Regulation of the Oxidase Mimetic Activity of Ceria Nanoparticles by Buffer Composition.

Ceria nanoparticles (CNPs) are important typical nanozymes with multiple enzyme mimetic activities, which could facilitate the oxidation of organic dyes in acidic conditions, because of the oxidase mimetic activity. Usually, the regulation of oxidase mimetic activity is focused on the adjustment of the structure, morphology, composition, surface, and other factors of nanozymes. However, the influence of the surrounding environment is not considered, which is very important during the reaction process. In this work, the oxidase mimetic activity of CNPs in buffer solutions including citric acid, acetic acid and glycine buffer solutions was investigated, with the results that carboxyl group in buffer solution could adsorb the CNPs on the surface to promote the oxidase mimetic activity. Due to the chelation with the cerium ion, the enhancement is more significant by molecules with polycarboxylic groups, and the enhancement is more efficient by carboxyl molecules in buffer solution, compared with the modification of the carboxyl groups on the surface, because of easier operation and smaller steric hindrance. From the viewpoint of increasing the oxidase mimetic activity of CNPs, the work is expected to provide references for the selection of the reaction systems to optimize the oxidase mimetic activity in bio-detection applications.

Cobalt-Doped Carbon Quantum Dots with Peroxidase-Mimetic Activity for Ascorbic Acid Detection through Both Fluorometric and Colorimetric Methods.

In this work, we fabricated cobalt-doped carbon quantum dots (Co-CQDs) by a one-pot hydrothermal method with cobalt tetraphenylporphyrin and 1,2-ethanediamine as precursors. The morphology and structure of the Co-CQDs were characterized through transmission electron microscopy, X-ray diffraction spectra, Fourier transform infrared, and X-ray photoelectron spectra. The Co-CQDs emitted intense blue luminescence under ultraviolet irradiation and exhibited a typical excitation-dependent emission property. Moreover, they can act as a fluorescent probe for the detection of Fe3+ and ascorbic acid (AA) with high selectivity and sensitivity through an "on-off-on" mode. The limit of detection (LOD) of Fe3+ was measured as 38 µM (S/N = 3). The quenched emission of carbon quantum dots can be recovered with the addition of ascorbic acid (AA) to the Co-CQDs/Fe3+ system. The change of fluorescence was linear with the concentration of AA (0.6-1.6 mM) with the LOD of 18 µM. Furthermore, the Co-CQDs exhibited high oxidase-like catalytic behavior, which could convert transparent 3,3',5,5'-tetramethylbenzidine (TMB) into blue ox-TMB by dissolved oxygen. After adding ascorbic acid to the Co-CQDs/TMB system, the blue color of the solution faded due to the reduction of blue ox-TMB to colorless TMB. Based on this phenomenon, the Co-CQDs were capable of detecting AA (10-400 µM) with the LOD of 0.27 µM. The fluorometric and colorimetric assays based on the Co-CQDs for the AA detection were then successfully applied in fresh fruits. Furthermore, the high biocompatibility of the Co-CQDs against HeLa cells was verified by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) method. Thus, the Co-CQDs could be used as a powerful tool for the detection of AA in real samples through a dual-mode method.

Using photo-induced p-n junction interface effect of CoMn2O4/ß-MnO2 oxidase mimetics for colorimetric determination of hydroquinone in seawater.

Detection of pollutants in seawater faces a great challenge of strong interference, and the facile detection method is lacked. The CoMn2O4/ß-MnO2 p-n junction oxidase mimetics were successfully prepared for colorimetric detection of hydroquinone in seawater. The catalysis ability was enhanced significantly by the photo-induced p-n junction interface effect. It not only promoted the formation of H2O2 by suppressing the recombination of photon-generated carriers, but also provided the driving force for electron transport. The colorimetric detection of hydroquinone was achieved by fading and exhibited good adaptability in seawater. The obtained good recovery rate (97.23%-101.37%) in seawater makes it an inspiring method for practical application. The photo-induced p-n junction interface effect provides an opportunity for developing the application of colorimetric sensing in seawater detection.

Preparation of NiMn2O4/C necklace-like microspheres as oxidase mimetic for colorimetric determination of ascorbic acid.

The NiMn2O4/C necklace-like microspheres (NLM) were successfully prepared by hydrothermal method and oil bath. This unique necklace-like structure makes them exhibit the enhanced intrinsic oxidase-like activity, as the special interface can help capture electrons from 3,3',5,5'-tetramethylbenzidine. The fabricated NiMn2O4/C NLM were successfully used as the high-performance oxidase mimetic to catalyze the oxidation of TMB directly for the color reaction. A simple colorimetric method for detection of ascorbic acid by fading was developed, and the high sensitivity with the low detection limit (0.047 µM) was achieved. It is a facile route to fabricate the NiMn2O4/C NLM as the high-performance oxidase mimetic for colorimetric biosensing.

A novel peroxidase/oxidase mimetic Fe-porphyrin covalent organic framework enhanced the luminol chemiluminescence reaction and its application in glucose sensing.

A Fe-porphyrin covalent organic framework (Fe-PorCOF) was prepared through a postmodification strategy and characterized using different techniques. Fe-PorCOF exhibits an inherent peroxidase/oxidase mimetic catalytic activity and sharply accelerates chemiluminescence (CL) reactions between luminol and hydrogen peroxide (H2 O2 ) or dissolved oxygen (O2 ) under alkaline conditions. The catalytic role was attributed to a significant increase in production of reactive oxygen species. Using the imminent peroxidase mimetic catalytic activity of Fe-PorCOF, a new CL method was developed for determination of H2 O2 over a linear range from 0.01 to 10.0 µmol·L-1 and with a limit of detection of 5.3 nmol·L-1 . The combination of the peroxidase mimetic catalytic activity of Fe-PorCOF with the catalytic activity of glucose oxidase on glucose oxidation presents a sensitive CL method for glucose assay. The linear range and the detection limit for glucose were 0.05-8.0 µmol·L-1 and 4.0 nmol·L-1 , respectively. The practicability of this method was assessed by determination of glucose in human sera. As a peroxidase/oxidase mimetic, Fe-PorCOF is easy to prepare and exhibits good catalytic efficiency in the luminol reaction. We believe that this strategy will promote the development of a CL field with functional COFs as a catalyst.

Hot Carriers and Photothermal Effects of Monolayer MoOx for Promoting Sulfite Oxidase Mimetic Activity.

Local surface plasmon resonance (LSPR)-enhanced catalysis has brought a substantial amount of opportunities across various disciplines such as photocatalysis, photodetection, and photothermal therapeutics. Plasmon-induced photothermal and hot carriers effects have also been utilized to activate the enzyme-like reactions. Compared with natural enzymes, the relatively low catalytic performance of nanozymes severely hampered the potential applications in the field of biomedicine. For these issues mentioned above, herein, we demonstrate a highly efficient sulfite oxidase (SuOx) mimetic performance of plasmonic monolayer MoOx (ML-MoOx) upon LSPR excitation. We also established that the considerable photothermal effect and the injection of hot carriers induced by LSPR are responsible for promoting the SuOx activity of ML-MoOx. The high transient local temperature on the surface of ML-MoOx generated by the photothermal effect facilitates to impact the reaction velocity and feed the SuOx-like activity, while the generation of hot carriers which are suggested as predominant effects catalyzes the oxidation of sulfite to sulfate through significantly decreasing the activation energy for the SuOx-like reaction. These investigations present a contribution to the basic understanding of plasmon-enhanced enzyme-like reaction and provided an insight into the optimization of the SuOx mimetic performance of nanomaterials.

Ascorbate Oxidase Mimetic Activity of Copper(II) Oxide Nanoparticles.

Although oxidase mimetic nanozymes have been widely investigated, specific biological molecules have rarely been explored as substrates, particularly in the case of ascorbate oxidase (AAO) mimetic nanozymes. Herein, we demonstrate for the first time that copper(II) oxide nanoparticles (CuO NPs) catalyze the oxidation of ascorbic acid (AA) by dissolved O2 (as a green oxidant) to form dehydroascorbic acid (DHAA), thus functioning as a new kind of AAO mimic. Under neutral conditions, the Michaelis-Menten constant of CuO NPs (0.1302 mm) is similar to that of AAO (0.0840 mm). Furthermore, the robustness of CuO NPs is greater than that of AAO, thus making them suitable for applications under various conditions. As a demonstration, a fluorescence AA sensor based on the AAO mimetic activity of CuO NPs was developed. To obtain a fluorescent product, o-phenylenediamine (OPDA) was used to react with the DHAA produced by the oxidation of AA catalyzed by CuO NPs. The developed sensor was cost-effective and easy to fabricate and exhibited high selectivity/sensitivity with a wide linear range (1.25×10-6 to 1.125×10-4 m) and a low detection limit (3.2×10-8 m). The results are expected to aid in expanding the applicability of oxidase mimetic nanozymes in a variety of fields such as biology, medicine, and detection science.

Oxygen Vacancy-Engineered PEGylated MoO3-x Nanoparticles with Superior Sulfite Oxidase Mimetic Activity for Vitamin B1 Detection.

Sulfite oxidase (SuOx ) is a molybdenum-dependent enzyme that catalyzes the oxidation of sulfite to sulfate to maintain the intracellular levels of sulfite at an appropriate low level. The deficiency of SuOx would cause severe neurological damage and infant diseases, which makes SuOx of tremendous biomedical importance. Herein, a SuOx mimic nanozyme of PEGylated (polyethylene glycol)-MoO3-x nanoparticles (P-MoO3-x NPs) with abundant oxygen vacancies created by vacancy-engineering is reported. Their level of SuOx -like activity is 12 times higher than that of bulk-MoO3 . It is also established that the superior increased enzyme mimetic activity is due to the introduction of the oxygen vacancies acting as catalytic hotspots, which allows better sulfite capture ability. It is found that vitamin B1 (VB1) inhibits the SuOx mimic activity of P-MoO3-x NPs through the irreversible cleavage by sulfite and the electrostatic interaction with P-MoO3-x NPs. A colorimetric platform is developed for the detection of VB1 with high sensitivity (the low detection limit is 0.46 µg mL-1 ) and good selectivity. These findings pave the way for further investigating the nanozyme which possess intrinsic SuOx mimicing activity and is thus a promising candidate for biomedical detection.

Co3O4/CuO hollow nanocage hybrids with high oxidase-like activity for biosensing of dopamine.

Here, we report the synthesis, characterization, and oxidase-like activity of Co3O4/CuO hollow nanocage (HNC) nanocomposites. The Co3O4/CuO HNCs were successfully prepared by hydrothermal treatment of ZIF-67 in copper nitrate solution, followed by carbonization in air. The obtained nanocomposites were characterized by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. The Co3O4/CuO HNCs possess enhanced oxidase-like activity compared with pure Co3O4 and CuO, and they can catalytically oxidize the 3,3',5,5'-tetramethylbenzidine (TMB) substrate in the absence of H2O2 to produce an intense blue product. Reactive oxygen species (ROS) measurements indicate that 1O2 and O2- radicals are the major ROS in catalytic oxidation of TMB by dissolved oxygen in the TMB-Co3O4/CuO HNC system. We then developed a simple, sensitive, visual, and colorimetric biosensing method for dopamine (DA) based on its inhibiting effect on TMB oxidation. The proposed method allows for DA detection with a limit of detection of 0.027 µM and a dynamic range of 0.05-8 µM. This new colorimetric method was successfully used to detect DA in biological samples. The present work demonstrates a simple strategy to fabricate an efficient oxidase mimic with potential applications in bioanalysis and clinical diagnosis.

Colorimetric determination of dopamine by exploiting the enhanced oxidase mimicking activity of hierarchical NiCo2S4-rGO composites.

A composite consisting of NiCo2S4 and reduced graphene oxide (rGO) was prepared via a hydrothermal process. Compared to individual NiCo2S4 nanomaterials or reduced graphene oxide, the composite exhibits enhanced oxidase-like activity. It is found that dopamine (DA) inhibits the ability of NiCo2S4-rGO to oxidize the substrate 3,3',5',5'-tetramethylbenzidine (TMB) to form blue colored ox-TMB. Based on these findings, a colorimetric method for determination of DA was worked out. The absorption, best measured at 652 nm, increases linearly in the 0.5-100 µM DA concentration range, and the limit of detection is 0.42 µM. This method was successfully applied to the detection of DA in spiked human serum samples. Graphical abstract A hierarchical NiCo2S4-rGO composite was prepared through two-step hydrothermal process. It exhibits enhanced oxidase-like activity which, however, is inhibited by dopamine (DA). Hence, less blue colored ox-TMB is formed by oxidation of 3,3',5,5'-tetramethylbenzidine in the presence of dopamine.

High oxidase-mimic activity of Fe nanoparticles embedded in an N-rich porous carbon and their application for sensing of dopamine.

The N-doped porous carbon (NC) has been regarded as one of the promising support materials for nanoparticles (NPs) catalyst due to its inherent virtues such as porosity, large surface areas, and heteroatom incorporation. In this work, Fe/NC-800 hybrid was facilely prepared by uniform dispersion of in situ formed FeNPs onto NC-800 from carbonization of ZIF-8 at 800 °C for the first time. The optimized Fe/NC-800 catalyst was characterized by TEM, XPS and XRD. Compared with sole FeNPs and NC-800, the Fe/NC-800 catalyst exhibited an enhanced oxidase-like activity that could oxidize the colorless 3,3',5,5'-tetramethylbenzidine (TMB) to the heavy blue without extra oxidants such as H2O2. The possible reason for the enhanced oxidase-like activity of the Fe/NC-800 was discussed on the basis of the experiments of radical scavengers, indicating the importance of superoxide (O2•-) and singlet (1O2) in colorimetric reaction between TMB and Fe/NC-800 hybrid. Furthermore, the oxidase-like activity of Fe/NC-800 was significantly inhibited by dopamine (DA), leading to blue color fading. On this basis, a sensitive and selective colorimetric sensor was fabricated for the quantitative analysis of DA with a linear range of 0.01-40 µM and a low detection limit of 10 nM. The proposed colorimetric method was successfully applied to determine DA in human serum and injection samples, suggesting a promising application in biological analysis.

NiCoBP-doped carbon nanotube hybrid: a novel oxidase mimetic system for highly efficient electrochemical immunoassay.

NiCoBP-doped multi-walled carbon nanotube (NiCoBP-MWCNT) was first synthesized by using induced electroless-plating method and functionalized with the biomolecules for highly efficient electrochemical immunoassay of prostate-specific antigen (PSA, used as a model analyte). We discovered that the as-synthesized NiCoBP-MWCNT had the ability to catalyze the glucose oxidization with a stable and well-defined redox peak. The catalytic current increased with the increment of the immobilized NiCoBP-MWCNT on the electrode. Transmission electron microscope (TEM) and energy dispersive X-ray spectrometry (EDX) were employed to characterize the as-prepared NiCoBP-MWCNT. Using the NiCoBP-MWCNT-conjugated anti-PSA antibody as the signal-transduction tag, a new enzyme-free electrochemical immunoassay protocol could be designed for the detection of target PSA on the capture antibody-functionalized immunosensing interface. Experimental results revealed that the designed immunoassay system could exhibit good electrochemical responses toward target PSA, and allowed the detection of PSA at a concentration as low as 0.035ngmL(-1). More importantly, the NiCoBP-MWCNT-based oxidase mimetic system could be further extended for the monitoring of other low-abundance proteins or disease-related biomarkers by tuning the target antibody.