Cobalt-Based Metal-Organic Framework Nanoparticles with Peroxidase-like Catalytic Activity for Sensitive Colorimetric Detection of Phosphate

Adenosine triphosphate (ATP) is produced mainly in the mitochondrion, and its primary task is to function as a ubiquitous energy currency to meet the cellular metabolic demands in biological system...

A peroxidase-like nanoenzyme based on strontium(II)-ion-exchanged Prussian blue analogue derivative SrCoO3/Co3O4 nanospheres and carbon quantum dots for the colorimetric detection of tigecycline in river water

The intrinsic peroxidase-like activity of hollow Prussian Blue nanoparticle-loaded with gold nanoparticles (Au@HMPB NPs) were applied to oxidize the substrate 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H2O2 to give a blue-green coloration. The morphology of the Au@HMPB NPs and its peroxidase-mimicking activity was characterized in detail. The catalytic activity follows Michaelis-Menten kinetics and is higher than that of HMPB NPs not loaded with gold nanoparticles. The NPs were employed to detect L-lactic acid colorimetrically (at 450nm) via detection of H2O2 that is generated during enzymatic oxidation by L-lactate oxidase (LOx). The limit of detection is 4.2μM. The assay was successfully applied to the quantitation of L-lactic acid in spiker human serum samples. Graphical abstract Gold nanoparticle-loaded hollow Prussian Blue nanoparticles (Au@HMPB NPs) with peroxidase-like catalytic activity can oxidize the substrate 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H2O2. The nanoparticles were applied for the detection of L-lactic acid through detection of H2O2 that is generated by L-lactate oxidase (LOx) catalyzed oxidation of L-lactic acid.

Engineering nickel-supported osmium bimetallic nanozymes with specifically improved peroxidase-like activity for immunoassay

Facile preparation of Fe3O4 nanospheres/reduced graphene oxide nanocomposites with high peroxidase-like activity for sensitive and selective colorimetric detection of acetylcholine

In the present study, we present nanostructured bimetallic Cu/CuCl/Cu2S/Au(Ag) supports that exhibit plasmonic electromagnetic field enhancement and peroxidase-like catalytic activity. The Cu2S component acts as the peroxidase-like catalyst, while the Au or Ag component provides the necessary light enhancement for surface enhanced Raman spectroscopic (SERS) studies of surface bound molecular reactants. As a test reaction the catalytic oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) in presence of H2O2 was investigated. The comparison of product evolution in solution measured by UV-Vis spectroscopy and on the surface measured via SERS is able to give more insight into the different steps involved in the overall catalysis.

In this study, FeTOMPP (Tetrakis(4-methoxyphenyl) phenylporphyrinatoiron(III)) was synthesized and investigated for its peroxidase-like activity. The catalytic performance of FeTOMPP as a peroxidase mimic was explored by utilizing the colorless peroxidase substrate, 3,3',5,5'-tetramethylbenzidine (TMB), in the presence of hydrogen peroxide (H2O2). The oxidation of TMB by FeTOMPP resulted in the formation of its blue oxidized state. This enzymatic reaction was employed for the quantitative detection of H2O2, with a linear detection range spanning from 1.0 to 100 µM. The detection limit achieved using FeTOMPP as the catalyst was determined to be 2.4 µM. Furthermore, kinetic studies were conducted to investigate the interaction between FeTOMPP and H2O2. The results indicated that FeTOMPP exhibited favorable affinity towards H2O2, further highlighting its potential as a peroxidase mimic. In addition to its peroxidase-like activity, a simple and sensitive visual and colorimetric method was developed for the detection of ethanol by combining FeTOMPP with alcohol oxidase. The method relied on the use of TMB as the substrate. Ethanol-containing samples were subjected to the enzymatic reaction, resulting in the generation of a color change. The detection of ethanol was achieved with a minimum detection limit of 0.95 % v/v, and the linear range for quantification extended from 0 to 15 % v/v. This study demonstrates the potential application of FeTOMPP as a peroxidase mimic for the sensitive detection of H2O2 and the development of a colorimetric method for ethanol detection. The findings highlight the versatility and promising capabilities of FeTOMPP in various analytical and diagnostic applications. HIGHLIGHTS The potential application of FeTOMPP as a peroxidase mimic for the sensitive detection of H2O2. The development of colorimetric method for ethanol detection by combining FeTOMPP with alcohol oxidase. GRAPHICAL ABSTRACT

Ultra-fast colorimetric detection of glutathione by magnetic Fe NPs with peroxidase-like activity

Two-dimensional metal-organic framework nanosheets are attractive as peroxidase mimicking nanocatalysts due to their rich chemical functional groups, large surface area, high porosity, and accessible active sites. In this study, we synthesized FeCu bifunctional 2D MOF nanosheets using a solvothermal method. Fe and Cu ions were added as metal precursors, while organic amine and acid served as the organic ligands to construct the FeCu-MOF nanosheets. These nanosheets demonstrated robust peroxidase-like catalytic activities and were employed to develop a visual detection system for multiple targets, such as glucose and kanamycin. In the detection mechanism, glucose was oxidized into gluconic acid by glucose oxidase (GOx), leading to the generation of H2O2. When H2O2 is present, the FeCu-MOF NSs demonstrate high intrinsic peroxidase-like activity, which might catalytically oxidize 3,3',5,5'-tetramethylbenzidine (TMB) into a blue-coloured oxTMB product with a strong UV absorption at 654 nm. Subsequently, kanamycin was added to the above sensing system. The kanamycin strongly interacted with the FeCu-MOF NSs through H-bonding and blocked electron transfer, resulting in a colour change of the solution from blue to colourless with a weak UV absorption at 654 nm. Under the optimal conditions, the proposed colorimetric sensor exhibits an excellent linear response to glucose and kanamycin over the 0.25-5 μM and 0.02-0.1 μM ranges, respectively. The proposed colorimetric assay detection limits for glucose and kanamycin were found to be as low as 0.1 μM and 8 nM, respectively, and such a sensor shows excellent selectivity and sensitivity against different potential interferents. Thus, our proposed colorimetric assay was satisfactory when applied to glucose and kanamycin detection in agricultural and livestock husbandry samples.

Modulating the peroxidase-like activity of Fe single-atom nanozymes via atomic-scale inter-site distance engineering.

Novel PEI–AuNPs–MnIIIPPIX nanocomposite with enhanced peroxidase-like catalytic activity in aqueous media

Nanomaterials as enzyme mimics have received considerable attention as they can overcome some serious disadvantages associated with the natural enzymes. In recently developed Co3O4 nanoparticles as peroxidase mimics, the influence of the crystal plane on the catalytic performance has not been demonstrated. In order to better understand their crystal plane-dependent catalysis, the present study was initiated using three different Co3O4 nanomaterials, nanoplates, nanorods and nanocubes, as model systems. According to HRTEM, the predominantly exposed planes of nanoplates, nanorods and nanocubes are {112}, {110} and {100} planes, respectively. The catalytic activities were explored by using H2O2 and different organic substrates as the substrates of peroxidase mimics, and were investigated in-depth by steady-state kinetics and electrochemistry methods in depth. The results show that the peroxidase-like activity increases from nanocubes to nanoplates, via nanorods. The effect of external conditions such as pH and temperature on the three nanomaterials is the same, which indicates that the difference in their catalytic activities originates from their different shapes. The peroxidase-like catalytic activities of Co3O4 nanomaterials are crystal plane-dependent and follow the order: {112} ≫ {110} > {100}. The three crystal planes have different arrangements of surface atoms, thus exhibiting different abilities of electron transfer, which induce their different peroxidase-like catalytic activities. This investigation clarifies that the peroxidase-like activity of Co3O4 nanomaterials can be enhanced by shape control. These findings show that Co3O4 nanomaterials can serve as catalyst models for designing other catalysts.

Enzyme-mimetic properties of nanomaterials can be efficiently tuned by controlling their size, composition, and structure. Here, ultrathin PdCu alloy nanosheet-assembled three-dimensional (3D) nanoflowers (Pd1Cux NAFs) with tunable surface composition are obtained via a generalized strategy. In presence of H2O2, the as-synthesized Pd1Cux NAFs can catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) to the oxidized form of TMB (oxTMB) with a characteristic absorption peak at 652 nm. Interestingly, Pd1Cux NAFs show obviously composition-dependent peroxidase-like catalytic activities because of the synergistic interaction of nanoalloy. Additionally, different from 2D Pd nanosheets, the distinctive 3D superstructures are featured with rich approachable sites and proper layer spacing, which are in favor of fast mass transport and electron transfers during the catalytic process. Among the studied Pd1Cux NAFs, the Pd1Cu1.7 NAFs show the highest enzyme-like activities and can be successfully applied for the colorimetric detection of glucose with a low detection limit of 2.93 ± 0.53μM. This work provides an efficient avenue to fabricate PdCu NAF nanozymes in biosensing toward glucose detection. Two-dimensional (2D) PdCu ultrathin nanosheet-assembled 3D nanoflowers (Pd1Cux NAFs) with tunable surface composition exhibit substantially enhanced intrinsic peroxidase-like catalytic activities. The Pd1Cu1.7 NAFs are successfully used as peroxidase mimic catalyst for the colorimetric detection of glucose with low detection limit of 2.93μM.

In this work, AuAgPd trimetallic nanoparticles (AuAgPd TNPs) with intrinsic and broad-spectrum peroxidase-like activity were synthesized through a one-pot method by co-reduction of HAuCl4, AgNO3, and Na2PdCl4 with NaBH4. The morphology and composition of AuAgPd TNPs were characterized. The peroxidase-like activity of AuAgPd TNPs were highly dependent on the composition and nanostructure of AuAgPd TNPs. Rationally designed AuAgPd TNPs could catalyze the oxidation of various chromogenic substrates including 3,3'5,5'-tetramethylbenzidine (TMB), 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS), and o-phenylenediamine (OPD) by H2O2 to generate blue, green, and yellow products, respectively. Kinetic assays indicated that AuAgPd TNPs exhibited high affinity to H2O2. Then, sensitive colorimetric assays were developed for H2O2 detection by using ABTS, OPD, and TMB as chromogenic substrates, respectively. Lowest limit of detection (LOD) of 3.1 μM with wide linear range of 6-250 μM was obtained by using ABTS as substrate. Hydrogen sulfide ion (HS-) could effectively inhibit the peroxidase-like activity of AuAgPd TNPs. Thus, a selective colorimetric assay was further fabricated for HS- detection with LOD of 2.3 μM. This work provides an effective way for the synthesis of trimetallic nanozyme with peroxidase-like activity and also for tailoring their catalytic activity for desired use. Graphical abstract.

Shikimic acid derived carbon-dots nanozyme with peroxidase-like activity: A dual-mode probe for ratiometric fluorescence and colorimetric detection of hymexazol.