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To regulate nanostructure synthesis is of crucial importance for developing various applications, including catalysis, bioanalysis, and optical devices. Herein, the morphology and peroxidase (POD)-mimicking activity of peptide-templated copper nanoassemblies (Cu NAs) are regulable with peptide types. The Cu NAs templated with peptide containing single cysteine are uniform nanoclusters with strong POD-like activity. However, the Cu NAs templated with peptide containing two cysteines are fusiform-like with very weak POD-like activity. Unexpectedly, the POD-like activity of Cu NAs templated with peptide containing two cysteines with lysine between the cysteines is significantly enhanced when trypsin is incubated, which is unchanged for the Cu NAs templated with peptide containing two cysteines without lysine between the cysteines. The remarkably enhanced POD-mimicking activity originates from trypsin specifically shearing the peptide bond on the lysine, thereby allowing the aggregated Cu NAs to unravel into individual nanoclusters. Therefore, a robust colorimetric sensing platform was constructed for sensitive and selective detection of trypsin, which showed a linear concentration range of 3-1000 nM and a detection limit of 0.82 nM (S/N = 3). More interestingly, featured by trypsin inhibitor restraining trypsin activity, it enabled us to screen trypsin inhibitors as well. Subsequently, the developed assay was applied to detect trypsin in serum samples with good accuracy and reproducibility. Thus, this strategy shows great potential application in the clinic for diagnosis of trypsin-indicating diseases as well as the screening of trypsin inhibitor-based anti-cancer drugs.

Nanozymes are artificial enzymes, which can substitute natural enzymes for wide range of catalysis-based applications. However, it is challenging to explore novel mimic enzymes or multi-enzyme mimics. Herein we report the facile preparation of uniform CuS nanoclusters (NCs), which possessed outstanding tetra-enzyme mimetic catalytic activities, including peroxidase (POD)-mimics, catalase (CAT)-mimics, ascorbic acid oxidase (AAO)-mimics and superoxide dismutase (SOD)-mimics. The catalytic mechanism of POD-like was coming from the oxygen vacancies of CuS. Furthermore, the steady-state kinetics of POD-, CAT- and AAO mimics of CuS NCs were systematically explored. On basis of the enzymatic cascade reaction that acid phosphatase (ACP) involved in a weak acidic environment, in the presence of O-phenylenediamine, quinoxaline fluorescent substance will be generated. Thus, a fluorescent biosensor platform was proposed for detection of ACP with the linear range of 0.05-25 U L -1 and limit of detection of 0.01 U L -1 . The as-proposed method was applicable to real serum sample detection accurately and reproducibly. Considering the simple preparation, good stability, excellent multi-enzyme activities and controllable experimental operation, CuS NCs would provide a basis for expanding to other biocatalytic and biomedical applications., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Nanozymes are artificial enzymes, which can substitute traditional biological enzymes for multifield applications. However, to date, it remains challenging to search novel mimic enzymes or multienzyme mimics. Herein, a facile and green method for preparing monodisperse, homogeneous copper nanoclusters (Cu NCs) with smaller size was developed, which used cysteamine as a template and hydrazine hydrate as a reductant to reduce Cu 2+ . The as-prepared Cu NCs exhibited excellent tetraenzyme-like activities, including peroxidase (POD)-, catalase (CAT)-, superoxide dismutase (SOD)-, and ascorbic acid oxidase (AAO)-mimic activities. The mechanisms, kinetics, and catalytic performances of Cu NCs were systematically studied. Moreover, based on the POD-like activity of Cu NCs, sensitive and simple colorimetric sensing glutathione (GSH) was explored, with the low limit of detection of 0.89 μM GSH ( S / N = 3). Additionally, a novel fluorimetric ascorbic acid (AA) sensor was developed with the linear range of 0.5-30 μM and limit of detection (LOD) of 0.144 μM, on the basis of the principle that AA is oxidized to dehydroascorbic acid (DHAA) specifically catalyzed by the AAO-like activity of Cu NCs, while DHAA can further react with o -phenylenediamine (OPDA) to generate a highly fluorescent quinoxaline (DFQ) derivative. The as-proposed colorimetric GSH sensor and the fluorimetric AA sensor were capable of detecting GSH and AA, respectively, in real samples accurately and reproducibly. Thus, the Cu NCs-based multienzyme mimic is a promising candidate for biocatalysis and biosensing.

A highly selective and sensitive electroanalysis strategy has been developed for sensing histamine (HTA) and histidine (His) with "turn-on" signal outputs using copper nanocomposites (Cu NCs) of reduced copper metal-organic frameworks (Cu MOFs). It was discovered that the Cu NC-modified electrodes could display the sharp and stable oxidation peaks of solid-state CuCl electrochemistry at a low potential (about -0.10 V). More interestingly, once HTA or His was introduced, the peaking currents of the electrodes would increase due to the specific interaction between Cu 2+ and imidazole groups of HTA or His. A highly selective electroanalysis method was thereby developed for the detection of both HTA and His in the concentration range of 0.010-100 μM. Besides, the application feasibility of the developed electroanalysis strategy was demonstrated for the evaluation of HTA and His separately in red wine and urine samples. Such an electroanalysis candidate for HTA and His holds great potential for wide applications in the fields of food analysis and clinical disease diagnosis.

A wettable well was fabricated on an electrode, which was further modified with carbon quantum dot-scaffolded nanocomposites of melamine and copper for probing histidine through a unique displacement reaction route. The developed electrode with wettable well enables the condensing enrichment of analytes from the sample droplets, improving the electroanalytical sensitivity.

Silver nanoclusters (AgNCs) were first coated with bovine serum albumin (BSA) and then encapsulated into porous metal-organic frameworks of ZIF-8 by the protein-mediated biomineralization process. Unexpectedly, the fluorescence intensities of the yielded AgNCs-BSA@ZIF-8 nanocomposites were discovered to be continuously enhanced during each of the BSA coating and ZIF-8 encapsulation steps. Compared to common AgNCs, greatly improved photostability and storage stability of AgNCs could also be expected. More importantly, having benefited from the ZIF-8 shells, the prepared nanocomposites could possess the specific accumulation and sensitive response to Cu 2+ ions, resulting in the rational quenching of their fluorescence intensities. Moreover, AgNCs-BSA@ZIF-8 nanocomposites were coated onto the hydrophobic arraying slides toward a microdots array-based fluorimetric method for the fast and sensitive evaluation of Cu 2+ ions. It was discovered that the developed fluorimetric strategy could ensure the high-throughput analysis of Cu 2+ ions in wide pH range, and especially some harsh and high-salt media. It can allow for the detection of Cu 2+ ions in blood with the concentrations ranging from 4.0 × 10 -4 to 160 μM, thus serving as a new copper detection candidate to be widely applied in clinical test, food safety, and environmental monitoring fields.

A simple colorimetric sensing strategy for Hg2+ ions was developed using silver/copper nanoclusters (Ag/Cu NCs) with excellent selectivity and sensitivity. Bimetallic Ag/Cu NCs were synthesized by using glutathione (GSH) as a template and sodium borohydride as a reducing agent. It was found that the peroxidase-like activity of Ag/Cu NCs was significantly enhanced in the presence of Hg2+. Therefore, a colorimetric method based on catalysis was developed to detect Hg2+ with a linear concentration range of 0.1–700 nM and a detection limit of 0.05 nM (S/N = 3). The common species have no effect on Hg2+ ion detection. Furthermore, this method is applicable to accurately detect Hg2+ in real aqueous samples and is reproducible. Therefore, owing to the merits of sensitivity, selectivity, rapid response and visual read-out, it can be promising in the development of a portable Hg2+ analyzer for on-site detection. [ABSTRACT FROM AUTHOR]

A highly selective and reproducible electroanalysis strategy was developed for probing histidine using tetrahedral copper metal organic frameworks. It can facilitate His detection through the stable "turn-on" signal output of solid-state CuCl electrochemistry at a potential approaching zero, with the level down to about 25 nM in blood. [ABSTRACT FROM AUTHOR]