Catechol oxidase nanozyme based colorimetric sensors array for highly selective distinction among multiple catecholamines.

In order to effectively monitor multiple catecholamine (CA) neurotransmitters with extreme similar structures, a rapid, sensitive and selective detection strategy has become an urgent problem to be solved. In this paper, a novel colorimetric sensors array based on CuNCs protected by various ligands such as tannic acid, ascorbic acid and polymethylacrylic acid (CuNCs@TA, CuNCs@AA and CuNCs@PMAA) was constructed. All of these CuNCs could mimic catechol oxidase to selective catalyze catechol-type analogues (such as CAs) to corresponding quinones along with color changes. Furthermore, experiments and theory calculations demonstrated that Cr6+-modification on the surface of CuNCs facilitated the steady-state kinetics of enzymatic activity. Based on these CuNCs as sensing probes, this sensors array can quickly detect different CAs (such as epinephrine (EP), including dopamine (DA), norepinephrine (NE) and l-dopa) with similar structures. When those analogues were added to the CuNC-based colorimetric array sensors, different absorbance changes were produced at 485 nm. Linear discriminant analysis (LDA) showed that the tri-probe colorimetric array sensors could recognize and distinguish these analogues, and corresponding binary and ternary mixtures could be well categorized. The value of Factor 1 of an array with varied CA concentrations had a good linear correlation, and the detection limit (LOD) was as low as 10-8∼10-9 mol/L. Four CA analogues in real samples were identified by CuNCs-based colorimetric array sensors. This work provides a fast and convenient experimental basis for monitoring the complex structure CAs neurotransmitters.

NH2-MIL-101(Fe) nanozyme-based dual-modality sensor for determination of alendronate sodium and study of two-dimensional correlation spectroscopy.

We developed a dual-modality sensing platform for ratiometric fluorescence and colorimetric determination of alendronate sodium (ALDS). This platform was performed by using a NH2- MIL-101(Fe) as a peroxidase mimic. Since preferential complexing between Fe3+ (active site for peroxidase) and ALDS, the production of 2,3-diaminophenazine (DAP, oxidized product of OPD) has been inhibited in the presence of H2O2. As a result, the ratiometric fluorescence value of F556/F456 and absorbance at 450 nm exhibited significant changes, which could be used as the dual-modality sensing platform. In addition, Two-dimensional correlation spectroscopy (2D-COS) analysis on Fourier-transform infrared (FTIR), ultraviolet visible and ratiometric fluorescence spectra were applied to investigate the binding features. Synchronous and asynchronous maps of these spectra confirmed our above hypothesis, in which Fe3+-ALDS complex was the critical factor that regulated dual-modality signals. To our knowledge, the 2D-COS method was applied to study the catalytic and sensing mechanism of nanozyme as NH2- MIL-101(Fe) for the first time. This technique was helpful to understand interaction of substrates on nanozyme and develop more sensitive sensors for assaying.

Supramolecule self-assembly synthesis of amyloid phenylalanine-Cu fibrils with laccase-like activity and their application for dopamine determination.

Laccases are multicopper proteins for dioxygen-involved oxidation of a broad spectrum of organic compounds. I Novel amyloid-like phenylalanine-Cu (F-Cu(II)) fibrils were developed, which were obtained via supramolecular self-assembly of Cu2+ and phenylalanine (F) under basic condition. The obtained amyloid-like fibrils represented highly periodic structure, of which the lattice unit was constructed via alternating hydrophobic (aromatic environment) and hydrophilic (both hydrogen bonding and Cu(II) coordination) interactions. Relative to natural laccases, the amyloid-like F-Cu(II) architecture exhibited comparable substrate affinity (Michaelis constant, Km = 0.75 mM) and higher catalytic efficiency (kcat/Km = 773.33 × 10-3 g-1 min-1L). Moreover, it exhibited remarkable tolerances in pH (4 ~ 10), temperature (room temperature ~ 200 ℃), organic solvent, and long-term storage (> 15 days). These stabilities were superior among the reported nature and artificial laccases, presenting a more promising candidate in various chemo- or bio-applications. In addition, F-Cu(II) fibrils could catalyze the oxidation of dopamine (DA) to a brown product, in which a new absorption band at 470 nm was observed. Based on this, a simple colorimetric assay for the detection of DA could be performed. We reported a novel amyloid-like phenylalanine-Cu fibrils, in which F-Cu+ complex can mimick the T1 site of natural laccase to oxidize the substrates. Then electrons transferred to F-Cu2+ complex via N-H···O=C hydrogen binding pathway. Finally, the dioxygen was transformed to water though radical reaction.

Synthesis of water-soluble, ultrabright Cu nanoclusters with core-shell structure via facile reduction approach for determination of 4-nitrophenol.

In this work, we reported a facile reduction approach for fabrication of water-soluble and ultrabright Cu nanoclusters with core-shell structure. A certain amount of reducing agent as NaBH4was introduced into the polyethyleneimine-stabilized Cu nanoclusters (CuNCs@PEI) system, which exhibited 4-fold fluorescence enhancement along with a blue shift of the emission peak. The variations of morphology, valence states and functional groups demonstrated that a Cu shell was formed surround CuNCs (defined as CuNCs-Cu@PEI), attributable to metal complex (PEI-Cu+and PEI-Cu2+) reduction. The effect of core-shell morphology on luminous and electron relaxation mechanism of CuNCs-Cu@PEI was investigated via temperature-dependent steady and time-resolved fluorescence measurements. The CuNCs-Cu@PEI with a high fluorescence quantum yields of 22.59% were able to homogeneously disperse in aqueous phase, indicating their potential applications in biological labeling, sensing and invivoimaging. Finally, the CuNCs-Cu@PEI was employed as a fluorescence probe to determine 4-nitrophenol, of which the detection limit was much lower than initial CuNCs@PEI.

Nitrogen-terminated silicon nanoparticles obtained via chemical etching and passivation are specific fluorescent probes for creatinine.

A method is described here to prepare water-dispersible nitrogen-functionalized silicon nanoparticles (N-SiNPs). It consists of two steps, viz. etching of the oxidized shell of SiNPs and nitrogen-passivation of the exposed silicon. The resulting N-SiNPs have an average diameter of 2.6±0.7 nm and show blue fluorescence (with excitation/emission peaks at 340/420 nm). The fluorescence quantum yield is 23% and the decay time is in the nanosecond regime. Compared to etching methods using a plasma or hydrofluoric acid, the process described here (etching and passivation) is mild, continuous, fast, and air-compatible. The N-SiNPs modified with chlorotetracycline are shown to be a viable fluorescent probe for creatinine. Fluorescence drops in the 0 to 20 µM creatinine concentration range, and the limit of detection is 0.14 µM.

11-Mercaptoundecanoic acid capped gold nanoclusters as a fluorescent probe for specific detection of folic acid via a ratiometric fluorescence strategy.

A novel ratiometric fluorescence strategy is developed for specific detection of folic acid (FA) by using 11-mercaptoundecanoic acid protected gold nanoclusters (AuNCs@MUA). In this design, the fluorescence color of the probe can be switched among red, pink, violet and blue by varying the concentration of FA. AuNCs@MUA possesses strong fluorescence peaking at 612 nm (R-signal) and FA exhibits blue emissive auto-fluorescence at 446 nm (B-signal), showing a large emission shift of ∼170 nm. When AuNCs@MUA approaches FA through electrostatic binding, the R-signal decreases while the B-signal increases with titration of FA. Based on the above phenomenon, a radiometric analysis platform is constructed for FA target detection, with a wide linear response range from 0 to 20 µM, and an excellent detection limit of 26 nM. This new ratiometric strategy exhibits low background, and wide signal changes in a low concentration range, which presents obvious advantages over most previous FA detections based on single-responsive fluorescence methods. Furthermore, the proposed method is successfully applied to determine FA in human serum samples.

Polyethyleneimine protected silver nanoclusters luminescence probe for sensitive detection of cobalt (II) in living cells.

A simple luminescence sensor, based on polyethyleneimine protected silver nanoclusters (AgNCs@PEI) is successfully fabricated via one-pot reduction method. The obtained AgNCs@PEI are characterized by high-resolution transmission electron microscopy (HR-TEM), Dynamic light scattering (DLS), transient and steady-state fluorescence, and UV-vis spectroscopy. The NCs show large Stocks-shift (∼130nm), high tolerability to extreme pH and high ionic strengths, and excellent photo-stability under UV irradiation, laying the basement for the practical applications. In addition, the sensor is used to detect the Co2+ basing on the luminescence quenching, which is interfered by pH conditions (from pH4.0 to pH7.4). As a luminescence probe for Co2+ ions, the detection limit of AgNCs@PEI is as low as 0.25nM, which is much lower than that of many other reports. Additionally, the AgNCs@PEI possess the advantages of good selectivity, fast response and abroad linear detection. A linear response range in 0.5nM-50µM is achieved for Co2+ when using 20µM AgNCs@PEI in BR buffer solution (neutral condition pH7.4). Incubation time of AgNCs@PEI toward Co2+ is only 2min and it can distinguish Co2+ from other 13 metal ions. Furthermore, the probe (AgNCs@PEI) is applied to sensing and imaging of HeLa cells, showing low cytotoxicity and good sensitivity.