Sensitive and selective detection of chromium (VI) based on two-dimensional luminescence metal organic framework nanosheets via the mechanism integrating chemical oxidation-reduction and inner filter effect.

Two-dimensional luminescence metal organic framework nanosheets (LMOF) named NH2-CuMOFs were synthesized using Cu (II) nodes coordinated with negatively charged 2-aminoterephthalic acid (NH2-BDC) via a bottom-up strategy, which were first used as the fluorescent probes for the detection of chromium Cr (VI). The nanosheets possess stable fluorescence with the maximum emission wavelength of 436 nm at excitation of 338 nm that can be effectively quenched by hexavalent chromium Cr (VI). The NH2-CuMOFs nanosheets show superior advantage over the linker of NH2-BDC for the excellent selectivity to Cr (Ⅵ) without the interferences of other metal ions. The mechanism investigation suggested that the sensitive detection of Cr (VI) was attributed to the chemical oxidation-reduction (redox) reaction and internal filtration effect (IFE) between Cr (VI) and NH2-CuMOFs nanosheets. Based on this mechanism, the quantitation of Cr (VI) was realized in the linear range of 0.1-20 µM with a detection limit of 18 nM. Moreover, the detection of Cr (VI) in real samples was also conducted with good recovery. This work provides an optical sensing nanoplatform for heavy metal ions based on two-dimensional LMOFs via a novel mechanism integrating chemical redox reaction and IFE, which may promise broad application prospect for two-dimensional luminescence nanosheets.

Universal Nanoplatform for Formaldehyde Detection Based on the Oxidase-Mimicking Activity of MnO2 Nanosheets and the In Situ Catalysis-Produced Fluorescence Species.

Formaldehyde (HCHO) pollution is a scientific problem of general concern and has aroused wide attention. In this work, a fluorometric method for sensitive detection of formaldehyde was developed based on the oxidase-mimicking activity of MnO2 nanosheets in the presence of o-phenylenediamine (OPD). The MnO2 nanosheets were prepared by the bottom-up approach using manganese salt as the precursor, followed by the exfoliation with bovine serum albumin. The as-prepared MnO2 nanosheets displayed excellent oxidase-mimicking activity, and can be used as the nanoplatform for sensing in fluorometric analysis. OPD was used as a typical substrate because MnO2 nanosheets can catalyze the oxidation of OPD to generate yellow 2,3-diaminophenazine (DAP), which can emit bright yellow fluorescence at the wavelength of 560 nm. While in the presence of formaldehyde, the fluorescence was greatly quenched because formaldehyde can react with OPD to form Schiff bases that decreased the oxidation reaction of OPD to DAP. The main mechanism and the selectivity of the platform were studied. As a result, formaldehyde can be sensitively detected in a wide linear range of 0.8-100 µM with the detection limit as low as 6.2 × 10-8 M. The platform can be used for the detection of formaldehyde in air, beer, and various food samples with good performance. This work not only expands the application of MnO2 nanosheets in fluorescence sensing, but also provides a sensitive and selective method for the detection of formaldehyde in various samples via a new mechanism.

Self-Catalyzed Surface Reaction-Induced Fluorescence Resonance Energy Transfer on Cysteine-Stabilized MnO2 Quantum Dots for Selective Detection of Dopamine.

A simple one-step ultrasonic method was developed for the synthesis of luminescent MnO2 quantum dots (MnO2 QDs) in the presence of cysteine, in which cysteine acted as the exfoliating agent and stabilization ligand. The cysteine-stabilized MnO2 QDs (Cys-MnO2 QDs) possess a fluorescence quantum yield of 4.7%, and the fluorescence intensity of Cys-MnO2 QDs is sensitive to dopamine (DA). The mechanism by which the Cys-MnO2 QDs catalyzed the self-polymerization of DA to form polydopamine nanoparticles (PDA NPs) and caused the fluorescence resonance energy transfer (FRET) between MnO2 QDs and PDA NPs was revealed. The sensing platform displayed a wide detection range (0.1-200 µM) with a low detection limit of 28 nM for the detection of DA. Moreover, the Michael addition/Schiff base reaction between the PDA NPs and cysteine on MnO2 QDs was demonstrated to facilitate the excellent selectivity toward DA detection in the presence of various interferences. This work not only develops a robust method for the preparation of highly luminescent MnO2 QDs but also provides a universal strategy on the basis of surface chemical reaction-induced FRET for the detection of DA with high sensitivity and selectivity, which is promising in the application of clinical diagnosis, drug delivery, and fluorescence-guided cancer therapy.

Facile Preparation of MnO2 Quantum Dots with Enhanced Fluorescence via Microenvironment Engineering with the Assistance of Some Reductive Biomolecules.

MnO2 nanomaterials have aroused widespread attention because of their nanozyme activity, redox properties, good biocompatibility, and therapy-related activities. However, not many reports on self-luminescent MnO2 materials have been concerned to date, which greatly hampered their further development in various fields. In this paper, luminescent MnO2 quantum dots (MnO2 QDs) have been first prepared via a facile one-step ultrasonic method. With the assistance of bovine serum albumin (BSA) or cysteine (Cys), the synthesized MnO2 QDs (BSA-MnO2 QDs or Cys-MnO2 QDs) display strongly enhanced fluorescence (FL). The prepared BSA-MnO2 QDs with a particle size of about 1 to 2 nm show the maximum excitation and emission peaks at 320 and 410 nm with excellent salt stability, anti-photobleaching ability, and time stability. It is confirmed that BSA plays a dual function as the exfoliating agent to promote the exfoliation of bulk MnO2 nanosheets and as the capping agent to provide a friendly microenvironment for MnO2 QDs. Ag ions can destroy the microenvironment of BSA-MnO2 QDs owing to the in situ formation of Ag nanoparticles (Ag NPs) mediated by BSA on the surface of the QDs. Then, these Ag NPs can quench the FL intensity of the QDs by fluorescence resonance energy transfer. However, the FL strength of the BSA-MnO2 QDs is recovered after adding H2O2 and NaHS since they may react with Ag NPs to produce Ag+ and Ag2S, which further confirmed the role of BSA. This work not only opens up a facile and universal avenue to synthesize luminescent MnO2 QDs with enhanced FL but also provides a possible sensing platform through tuning the microenvironment of the MnO2 QDs. The MnO2 QDs with outstanding performance may show great potential as fluorescent probes in the fields of biological imaging, optical sensing, drug delivery, and therapy.

A dual (colorimetric and fluorometric) detection scheme for glutathione and silver (I) based on the oxidase mimicking activity of MnO2 nanosheets.

A fluorimetric and colorimetric method is described for the determination of glutathione (GSH) and silver (I). It is based on the use of MnO2 nanosheets that were prepared by solution mixing and exfoliation. They display oxidase-mimicking activity and can catalyze the oxidation of o-phenylenediamine (OPD) to form yellow 2,3-diaminophenazine (DAP) with an absorption maximum at 410 nm. DAP also has a yellow fluorescence (with a peak at 560 nm). The MnO2 nanosheets can be rapidly reduced to Mn2+ by GSH. This reduces the efficiency of the oxidase mimic MnO2 and causes a decrease in fluorescence and absorbance intensity. However, on addition of Ag+, a complex is formed with GSH. It prevents the destruction of MnO2 nanosheets so that the enzyme mimicking activity is retained. A dual-method for the determination of GSH and Ag(I) was developed. It has excellent sensitivity for GSH with lower detection limits of 62 nM (fluorimetric) and 0.94 µM (colorimetric). The respective data for Ag(I) are 70 nM and 1.15 µM. The assay was successfully applied to the determination of GSH and Ag(I) in spiked serum samples. Graphical abstract Schematic presentation of a method for colorimetric and fluorometric determination of glutathione (GSH) and silver(I). MnO2 nanosheets are reduced to Mn(II) by GSH. This reduces the enzyme-mimicking activity of MnO2 nanosheets and causes a decrease in fluorescence and absorbance. On addition of Ag(I), the enzyme-like activity is increasingly retained. A decrease in fluorescence and absorbance is not observed any longer.

Colorimetric detection of ascorbic acid and alkaline phosphatase activity based on the novel oxidase mimetic of Fe-Co bimetallic alloy encapsulated porous carbon nanocages.

A novel catalyst of FeCo nanoparticles (FeCo NPs) incorporated porous nanocages (FeCo NPs@PNC) was first synthesized by encapsulating of FeCo alloy into ZIF-8 and further carbonation of the composite. The FeCo NPs@PNC displays enhanced intrinsic oxidase-like activity compared to the individual FeCo NPs and porous nanocages (PNC). The FeCo NPs@PNC can catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) to oxidized TMB (oxTMB) without H2O2, producing a blue color with a maximum absorption peak at 652 nm. The catalytic mechanism was investigated and it found that the intermediate (O2·-) produced from the catalytic process in the system of TMB-O2-FeCo NPs@PNC can accelerate the oxidation of TMB to oxTMB. However, ascorbic acid (AA) can reduce the oxTMB and result in a conspicuous blue color fading. Therefore, a novel colorimetric platform was constructed to quantify AA with the linear range of 0.5-28 µM and detection limit of 0.38 µM (at 3σ/m). Owing to the alkaline phosphatase (ALP) can catalyze the hydrolysis of AA 2-phosphate (AAP) into AA, ALP can also be quantified by the above method. And the linear range for ALP is 0.6-10 U L-1 and the limit of detection is 0.49 U L-1. The FeCo NPs@PNC also shows excellent stability and reproducibility. This study provides a new alternative oxidase mimetic on the basis of easily obtained metal-organic frameworks derivatives to replace the expensive natural enzymes and noble metal based nanoenzymes, which will show great potential in biological assays.

A novel biomimetic nanoenzyme based on ferrocene derivative polymer NPs coated with polydopamine.

In this paper, ferrocene derivative polymer nanoparticles (FcP NPs) with uniform size and good photostability was synthesized using 1,1'-ferrocene dicarboxylic acid as precursor and methanol as solvent. FcP NPs-PDA was further obtained by coating of polydopamine (PDA) on FcP NPs in tris-HCl (pH=8.5) buffer solution at room temperature in the presence of dopamine (DA). The structure and morphology of FcP NPs and FcP NPs-PDA were characterized by transmission electron microscope (TEM), ultraviolet-visible spectroscopy (UV-Vis), and infrared radiation (FT-IR). The as-prepared FcP NPs-PDA showed better peroxidase-like activity than FcP NPs, which could catalyze the chromogenic reaction of peroxidase substrate TMB, OPD and ABTS. Based on the high peroxidase-like property of FcP NPs-PDA, a sensitive and convenient means to detect H2O2 has been proposed with TMB as the substrate, which displays wide linear range of 10-600 µM and 600 µM-4 mM with low detection limit of 5 µΜ. Compared with other Fe-containing NPs, such as magnetic materials and noble metal@Fe bimetallic NPs, the preparation approach for FcP NPs-PDA is simple, time and energy saving and environment friendly. This mild and simple synthesis route of FcP NPs-PDA will provide new ideas for the preparation of non-noble metal-based peroxidase-like nanomaterials and widen the applications in the fields of catalytic and analytical chemistry.

Colorimetric determination of ascorbic acid and the activity of alkaline phosphatase based on the inhibition of the peroxidase-like activity of citric acid-capped Prussian Blue nanocubes.

Colorimetric methods are described for the determination of ascorbic acid (AA) and alkaline phosphatase (ALP). Both assays are based on the inhibition of the peroxidase (POx)-like activity of Prussian Blue nanocubes (PB NCs) capped with citric acid. They catalyze the oxidation of 3,3,5,5-tetramethylbenzidine (TMB) by H2O2 to produce a blue color with an absorption maximum at 652 nm. On addition of AA, the PB NCs are reduced to Prussian White (PW) which does not act as a POx mimic. This results in a decreased rate of the formation of the blue coloration whose intensity decreases with increasing concentration of AA. The assay allows AA to be quantified with a 35 nM detection limit (at 3σ/m). The hydrolysis of AA phosphate by ALP leads to the formation of AA which can be quantified by the above method. Based on this, the activity of ALP can be determined by measurement of the intensity of the blue coloration thus formed. The method can be used to determine the activity of ALP with a detection limit as low as 0.23 U·L-1. Graphical abstract Schematic presentation of a method for colorimetric determination of ALP activity. AA obtained by ALP-catalyzed hydrolysis of ascorbic acid phosphate (AAP) inhibits the intrinsic peroxidase-like activity of PB NCs by reducing Prussian Blue nanocrystals (PB NCs) to form inactive Prussian White (PW).

miR-219 Cooperates with miR-338 in Myelination and Promotes Myelin Repair in the CNS.

A lack of sufficient oligodendrocyte myelination contributes to remyelination failure in demyelinating disorders. miRNAs have been implicated in oligodendrogenesis; however, their functions in myelin regeneration remained elusive. Through developmentally regulated targeted mutagenesis, we demonstrate that miR-219 alleles are critical for CNS myelination and remyelination after injury. Further deletion of miR-338 exacerbates the miR-219 mutant hypomyelination phenotype. Conversely, miR-219 overexpression promotes precocious oligodendrocyte maturation and regeneration processes in transgenic mice. Integrated transcriptome profiling and biotin-affinity miRNA pull-down approaches reveal stage-specific miR-219 targets in oligodendrocytes and further uncover a novel network for miR-219 targeting of differentiation inhibitors including Lingo1 and Etv5. Inhibition of Lingo1 and Etv5 partially rescues differentiation defects of miR-219-deficient oligodendrocyte precursors. Furthermore, miR-219 mimics enhance myelin restoration following lysolecithin-induced demyelination as well as experimental autoimmune encephalomyelitis, principal animal models of multiple sclerosis. Together, our findings identify context-specific miRNA-regulated checkpoints that control myelinogenesis and a therapeutic role for miR-219 in CNS myelin repair.