An all-inorganic lead-free metal halide double perovskite for the highly selective detection of norfloxacin in aqueous solution.

Lead-based perovskites are highly susceptible to environmental influences, and their application in analytical chemistry, especially in aqueous solution, has been reported rarely. All-inorganic lead-free metal halide perovskites have been considered as a substitute for lead-based perovskites. Herein, a Cs2RbTbCl6 perovskite microcrystal (PMCs), which emits strong yellow-green fluorescence with a maximum emission wavelength at 547 nm, was for the first time  synthesized and characterized. The Cs2RbTbCl6 PMCs could be well dispersed in N,N-dimethylacetamide (DMF), and its fluorescence could be significantly enhanced by the addition of norfloxacin (NOR) in the aqueous solution. We found that the Cs2RbTbCl6 PMCs can be used as fluorescent probes (excitation, 365 nm; emission, 547 nm) to selectively detect NOR in a concentration range from 10.0 to 200.0 µM with the limit of detection (LOD) being 0.04 µM. The Cs2RbTbCl6 PMCs could also be adsorbed on filter paper to fabricate as a fluorescent test paper for visual detection of NOR under 365-nm ultraviolet (UV) lamp irradiation. The proposed method has the potential to establish a new analytical method to visualize the detection of NOR in aqueous environments and also promotes the application of all-inorganic lead-free perovskites for analytical detection in aqueous environments.

Hydroxyl-Directed Rh(III)-Catalyzed C-H Functionalization: Access to Benzo[de]chromenes.

A cascade oxidative annulation reaction of heterocyclic ketene aminals (HKAs) with internal alkynes catalyzed by [Cp*RhCl2]2 and oxidized by Cu(OAc)2·H2O was developed to efficiently synthesize highly functionalized benzo[de]chromene derivatives in good to excellent yields. The reaction proceeded by the sequential cleavage of C(sp2)-H/O-H and C(sp2)-H/C(sp2)-H bonds. These multicomponent cascade reactions were highly regioselective. In addition, all of the benzo[de]chromene products exhibited intense fluorescence emission in the solid state, and they demonstrated concentration-dependent quenching in the presence of Fe3+, indicating that these compounds could be used in the recognition of Fe3+.

A lead-free Cs2ZnCl4 perovskite nanocrystals fluorescent probe for highly selective detection of norfloxacin.

The abuse of antibiotics would seriously affect human health and has become of worldwide critical concern, thus it is urgent to develop an environmentally friendly and nontoxic fluorescent probe for antibiotics sensing. In this work, a lead-free Cs2ZnCl4 perovskite nanocrystals (PNCs) probe was fabricated for sensing norfloxacin (NOR) employing a modified ligand-assisted reprecipitation method. The prepared Cs2ZnCl4 PNCs probe had strong blue emission around 440 nm, and the characteristics of PNCs were systematically characterized by X-ray photoelectric spectroscopy (XPS), Fourier transforms infrared spectroscopy (FTIR), transmission electron microscope (TEM) and powder X-ray diffraction (XRD). The results revealed that the fluorescence intensity of the Cs2ZnCl4 PNCs was significantly enhanced after the introduction of norfloxacin. The Cs2ZnCl4 PNCs can be used as a fluorescent probe to selectively and sensitively detect norfloxacin in the concentration range from 0.2 to 50.0 µM, with a correlation coefficient (R2) of 0.9954 and the limit of detection (LOD, 3σ) of 0.1499 µM. The preparation and application of a lead-free perovskite fluorescent probe for norfloxacin would promote the application of perovskite fluorescent probes in biochemical assays.

Highly selective and rapid detection of silver ions by using a "turn on" non-fluorescent cysteine stabilized gold nanocluster probe.

Cysteine is widely used as a stabilizer for the preparation of fluorescent gold nanoclusters (Au NCs) with different fluorescence properties. Herein, by using cysteine as a stabilizer and controlling the synthesis conditions, a new non-fluorescent cysteine stabilized gold nanocluster (Cys-Au NCs) probe was prepared and a new strategy for "turning on" the fluorescence of the Cys-Au NCs was studied for rapid and selective detection of silver ions. In this strategy, the addition of silver ions to non-fluorescent Cys-Au NCs solution could quickly induce a visible fluorescence "turn on" phenomenon in 30 s. Further studies indicated that this fluorescence "turn on" phenomenon is specific for silver ions and the "turn on" fluorescence intensity has a linear relationship with the amount of silver ions in the range from 3.0 to 30.0 µM. Therefore, the non-fluorescent Cys-Au NCs were applied to the detection of silver ions in environmental water samples and a limit of detection (LOD) of 0.26 µM was obtained. This research sheds light on new applications of Au NCs and proposes a simple, rapid, sensitive, and visual method for the detection of metal ions.

Glutathione stabilized green-emission gold nanoclusters for selective detection of cobalt ion.

A glutathione stabilized Au nanoclusters (GSH-Au NCs) was synthesized here and used to selective detection of cobalt ion. The as-prepared GSH-Au NCs had strong green light emission around 500 nm, and the features of the NCs have been systematically characterized by UV-vis absorption, X-ray photoelectronic spectroscopic, Fourier transform infrared spectroscopy and transmission electron microscope characterization. The interactions between the GSH-Au NCs and metal ions was studied, and the results indicated that the fluorescence of the GSH-Au NCs could be quenched in the presence of Co2+ ion at pH of 6.0. The quenching ratio was linear with the concentration of Co2+ ions, and the calibration curve was I0/I = 0.1187cco + 0.6085 in the Co2+ concentration ranges from 2.0 to 50.0 µM with correlation coefficient (R2) of 0.9950 and the limit of detection (LOD, 3σ) of 0.124 µM. In addition, we collected environmental water samples to test the reliability of the method and demonstrated this method is simple, rapid, and selective.

One-pot synthesis of green-emitting gold nanoclusters as a fluorescent probe for determination of 4-nitrophenol.

A hydrothermal method was applied to the synthesis of green-emitting gold nanoclusters (Au NCs) which are shown to be viable fluorescent probes for 4-nitrophenol (4-NP). The Au NCs were prepared by using thiol-ß-cyclodextrin as a template. Under 365 nm excitation, their green fluorescence has a peak at 502 nm, with a narrow emission bandwidth of only 30 nm. The fluorescence and composition of the Au NCs were characterized and the mechanism of the nanocluster formation is discussed. Due to host-guest recognition of ß-cyclodextrin and 4-NP, fluorescence is quenched. The probe can selectively recognize 4-NP among other nitrophenols. A fluorometric and colorimetric assay was developed for 4-NP that works in the 0.1 to 100 µM concentration range and has a detection limit of 90 nM (at 3σ). Graphical abstractSchematic representation of hydrothermal synthesis of green-emitting gold nanoclusters using thiol-ß-cyclodextrin. Fluorescence is quenched and the absorption of the nanoclusters is increases in the presence of 4-nitrophenol.

DNA bioassays based on the fluorescence 'turn off' of silver nanocluster beacon.

Recognition and quantification of oligonucleotide sequences play important roles in medical diagnosis. In this study, a new fluorescent oligonucleotide-stabilized silver nanocluster beacon (NCB) probe was designed for sensitive detection of oligonucleotide sequence targets. This probe contained two tailored DNA strands. One strand was a signal probe strand containing a cytosine-rich strand template for fluorescent silver nanocluster (Ag NC) synthesis and a detection sections at each end. The other strand was a fluorescence enhancing strand containing a guanine-rich section for signal enhancement at one end and a linker section complementary to one end of the signal probe strand. After synthesis of the Ag NCs and hybridization of the two strands, the fluorescence intensity of the as-prepared silver NCB was enhanced 200-fold compared with the Ag NCs. Two NCBs were designed to detect two disease-related oligonucleotide sequences, and results indicated that the two target oligonucleotide sequences in the range 50.0-600.0 and 50.0-200.0 nM could be linearly detected with detection limits of 20 and 25 nM, respectively. The developed fluorescence method using NCBs for oligonucleotide sequence detection was sensitive, facile and had potential for use in bioanalysis and diagnosis.

Rapid synthesis of cesium lead halide perovskite nanocrystals by l-lysine assisted solid-phase reaction at room temperature.

Nowadays, there are many ways to obtain cesium lead halide perovskite nanocrystals. In addition to the synthesis methods carried out in solution, the solid-phase synthesis was reported involving grinding and milling. In this paper, we synthesized luminescent CsPbBr3/Cs4PbBr6 perovskite nanocrystals (PNCs) by three solid-phase synthesis methods (grinding, knocking, stirring) using l-lysine as a ligand. This is the first attempt to use an amino acid for assisting the solid phase synthesis of perovskite and to study the difference in the products obtained by the three solid phase synthesis methods. The results show that the productivity of the solid-phase synthesis methods can be greatly improved by adding l-lysine and the perovskites obtained by the methods are more resistant to water due to the addition of l-lysine. The simplicity of the synthesis process expanded the use of solid-phase synthesis to obtain more perovskites and provided potential applications of perovskite in analytical detection and sensing in aqueous solution.

Fluorescent carbon quantum dots synthesized using phenylalanine and citric acid for selective detection of Fe3+ ions.

A facile, economical and one-step hydrothermal method was used to synthesize fluorescent carbon dots by utilizing citric acid as carbon source and phenylalanine to provide nitrogen. The as-prepared fluorescence carbon dots had strong blue light emission around 440 nm. As confirmed by UVvis absorption, X-ray photoelectron spectroscopic, Fourier transform infrared spectroscopy and transmission electron microscope characterization, the carbon dots were small and very stable in water for using as a fluorescent probe. It was also found that the fluorescence of the carbon dots could be quenched in the presence of Fe3+ ions, and the quenching rate was linear with the concentration of Fe3+ ions. We here proposed a static quenching mechanism about the fluorescence of the Phe-CDs could be selectively quenched by Fe3+ ions, which was because these Fe3+ ions could easily combine with the hydroxyl or carboxyl groups on the surface of Phe-CDs and induced aggregation. In addition, the pH had little effect on the fluorescence intensity of the Phe-CDs and maintained excellent fluorescence intensity even under extreme pH value conditions and could be used for the detection of Fe3+ ions. We have demonstrated that the method using the carbon dots for Fe3+ ions detection was rapid, reliable, and selective with a detection limit as low as 0.720 µM and a dynamic range from 5.0 to 500.0 µM. Moreover, the results of determination Fe3+ ions in tap water samples indicated that the presented method has potential for practical application in environmental metal analysis.

The presence of a single-nucleotide mismatch in linker increases the fluorescence of guanine-enhanced DNA-templated Ag nanoclusters and their application for highly sensitive detection of cyanide.

Fluorescence of DNA-templated silver nanoclusters can be enhanced by more than 100-fold by placing the nanoclusters in proximity to guanine-rich DNA sequences after hybridization. We found that the fluorescence of the guanine-enhanced silver nanoclusters is not increased with the guanine-rich DNA sequence closer to the silver nanoclusters. By studying the different numbers of mismatches in the linker sequences, we found that the presence of a single-nucleotide mismatch in the linker increases fluorescence more than the complementary nucleotide. Further study indicated the mismatch position of the linker sequence also affects the fluorescence of the hybridized DNA-Ag NCs. The evidence reported here indicated that the mismatch of the linker sequence affects the fluorescence enhancement of guanine-enhanced silver nanoclusters. We also found that DNA-Ag NCs is an excellent fluorescence sensor for cyanide, as cyanide effectively quenches the fluorescence of NCs at a very low concentration with high selectivity. Cyanide in the range from 0.10 µM to 0.35 µM could be linearly detected, with a detection limit of 25.6 nM.