A dual-channel ratiometric fluorescent probe for determination of the activity of tyrosinase using nitrogen-doped graphene quantum dots and dopamine-modified CdTe quantum dots.

A dual-channel ratiometric fluorometric assay is described for the determination of the activity of the enzyme tyrosinase (TYR). It is making use of blue-emitting nitrogen-doped graphene quantum dots (bQDs) and of red-emitting dopamine-modified CdTe quantum dots (DA-rQDs). A mixture of the two kinds of quantum dots was prepared, with the ratiometric fluorescence intensity of red to blue adjusted to 5:1. The dopamine on the rQDs is catalytically oxidized by TYR to form dopamine quinone, and this leads to a reduction of the intensity of red fluorescence (peaking at 644 nm). The emission of the bQDs (peaking at 440 nm) represents a stable reference signal. After adding different activities of TYR, the color of the fluorescence of the system continuously changes from red to blue. This can also be visually observed. The ratio of luminescence intensities (at 644/440 nm) can be used to quantify the activity of TYR, and the detection limit is 4.5 mU mL-1. In addition, a test strip is described based on the above method. Graphical abstract Schematic representation of the ratiometric fluorometric method for determination of the activity of tyrosinase (TYR). (The full name of the abbreviation in the Scheme: 1-ethyl-3-[3-(dimethylamino)-propyl] carbodiimide hydrochloride (EDC), dopamine (DA), N-hydroxysuccinimide (NHS), nitrogen-doped graphene quantum dots (bQDs), CdTe quantum dots (rQDs)).

Hydroxyapatite Nanowires@Metal-Organic Framework Core/Shell Nanofibers: Templated Synthesis, Peroxidase-Like Activity, and Derived Flexible Recyclable Test Paper.

The templated synthesis of hydroxyapatite (HAP) nanowires@metal-organic framework (MOF) core/shell nanofibers (named HAP@MIL-100(Fe) nanofibers) is demonstrated. The ultralong hydroxyapatite nanowires are adopted as a hard template for the nucleation and growth of MIL-100(Fe) (a typical MOF) through the layer-by-layer method. The Coulombic and chelation interactions between Ca2+ ions on the surface of the HAP nanowires and the COO- organic linkers of MIL-100(Fe) play key roles in the formation process. The as-prepared, water-stable HAP@MIL-100(Fe) nanofibers exhibit peroxidase-like activity toward the oxidation of different peroxidase substrates in the presence of H2 O2 , accompanied by a clear color change of the solution. Furthermore, a flexible, recyclable HAP@MIL-100(Fe) test paper is prepared successfully by using HAP@MIL-100(Fe) nanofibers as building blocks. A simple, low-cost, and sensitive colorimetric method for the detection of H2 O2 and glucose is established based on the as-prepared, flexible, recyclable HAP@MIL-100(Fe) test paper. More importantly, the HAP@MIL-100(Fe) test paper can be recovered easily for reuse by simply dipping in absolute ethanol for just 30 min, thus showing excellent recyclability. With its combination of advantages such as easy transportation, easy storage and use, rapid recyclability, light weight, and high flexibility, this HAP@MIL-100(Fe) test paper is promising for wide applications in various fields.

Phenanthroimidazole-based fluorescence probe for discriminative detecting of hydrazine and bisulfite and its applications in environmental samples.

Hydrazine (N2H4) and bisulfite (HSO3-) detection methods are urgently needed due to its harmful to the human health and environment safety. Herein, we reported a dual-response fluorescence probe EPC, which is capable of sequential detection of N2H4 and HSO3- by two different fluorescence signals. The probe EPC itself showed yellow florescence. In presence of N2H4, probe EPC exhibited an obviously fluorescence change (from yellow to green). However, a new addition product came into being after probe EPC mixed with HSO3-, followed with weak yellow emission. More important, probe EPC exhibited excellent fluorescence response properties for N2H4 and HSO3-, such as high sensitivity (0.182 µM for N2H4, 0.093 µM for HSO3-), rapid response (55 s for N2H4, 45 s for HSO3-), excellent selectivity and anti-interference performance. The sensing mechanisms for N2H4 and HSO3- were proved by 1H NMR and MS spectra. Practical applications were studied. EPC based test paper can be utilized for quantitative detecting N2H4 in actual water samples. And, probe EPC has been successfully applied to recognize N2H4 contaminant in soil samples. Moreover, EPC has great potential to be used to detect HSO3- in real food samples.

Synthesis of a super-low detection limit fluorescent probe for Al3+ and its application in fluorescence imaging of zebrafish and cells.

A novel fluorescent probe N'-(2-hydroxybenzylidene)-indole-3-formylhydrazine (JHK) was designed and synthesized based on the condensation reaction of indole-3-formylhydrazine and salicylaldehyde. The probe JHK solution could highly selectively recognize Al3+ by the obvious fluorescence enhancement (288-fold) after adding Al3+. And the probe solution with Al3+ had a very high fluorescence quantum yield (89.29 %). The detection limit was calculated to be 1.135 nM, which was significantly lower than many reported detection limits, indicating that the probe JHK had pretty good sensitivity. The ratio of JHK to Al3+ (1:1) and the sensing mechanism were determined by Job's plot, 1H NMR spectra, FTIR spectra, ESI-MS and Gaussian calculation. The probe solution and medium-speed filter paper were successfully used to make test papers for more convenient detection of Al3+. Furthermore, the probe JHK had been successfully applied to the detection of Al3+ in real water, zebrafish and living cells.

Fluorescent Biomass-Based Platform for Detection of ClO- in Cells and Water-Soluble Systems.

The generation and presence of excessive hypochlorous acid derivative ionic form (ClO-) could cause various diseases, such as arteriosclerosis, DNA damage, and cardiovascular illness. It is a critical need to develop a highly sensitive sensor for reliable detection of ClO- in cells and water-soluble systems. In this work, a hydroxyl group has been introduced into the compound 2-amino-3-(((E)-4-(2-(2-(2-hydroxyethoxy)ethyl)-1,3-dioxo-2,3-dihydro-1H-benzo[de]isoquinolin-6-yl)benzylidene)amino)maleonitrile (NDC) to increase its solubility in water, at the same time, the hydrazone unit was designed as a specific recognition group for the "off-on" fluorescence probe of ClO-. The probe NDC presents high selectivity, sensitivity, anti-interference, and low detection limit (67 nM) for ClO-. The recognition mechanism that ClO- breaks the C=N bond and forms the fluorescent compound 4-(2-(2-(2-hydroxyethoxy)ethyl)-1,3-dioxo-2,3-dihydro-1H-benzo[de]isoquinolin-6-yl)benzaldehyde (ND-3) has been confirmed by time-of-flight mass spectrometry. The probe NDC presents a good performance in the actual test of water samples and can be designed as the test papers for the quick and convenient detection of ClO- range from 0 to 1 µM. Moreover, the practical application was demonstrated by the successful imaging of endogenous and exogenous ClO- in HeLa cells. Our fluorescent biomass-based platform opens vast possibilities for repeatability, sensitivity, and selectivity detection of ClO- in cells and water-soluble systems.

Investigating the AIE and water sensing properties of a concise naphthalimide fluorophore.

A simple naphthalimide fluorophore NAP-H2O was designed and synthesized. Basic photophysical properties were investigated, especially found that the probe showed robust green fluorescence in water compared with that in various organic solvents, and the specific mechanism was conformed to be the aggregation induced emission (AIE) through dynamic light scattering (DLS) analysis, solid-state luminescence and fluorescence imaging. Accordingly, the capability of NAP-H2O for water sensing was examined, and good linear relationships between fluorescence intensities at the green emission band and the water content were obtained, enabling quantitative detection of water in organic solvents. The detection limits were calculated to be 0.004 % (v/v) in ACN, 0.117 % (v/v) in 1,4-dioxane, 0.028 % (v/v) in THF, 0.022 % (v/v) in DMF and 0.146 % (v/v) in DMSO, respectively. In addition, the probe presented fast response time within 5 s to water and good photostability. Furthermore, the probe was successfully applied for fast and naked-eye detection of water in organic solvents via test papers. This work provides a rapid, sensitive and naked-eye method for trace amount detection of water in organic solvents and has potential for practical applications.

A Novel Fluorescent Test Papers Based on Carbon Dots for Selective and Sensitive Detection of Cr (VI).

In recent years, carbon dots (CDs) are promising fluorescence probes for ions detection. In this paper, the CDs which are with an average diameter of 5.5 nm were synthesized through a simple one-step hydrothermal carbonization of ethylene diamine tetraacetic acid (EDTA) salt. The CDs have strong yellow photoluminescence (PL) with a maximum emission intensity at 550 nm under an excitation wavelength of 450 nm. As the electron transfer will occur between Cr (VI) and the CDs, yellow fluorescence was quenched after adding the Cr (VI) ions. The CDs probe allows the detection of Cr (VI) ions over a concentration range from 0 to 0.1 M (R 2 = 0.987) and the lower detection limit is 10-5 M. Simultaneously, the CDs show highly selectivity and stability toward the detection of Cr (VI) ions.

Substituent effect on colorimetric detection of biologically and environmentally relevant anions: Insight in real-life applications.

A new set of chromogenic anion receptors R1-R4 have been synthesized with a different substituent, including electron withdrawing (nitro moiety in R1), conjugated group (naphthyl in R2), and electron donating (methyl in R3), respectively. The receptors R1-R4 exhibited very good sensitivity towards the F- and AcO- anions in the DMSO. In addition, R1 showed selectivity towards H2PO4- ions over other tested anions. R1 especially acted as an effective sensor for sodium salts of F-, AcO-, AsO2-, and AsO42- ions in an aqueous medium due to the presence of two electron-withdrawing nitro substituents, which showed hydrogen bond donor tendency and acidity of the OH proton. This result indicates that R1 is highly capable of competing with an aqueous medium to detect anions without counter Na+ ion interference. Interestingly, R1 displays solvatochromic property in the presence of AcO- ions in different aprotic solvents. Additionally, the receptor R1 shows high binding affinity towards AcO- ions in the buffer medium (DMSO: HEPES, 9:1 v/v), which displayed remarkable colour change from pale yellow to blue with a large ∆λred shift of 170 nm. The CV studies reveal the deprotonation of the -NH proton upon interaction with the AcO- ions. The receptor R1 is subjected to practical application to sense F- and AsO2- ions using the test strip. In addition, the receptor R1 proves itself as a potential applicant for the detection of F- ions quantitatively in commercially available mouthwash.