A sensitive and selective BINOL based ratiometric fluorescence sensor for the detection of cyanide ions

A highly selective, novel BINOL based sensor BBCN has been developed for the fluorescent ratiometric detection of cyanide ions (CN⁻). The optical study revealed that BBCN exhibited unique spectral changes only with cyanide ions in the presence of other competing ions. Besides, an apparent fluorescent colour change from green to blue was observed. A clear linear relationship was observed between the fluorescence ratiometric ratio of BBCN and the concentration of CN⁻ with a reasonably low detection limit (LOD) of 189 nM (507 ppb). The optical response was due to the nucleophilic addition of CN⁻ to the dicyanovinyl group of the sensor, which compromises the probe''s intramolecular charge transfer. This mechanism was well confirmed by Job''s plot, ¹H-NMR and ESI-MS studies. BBCN showed immediate spectral response towards (1 second) CN⁻ and detection could be realized in a broad pH window. Furthermore, the practical utility of BBCN was studied by test paper-based analysis and the detection of CN⁻ in various water resources.

A highly selective, novel BINOL based sensor BBCN has been developed for the fluorescent ratiometric detection of cyanide ions (CN⁻).     

A reference method for measurement of alkaline phosphatase activity in human serum

We present an official AACC reference method for the measurement of alkaline phosphatase, the culmination of optimization experiments conducted by a group of independent laboratories. The details of this method and evaluation of factors affecting the measurement are described. A metal ion buffer has been incorporated that maintains optimal and constant concentrations of zinc(II) and magnesium(II) ions. Final reaction conditions are: pH (30 degrees C), 10.40 +/- 0.05; 2-amino-2-methyl-1-propanol buffer, 0.35 mol/L; 4-nitrophenyl phosphate, 16.0 mmol/L; magnesium acetate, 2.0 mmol/L; zinc sulfate, 1.0 mmol/L; and N-(2-hydroxyethyl)ethylenediaminetriacetic acid, 2.0 mmol/L.     

A bis-benzimidazole PMO ratiometric fluorescence sensor exhibiting AIEE and ESIPT for sensitive detection of Cu2+

A novel bis-benzimidazole organic siloxane precursor (BBM-Si) was prepared, and was combined with tetraethylorthosilicate (TEOS) as a mixed Si source. Then, bridged periodic mesoporous organosilica (BBM-PMO) spherical nanoparticles were synthesized by co-condensation using cetyltrimethylammonium bromide (CTAB) as structure directing agent. The optical properties showed that BBM qualifies as an “aggregation induced emission enhanced” (AIEE) molecule, exhibiting characteristics of excited-state intramolecular proton transfer (ESIPT), such as a large Stokes shift and dual fluorescence emission. For the BBM-PMO materials, the silica skeleton provides a rigid environment that limits molecular rotation, resulting in improved fluorescence emission. In particular, the BBM-PMOs exhibited dual emission of the enol and keto forms, achieving a ratiometric response to Cu²⁺ with high sensitivity and selectivity in a broad pH range. Additionally, the limit of detection was as low as 7.15 × 10⁻⁹ M in aqueous solution. The X-ray absorption near-edge spectroscopy (XANES) showed the coordination structure through the interaction between copper ions and N atoms of benzimidazole in the BBM-PMO coordinated to Cu²⁺. These results demonstrate that BBM-PMO hybrid materials have potential applications in the fields of bio-imaging and environmental monitoring.

A novel bis-benzimidazole organic siloxane precursor (BBM-Si) was prepared, and was combined with tetraethylorthosilicate (TEOS) as a mixed Si source.     

A new ratiometric fluorescence assay based on resonance energy transfer between biomass quantum dots and organic dye for the detection of sulfur dioxide derivatives

Sulfur dioxide (SO₂) is considered as the fourth gas signal molecule after nitric oxide (NO), carbon monoxide (CO) and hydrogen sulfide (H₂S). It plays important roles in several physiological processes. Therefore, the design and synthesis of nanoprobes for the detection of SO₂ derivatives in cells is of great significance. Herein, we report a new ratiometric fluorescence nanoprobe based on resonance energy transfer (RET) between biomass quantum dots (BQDs) and organic dye (DMI) for the detection of SO₂ derivatives. The proposed ratiometric fluorescence assay allows the determination of HSO₃⁻ in the range of 1.0 to 225 μM with a detection limit of 0.5 μM. Importantly, the proposed ratiometric fluorescence nanoprobe exhibits a high photostability and good selectivity for HSO₃⁻ over other chemical species including H₂S and biological mercaptans. Quantitation of HSO₃⁻ in cell lysates by using the nanoprobe is demonstrated.

A new ratiometric fluorescence assay has been developed for the detection of sulfur dioxide derivatives with repeatability and selectivity. The assay was applied to quantitate HSO₃⁻ in cell lysates with accurate results.     

A continuous-flow method for the determination of the activity of serum alkaline phosphatase in diethanolamine buffer.

A procedure for determination of serum alkaline phosphatase activity (EC 3.1.3.1) in diethanolamine (DEA) buffer with an AutoAnalyzer II apparatus was designed. The buffer used was 1.0 mol/l DEA-HC buffer, pH 9.8 at 37 degree C, containing 0.5 mmol/l of MgCl2 and 10 mmol/l of substrate 4-nitrophenyl-phosphate. The reaction time was about 3 min at 37 degree C. The enzyme activity (U/l) was calculated by determining the amount of 4-nitrophenol formed in reaction. A sampling rate of 70 samples per hour can be used with good linearity up to 1000 U/l. The results obtained by the new continuous-flow system were compared with those measured by the kinetic method according to the Scandinavian recommendation (10). A close correlation between the two methods was observed.     

A ratiometric fluorescent sensor for detection of metformin based on terbium–1,10-phenanthroline–nitrogen-doped-graphene quantum dots

Metformin (MTF), an effective biguanide and oral antihyperglycemic agent, is utilized to control blood glucose levels in patients with type II diabetes mellitus, and the determination of its concentration in biological fluids is one of the main issues in pharmacology and medicine. In this work, highly luminescent nitrogen-doped graphene quantum dots (N-GQDs) were modified using terbium (Tb³⁺)–1,10-phenanthroline (Phen) nanoparticles (NPs) to develop a dual-emission ratiometric fluorescent sensor for the determination of MTF in biological samples. The synthesized N-GQDs/Tb–Phen NPs were characterized using different techniques to confirm their physicochemical properties. The N-GQDs/Tb–Phen NPs showed two characteristic emission peaks at 450 nm and 630 nm by exciting at 340 nm that belong to N-GQDs and Tb–Phen NPs, respectively. The results indicated that the emission intensity of both N-GQDs and Tb–Phen NPs enhanced upon interaction with MTF in a concentration-dependent manner. Also, a good linear correlation between the enhanced fluorescence intensity of the system and MTF concentration was observed in the range of 1.0 nM–7.0 μM and the limit of detection (LOD) value obtained was 0.76 nM. In addition, the prepared probe was successfully used for the estimation of MTF concentration in spiked human serum samples. In conclusion, the reported dual-emission ratiometric fluorescent sensor can be used as a sensitive and simple fluorimetric method for the detection of MTF in real samples.

Shcematic representation of the MTF detection by an enhancing mechanism.     

Criteria for establishing a standardized method for determining alkaline phosphatase activity in human serum.

We investigated factors influencing alkaline phosphatase activity in the course of developing criteria for the establishment of a standardized method for its determination in human serum at 30 degrees C. The effects of pH, phosphorylatable acceptor (2-amino-2-methyl-1-propanol and diethanolamine), 4-nitrophenyl phosphate, magnesium ion, zinc ion, temperature, volume fraction of specimen, and details of initiation of the reaction have been studied, with use of partly purified enzymes from bone, intestine, liver, and placenta, and sera from patients with a predominant characterized isoenzyme. The purity of the diethanolamine was examined and contaminant monoethanolamine was characterized as a competitive inhibitor. Two sets of recommended conditions are: 2-amino-2-methyl-1-propanol, 0.9 mol/liter; 4-nitrophenyl phosphate, 16 mmol/liter; magnesium ion, 1 mmol/liter; volume fraction of specimen 1/30, and pH30 degrees C 10.5; diethanolamine, 1.8 mol/liter; 4-nitrophenyl phosphate, 18 mmol/liter; magnesium ion, 1 mmol/liter; volume fraction of specimen 1/60, and pH30 degrees C 10.1. Serum is preincubated with all reagents but 4-nitrophenyl phosphate, which is used as the reaction-initiating substrate.     

A FRET based ratiometric fluorescent probe for detection of sulfite in food

A new fluorophore pyrido[1,2-a]benzimidazole based ratiometric fluorescent probe for the selective detection of sulfite ions in water was investigated. It shows large (pseudo) Stokes shifts (260 nm), high FRET efficiency, high selectivity and sensitivity. A distinct color change from red to colorless was observed and importantly, it proves to be a convenient and efficient tool to detect the sulfite levels in sugar samples.

A new fluorophore pyrido[1,2-a]benzimidazole based ratiometric fluorescent probe for the selective detection of sulfite ions in water was investigated.