Fluorescent sensor for fluoride anion based on a sulfonamido-chromone scaffold

New scaffolds of sulfonamido-chromone derivatives recently synthesized were found to be effective fluorescent sensors for fluoride anion. This new class of fluorophore showed a blue shift in the emission spectra upon addition of various equivalents of fluoride. These compounds also exhibit excellent selectivity for the fluoride anion via a deprotonation process. They were also shown to have a detection limit of F^? down to 0.5?ppm.     

A photochromic phenoxyquinone based cyanide ion sensor

We have developed a new chemosensor system for cyanide ion that is based on a photochromic material. We observed that addition of cyanide anion to a UV irradiated solution of a phenoxynaphthacenequinone derivative brought about a significant change in the absorption spectra that enabled detection of cyanide ion in a selective and sensitive manner. A carbanion intermediate was shown to be responsible for the long wavelength absorption band (630-940 nm) that is generated by cyanide addition.     

Thiourea based novel chromogenic sensor for selective detection of fluoride and cyanide anions in organic and aqueous media

Novel chromogenic thiourea based sensors 4,4′-bis-[3-(4-nitrophenyl) thiourea] diphenyl ether 1 and 4,4′-bis-[3-(4-nitrophenyl) thiourea] diphenyl methane 2 having nitrophenyl group as signaling unit have been synthesized and characterized by spectroscopic techniques and X-ray crystallography. The both sensors show visual detection, UV-vis and NMR spectral changes in presence of fluoride and cyanide anions in organic solvent as well as in aqueous medium. The absorption spectra indicated the formation of complex between host and guest is in 1:2 stoichiometric ratios.     

A highly selective and sensitive dual-channel chemosensor for cyanide based on sulfahydrazone derivative

A colorimetric and fluorescent cyanide probe bearing naphthol and sulfahydrazone groups has been designed and synthesized. This structurally simple probe displays a rapid response and high selectivity for cyanide in DMSO/EtOH (v/v = 2:8) solution. The addition of CN^? to the sensor p-toluenesulfonyl-2-hydroxy-1-naphthylhydrazone (L3) induced a remarkable color change from pale-yellow to yellow, and green fluorescence changed to yellow. The ¹H NMR titration and DFT calculations suggested that the selective sensing process is based on a nucleophilic addition reaction of cyanide to imine. Test strips based on sensor L3 were fabricated, which could act as a convenient and efficient test kit to detect CN^? for “in-the-field” measurements.     

A fluoride selective dipyrromethane-TCNQ colorimetric sensor based on charge-transfer

A colorimetric sensor based on dipyrromethane(donor)-7,7′,8,8′-tetracyanoquinodimethane (acceptor) charge-transfer compound depicts excellent selectivity for naked-eye as well as spectrophotometric determination of F⁻ even in co-existence with other halide ions (Cl⁻, Br⁻ and I⁻). The sensing mechanism is ascribed to the interrupted charge-transfer between donor-acceptor in the presence of F⁻. The sensing on solid support mimics the solution sensing process supported by the reflectance values. Thus this compound has potential for practical applications.     

An azo dye-coupled tripodal chromogenic sensor for cyanide

A tripodal receptor bearing phenol as a hydrogen bond donor site and azo dye as the signaling subunit was synthesized. The receptor had a high binding affinity for CN⁻ as signaled by the change in the color of a solution of sensor 4 upon addition of CN⁻. Using UV-Vis spectroscopy, the system can be used to quantify 0-19 × 10⁻⁵ mol L⁻¹ of CN⁻, and the sensor was found to successfully function in the presence of other anions.     

A high selective anion colorimetric sensor based on salicylaldehyde for fluoride in aqueous media

A new and simple salicylaldehyde-based sensor 1 designed for fluoride sensing has been investigated in DMSO and even in the 9/1 DMSO/H₂O (v/v) mixtures. The affinity constants of receptor 1 for anionic species in the 9/1 DMSO/H₂O (v/v) reveal that it is sensitive to F. Also, the color changes induced by anions can provide a way of detection by ‘naked-eye’. These result can be substantiated by the spectrum changes upon the addition of 25 equiv. anions to 1 in the 9/1 DMSO/H₂O solution. The further insights to the nature of interactions between the sensor 1 and F⁻ were investigated by ¹H NMR titration experiments in 9/1 DMSO-d₆/H₂O (v/v). In addition, the proposed binding mode between 1 and F⁻ was suggested.     

Fabrication of an electrochemical sensor based on spiropyran for sensitive and selective detection of fluoride ion

In the past decades, numerous electrochemical sensors based on exogenous electroactive substance have been reported. Due to non-specific interaction between the redox mediator and the target, the instability caused by false signal may not be avoided. To address this issue, in this paper, a new electrochemical sensor based on spiropyran skeleton, namely SPOSi, was designed for specific electrochemical response to fluoride ions (F⁻). The breakage of Si–O induced by F⁻ based on the specific nucleophilic substitution reaction between F⁻ and silica would directly produce a hydroquinone structure for electrochemical signal generation. To improve the sensitivity, SPOSi probe was assembled on the single-walled carbon nanotubes (SWCNTs) modified glassy carbon electrode (GCE) through the π–π conjugating interaction. This electrode was successfully applied to monitor F⁻ with a detection limit of 8.3 × 10⁻⁸ M. Compared with the conventional F⁻ ion selected electrode (ISE) which utilized noncovalent interaction, this method displays higher stability and a comparable sensitivity in the urine samples.     

Amperometric sensor for cyanide utilizing cyanidase and formate dehydrogenase

An amperometric sensor for the detection of cyanide integrated in a flow injection analysis (FIA) system is presented. The specificity of the sensor for cyanide is achieved by a reaction cascade involving two enzymes, cyanidase (EC 3.5.5.1) and formate dehydrogenase (FDH, EC 1.2.1.2). The limit of detection (LOD) and the limit of quantification (LOQ) were determined to be in the low micromolar range. The sensor showed very good long term stability and the linear range of detection extends from 0.7 up to 800 M. The sensor’s ability to measure cyanide in complex matrices, such as plant extracts, is demonstrated. Although the sensor is susceptible to formate and to a lesser extent to thiocyanate, sulfide does not interfere significantly.     

A highly sensitive colorimetric and ratiometric sensor for fluoride ion

A new benzoimidazole-naphthalimide derivative 4 was synthesized and its photophysical properties were studied. This compound showed highly selectively and sensitive colorimetric and ratiometric sensing ability for fluoride anion.     

Urea-based polyacetylenes as an optical sensor for fluoride ions

Novel acetylenes carrying urea groups, 1-(4-ethynylphenyl)-3-(4-nitrophenyl) urea (1), 1-(4-propargyl)-3-(4-nitrophenyl) urea (2), were synthesized and polymerized with rhodium catalyst. Polymers [poly(1) and poly(2)] with moderate molecular weights were obtained in good yields. The anion sensing ability of poly(1) and poly(2) was estimated using the tetra-n-butylammonium (TBA) salts of a series of anions in DMF. Upon the addition of F-, the color of the DMF solution of poly(1) and poly(2) immediately turned to a different color, while the color of solution changed slightly upon addition of Cl-, HSO4-, Br-, and NO3-, indicating the F- sensing ability of poly(1) and poly(2). The 1H-NMR titrations of poly(1) revealed that the colorimetric response of poly(1) was triggered by the urea/F- interaction through the hydrogen bonding and/or deprotonation process. The absorption spectra titration and Hill plot analysis were carried out to measure the F- binding ability, and the Hill coefficient in the poly(1)/F- complexation was found to be 5.8. This result clearly indicated that this binding mode between poly(1) and F- was based on a positive homotropic allosterism.     

New methods for the detection of cyanide based on displacement of the glutathione ligand of glutathionylcobalamin by cyanide

Glutathionylcobalamin (GSCbl) is a vitamin B₁₂ derivative that contains glutathione as the upper axial ligand to cobalt via a Co–S bond. In the present study, we discovered that cyanide reacted with GSCbl, generating cyanocobalamin (CNCbl) and reduced glutathione (GSH) via dicyanocobalamin (diCNCbl) intermediate. This reaction was induced specifically by the nucleophilic attack of cyanide anion displacing the glutathione ligand of GSCbl. Based on the reaction of GSCbl with cyanide, we developed new methods for the detection of cyanide. The reaction intermediate, violet-coloured diCNCbl, could be applied for naked eye detection of cyanide and the detection limit was estimated to be as low as 520 μg L^?1 (20 μM) at pH = 10.0. The reaction product, CNCbl, could be applied for a spectrophotometric quantitative determination of cyanide with a detection limit of 26 μg L^?1 (1.0 μM) at pH = 9.0 and a linear range of 26–520 μg L^?1 (1.0–50 μM). In addition, the other reaction product, GSH, could be applied for a fluorometric quantitative determination of cyanide with a detection limit of 31 μg L^?1 (1.2 μM) at pH = 9.0 and a linear range of 31–520 μg L^?1 (1.2–20 μM). These new GSCbl-based methods are simple, highly specific and sensitive with great applicability for the detection of cyanide in biological and non-biological samples.     

席夫碱类高选择性氟离子化学传感器的研究

以邻羟基萘甲醛和水合肼合成了席夫碱类化合物荧光黄101(DHNA),在F-存在的情况下,其紫外可见光谱和荧光光谱都发生明显的变化,同时溶液颜色和荧光的变化可以通过肉眼直接观测到.在Cl-、Br-、1-、HSO4-、H2PO4-;等干扰离子存在的情况下,DHNA对F-具有良好的选择性.因此,荧光黄101可用于制备检测F-的高灵敏度颜色.荧光传感器.     

A colorimetric and fluorescent sensor for sequential detection of copper ion and cyanide

A simple cation sensor 1 ((E)-9-((2-hydroxynaphthalen-1-ylimino)methyl)-1,2,3,5,6,7-hexahydropyrido[3,2,1-ij]quinolin-8-ol) bearing both a julolidine moiety and a naphthol moiety was designed and synthesized as a colorimetric sensor for Cu²⁺. In methanol solution of 1, the presence of Cu²⁺ led to a distinct naked-eye color change from yellow to purple. The proposed sensing mechanism might be attributed to the decrease in internal charge transfer band. Moreover, the resulting 1–Cu²⁺ complex sensed cyanide in a fluorometric way via fluorescent changes. These results demonstrate a novel type of the sequential recognition of Cu²⁺ and CN⁻ using two different sensing methods, color change, and fluorescence.     

New color chemosensors for cyanide based on water soluble azo dyes

Cyanide detection in pure water is important for many applications. We present a novel type of chemodosimeter azo dye developed on the basis of the benzophenone as the electrophilic receptor of the cyanide anion and a saccharidic moiety to render the dye water soluble. This chemodosimeter is found to be highly selective and tunable toward only cyanide in pure water.     

An inhibition type amperometric biosensor based on tyrosinase enzyme for fluoride determination

In this study, a new biosensor based on the inhibition of tyrosinase for the determination of fluoride is described. To construct the biosensor tyrosinase was immobilized by using gelatine and cross-linking agent glutaraldehyde on a Clark type dissolved oxygen (DO) probe covered with a teflon membrane which is sensitive for oxygen. The phosphate buffer (50 mM, pH 7.0) at 30 °C were established as providing the optimum working conditions. The method is based on the measurement of the decreasing of dissolved oxygen level of the interval surface that related to fluoride concentration added into reaction medium in the presence of catechol. Inhibitor effect of fluoride results in decrease in dissolved oxygen concentration. The biosensor response depends linearly on fluoride concentration between 1.0 and 20 μM with a response time of 3 min.In the characterization studies of the biosensor some parameters such as reproducibility, substrate specificity and storage stability were carried out. From the experiments, the average value (x), Standard deviation (S.D) and coefficient of variation (C.V %) were found as 10.5 μM, ± 0.57 μM, 5.43%, respectively for 10 μM fluoride standard.     

Impedance spectroscopy and conductometric biosensing for probing catalase reaction with cyanide as ligand and inhibitor

In this work, a new biosensor was prepared through immobilization of bovine liver catalase in a photoreticulated poly (vinyl alcohol) membrane at the surface of a conductometric transducer. This biosensor was used to study the kinetics of catalase–H₂0₂ reaction and its inhibition by cyanide. Immobilized catalase exhibited a Michaelis–Menten behaviour at low H₂0₂ concentrations (< 100 mM) with apparent constant K_M^app = 84 ± 3 mM and maximal initial velocity V_M^app = 13.4 μS min^? 1. Inhibition by cyanide was found to be non-competitive and inhibition binding constant K_i was 13.9 ± 0.3 μM. The decrease of the biosensor response by increasing cyanide concentration was linear up to 50 μM, with a cyanide detection limit of 6 μM. In parallel, electrochemical characteristics of the catalase/PVA biomembrane and its interaction with cyanide were studied by cyclic voltammetry and impedance spectroscopy. Addition of the biomembrane onto the gold electrodes induced a significant increase of the interfacial polarization resistance R_P. On the contrary, cyanide binding resulted in a decrease of Rp proportional to KCN concentration in the 4 to 50 μM range. Inhibition coefficient I₅₀ calculated by this powerful label-free and substrate-free technique (24.3 μM) was in good agreement with that determined from the substrate-dependent conductometric biosensor (24.9 μM).     

Continuous monitoring for cyanide in waste water with a galvanic hydrogen cyanide sensor using a purge system

A continuous monitoring system for cyanide with a galvanic hydrogen cyanide sensor and an aeration pump for purging was developed. Hydrogen cyanide evolved from cyanide solution using a purging pump was measured with the hydrogen cyanide sensor. The system showed good performance in terms of stability and selectivity. A linear calibration curve was obtained in the concentrating range from 0 to 15 mg dm³ of cyanide ion with a slope of −0.24 μA mg⁻¹ dm⁻³. The lower detection limit was 0.1 mg dm⁻³. The 90% response time of the sensor system was within 3.5 min for a 0.5 mg dm⁻³ cyanide solution, when the flow rate of the purging air was 1 dm³ min⁻¹. The system maintained the initial performance for 6 months in the field test. The developed galvanic sensor system was not subject to interference from sulfide and residual chlorine, compared with a potentiometric sensor system developed previously. The analytical results obtained by the present system were in good agreement with those obtained by the pyridine pyrazolone method. The correlation factor and regression line between both methods were 0.979 and Y=2.30×10⁻⁴+1.12X, respectively. This system was successfully applied for a continuous monitoring of cyanide ion in waste water.     

A simple dual-channel sensor for detecting cyanide in water with high selectivity and sensitivity

Taking advantage of the special nucleophilicity of cyanide, a new simple colorimetric chemosensor has been synthesised. This allows a deprotonation reaction to monitoring the cyanide. With the addition of CN^? to the chemosensor aqueous solution, which could induce a change in the solution colour from yellowish to deep yellow, while no colour change could be observed in the presence of other hackneyed anions, by which CN^? can be distinguished from other anions immediate with the naked eye. At the same time, a fluorescence quenching was implemented upon adding cyanide into the chemosensor aqueous solution. The absorption spectra detection limits of the chemosensor for cyanide was 5.35 × 10^?8 M and the fluorescence spectra detection limit was 2.63 × 10^?8 M. The cyanide test strips based on the chemosensor could serve as a convenient cyanide test kits. Furthermore, the chemosensor was successfully applied to detect cyanide in sprouting potatoes.