Coumarinyl aldehyde as a Michael acceptor type of colorimetric and fluorescent probe for cyanide in water

A simple aldehyde-functionalized coumarin (1) was utilized as a doubly activated Michael acceptor type of chemodosimeter for cyanide in water. The probe has shown a selective and sensitive response to the cyanide anion over other various anions through the Michael addition reaction of the cyanide to 1. When cyanide anions were added, the prominent color changes as well as fluorescence changes of 1 were observed so that millimolar concentrations of cyanides were detectable by the naked eye.     

Doubly activated coumarin as a colorimetric and fluorescent chemodosimeter for cyanide

A new α,β-unsaturated nitro group and coumarin conjugate-based fluorescent chemodosimeter 1 was developed for the selective detection of cyanide anions. The chemodosimeter has shown a selective and sensitive response to cyanide anions over other various anions through a nucleophilic aromatic substitution reaction of the cyanide to 1. When cyanide anions were added, the enhanced fluorescence intensity as well as the color changes of 1 was observed so that micromolar concentrations of cyanides were detectable by the naked eye.     

A ratiometric chemodosimeter for highly selective naked-eye and fluorogenic detection of cyanide

A simple indole-based chemosensor (1) with a very low molecular weight of 207 g mol⁻¹ has been synthesized for the highly reactive and selective detection of CN⁻ in aqueous media, even in the presence of other anions, such as F⁻, Cl⁻, Br⁻, AcO⁻, S₂⁻${{\mathrm{S}}_2}^{-}$, SCN⁻, NO₂⁻${{\text{NO}}_2}^{-}$, NO₃⁻${{\text{NO}}_3}^{-}$, CO₃⁻${{\text{CO}}_3}^{-}$, BzO⁻, H₂PO₄⁻${{\mathrm{H}}_2{\text{PO}}_4}^{-}$, and HSO₄⁻${{\text{HSO}}_4}^{-}$. The sensor achieves rapid detection of cyanide anion in 2 min, and the pseudo-first-order rate constant is estimated as 1.576 min⁻¹. The colorimetric and ratiometric fluorescent response of the sensor to CN⁻ is attributable to the addition of CN⁻ to the electron-deficient dicyanovinyl group of 1, which prevents intramolecular charge transfer. The sensing mechanism is supported by density functional theory and time-dependent density functional theory calculations. Moreover, sensor 1 exhibits both high accuracy in determining the concentration of CN⁻ in real samples and 1-based test strips can conveniently detect CN⁻ without any additional equipment. The detection limit of the sensor 1 (1.1 μM) for cyanide is lower than the maximum permissible level of CN⁻ (1.9 μM) in drinking water.     

A selective quinoline-derived fluorescent chemodosimeter to detect cyanide in aqueous medium

A simple quinoline derived probe 3 has been described. Probe 3 having aldehyde function upon interaction with cyanide undergo nucleophilic addition reaction to form cyanohydrin derivative 4 in which fluorescence intensity enhances significantly, ‘turn-on’ by photoinduced electron transfer (PET) OFF–ON mechanism. The color of probe solution switched-on to fluorescent blue which is visible to the naked-eye. Job’s plot analysis revealed a 1:1 stoichiometry for an interaction between 3 and cyanide along with detection limit 0.058 μM (1.5 ppb). The mode of interaction to detect cyanide in aqueous medium through a reaction based chemodosimeter approach has been confirmed by NMR, mass, FTIR, and DFT data analysis.     

Simple Michael acceptor type coumarin derived turn-on fluorescence probes to detect cyanide in pure water

The present article describes design and synthesis of coumarin derived chemical reaction based chemodosimeter to recognize cyanide in aqueous medium. The Michael acceptor type coumarin derived probes 3 and 4 upon interaction with cyanide undergo Michael type nucleophilic addition reaction to form adducts in which fluorescence intensity was significantly enhanced, ‘turn-on’ by the change in intramolecular charge transfer (ICT) mechanism. The nonfluorescent color of solutions changed to a naked-eye sensitive fluorescent blue (switched-on). Job’s plot analysis revealed a 1:1 stoichiometry for the interaction between the probe and cyanide anion with a high detection limit.     

A fluorescein-based fluorogenic and chromogenic chemodosimeter for the sensitive detection of sulfide anion in aqueous solution

A highly sensitive chromo- and fluorogenic chemodosimeter for sulfide anion was developed based on its nucleophilicity. 2,4-Dinitrobenzenesulfonyl-fluorescein (I) is a weakly fluorescent compound. Upon mixing with sulfide anion in aqueous acetone solution, the 2,4-dinitrobenzenesulfonyl group of I was efficiently removed and highly fluorescent fluorescein was released, hence leading to the dramatic increases in both fluorescence and absorbance of the reaction solution. The fluorescence increment is linear with sulfide anion concentration in the range 50-1000 nmol L⁻¹ with a detection limit of 4.3 nmol L⁻¹ (3σ). The proposed chemodosimeter showed excellent selectivity toward sulfide anion and was successfully applied to the determination of sulfide anion in synthetic wastewater samples.     

Rhodamine-based chemodosimeter for fluorescent determination of Hg in 100% aqueous solution and in living cells

A rhodamine spirolactam derivative (1) bearing a hydrophilic carboxylic acid group is developed as a fluorescent chemodosimeter for bivalent mercury ions (Hg²⁺) in 100% aqueous solution. It exhibits a highly sensitive “turn-on” fluorescent response toward Hg²⁺ with a 42-fold fluorescence intensity enhancement under 1 equiv. of Hg²⁺ added. The chemodosimeter can be applied to the quantification of Hg²⁺ with a linear range covering from 3.0 × 10⁻⁷ to 1.0 × 10⁻⁵ M and a detection limit of 9.7 × 10⁻⁸ M. Most importantly, the fluorescence changes of the chemodosimeter are remarkably specific for Hg²⁺ in the presence of other metal ions, which meet the selective requirements for practical application. Moreover, the experiment results show that the response behavior of 1 towards Hg²⁺ is pH independent in neutral condition (pH 5.0–8.0) and the response is fast (response time less than 3 min). Furthermore, the ring-opening mechanism of the rhodamine spirolactam induced by Hg²⁺ was supported by NMR, MS, and DFT theoretical calculations. In addition, the proposed chemodosimeter has been used to detect Hg²⁺ in water samples and image Hg²⁺ in living cells with satisfying results.     

A rapid responsive and highly selective probe for cyanide in the aqueous environment

A colorimetric and fluorescent cyanide probe based on 7-(trifluoroacetamino)coumarin has been prepared. This structurally simple probe displays rapid response and high selectivity for cyanide over other common anions in the aqueous solution. The sensing of cyanide was performed via the nucleophilic attack of cyanide anion to carbonyl of the probe with a 1:1 binding stoichiometry, which could be confirmed by Job’s plot, ¹H NMR, and MS studies. DFT/TDDFT calculations support that the fluorescence enhancement of the probe is mainly due to the ICT process improvement. The detection limit of the fluorescent assay for cyanide is as low as 0.3 μM in a rapid response of less than 30 s. Thus, the present probe should be applicable as a practical system for the monitoring of cyanide concentrations in aqueous samples.     

Colorimetric and fluorometric dual-modal probes for cyanide detection based on the doubly activated Michael acceptor and their bioimaging applications

In this study, we synthesized CTB and CB probes based on doubly activated Michael acceptors to selectively detect cyanide (CN⁻) anions through a one-step condensation reaction of coumarinyl acrylaldehyde with the corresponding derivatives of malonyl urea (thiourea). Through the conjugated addition of CN⁻ to the β-site of the Michael acceptor, both probes displayed colorimetric and fluorometric dual-modal responses that were highly reactive and selective. CTB generates an active fluorescent response, whereas CB displays a ratiometric fluorescent response. The fluorescent signal of the probes reached its maximum given only 1 CN⁻ equivalent and the signal change was linearly proportional to CN⁻ concentrations ranging from 0 to 5 μM with the detection limits 18 and 23 nM, respectively. The reaction rate of the probes is highly dependent on the methylene acidity of malonyl urea derivatives. Thus, the response rate of CTB to CN⁻ is 1.2-fold faster than that of CB, and the response rate of CB to CN⁻ is 1.2-fold faster than that of the previously examined CM. We then verified the highly reactive nature of the β-site of the probes through density functional reactivity theory calculations. In addition, according to proof-of-concept experiments, these probes may be applied to analyze CN⁻ contaminated water and biomimetic samples. Finally, cell cytotoxicity and bioimaging studies revealed that the probes were cell-permeable and could be used to detect CN⁻ with low cytotoxicity.     

Rapid colorimetric sensing of cyanide anion in aqueous media with a spiropyran derivative containing a dinitrophenolate moiety

A spiropyran derivative containing a dinitrophenolate moiety (2: 1′,3′,3′-trimethyl-6,8-dinitro-spiro-[2H-1-benzopyran-2,2′-indoline]) behaves as a receptor for selective detection of cyanide anion (CN⁻) in aqueous media. Compound 2, when dissolved in aqueous media, spontaneously produces the spirocycle-opened merocyanine (MC) form even in dark condition. The absorption band of the MC form decreases selectively upon addition of CN⁻, via a nucleophilic addition of CN⁻ to the spirocarbon of the MC form. The nucleophilic addition occurs very rapidly (within 1 min) and enables rapid and selective quantification of very low levels of CN⁻ (>0.8 μM) by an absorption analysis.     

A highly selective and sensitive fluorescein-based chemodosimeter for Hg2+ ions in aqueous media

A new fluorescein-based chemodosimeter (II) for Hg²⁺ ion was designed and synthesized, and it displayed excellent selective and sensitive toward Hg²⁺ ion over other commonly metal ions in aqueous media. II was a colorless, non-fluorescent compound. Upon addition of Hg²⁺ to the solution of II, the thiosemicarbazide moiety of II would undergo an irreversible desulfurization reaction to form its corresponding oxadiazole (IV), a colorful and fluorescent product. During this process, the spirocyclic ring of II was opened, causing instantaneous development of visible color and strong fluorescence emission in the range of 500-600 nm. Based on the above mechanism, a fluorogenic Hg²⁺-selective chemodosimeter was developed. The fluorescence increase is linearly with Hg²⁺ concentration up to 1.0 μmol L⁻¹ with a detection limit of 8.5 × 10⁻¹⁰ mol L⁻¹ (3σ). Compared with the rhodamine-type chemodosimeter, II is more stable in aqueous media and exhibits higher sensitivity toward Hg²⁺. The findings suggest that II will serve as a practical chemodosimeter for rapid detection of Hg²⁺ concentrations in realistic media.     

Simple photometric determination of free cyanide ion in aqueous solution with 2,6-dichlorophenolindophenol

In this work, a simple photometric method with high accuracy and precision for measuring trace amounts of free cyanide ion in aqueous solution is demonstrated. Under the evaluated conditions, we could determine CN⁻ concentration in the range of 5–70 ppm easily. The work is based upon the photometric titration of CN⁻ with Co(II) in the presence of 2,6-dichlorophenolindophenol (DCPIP) at λ_max = 602 nm in aqueous solution. The optimal conditions, such as pH, ionic strength, and concentration of chromopher were evaluated. The interence effect of many other cations and anions studied and the results are given here. The optimized titration was successfully used to determine the concentration of free cyanide ion in aqueous solutions.     

Turn-on fluorescence sensing of cyanide ions in aqueous solution简

A sensitive fluorescent probe, 2,2＇-bisbenzimidazole （L）, for CN has been developed. This structurally simple receptor displays great selectivity for the cyanide anion over other common inorganic anions in an aqueous environment. In addition, further study demonstrates the lower detection of the fluorescence response of the sensor to CN is in 10 9 mol/L range. Thus, the present probe should be applicable as a practical system for the monitoring of cyanide concentrations in aqueous samples.     

Naked-eye detection of cyanide ions in aqueous media based on an azo-azomethine chemosensor

The optical and colorimetric properties of a new chemosensor 4-((2,4-dichlorophenyl)diazenyl)-2-(3-hydroxypropylimino)methyl)phenol (L) for cyanide ions were investigated by the naked-eye detection and UV–vis spectroscopy. This receptor reveals visual changes toward CN⁻ anions in aqueous media. No significant color changes were observed upon the addition of any other anions. The cyanide recognition properties of the receptor through proton-transfer were monitored by UV–vis titration and ¹H NMR spectroscopy. The binding constant (K_a) and stoichiometry of the formed host–guest complex were calculated by the Benesi–Hildebrand (B–H) plot and Job's plot method, respectively. The detection limit of the probe towards CN⁻ was 1.03 × 10⁻⁶ mol L⁻¹, which is lower than the maximum value of cyanide (1.9 × 10⁻⁶ mol L⁻¹) permitted by the World Health Organization in drinking water. Thus, this chemosensor was sensitive enough to detect cyanide in aqueous solutions. ¹H NMR experiments were conducted to investigate the nature of interaction between the receptor and CN⁻ anions. Notably, the designed sensor can be applied for the rapid detection of cyanide anions in the basic pH range and also under physiological conditions, for practical purposes for a long duration. The sensing behavior of the receptor was further emphasized by computational studies. Quantum-chemical calculations and molecular studies via Density Functional Theory (DFT) were carried out to supplement the experimental results.     

A green synthesis of a simple chemosensor that could instantly detect cyanide with high selectivity in aqueous solution

A novel and simple cyanide chemosensor 2-(naphthalen-1-ylmethylene)malononitrile(L) was designed and synthesized via a green chemistry method in water without using any catalyst.The chemosensor showed an excellent sensitivity and selectivity for CN in aqueous solution.The detection limit could be as low as 1.6×10~7 moI/L(0.16μmol/L),which is far lower than the WHO guideline of 1.9μmol/L cyanide for drink water.     

Development of a new fluorescence ratiometric switch for endogenous hypochlorite detection in monocytes of diabetic subjects by dye release method

Increased oxidative stress in metabolic complications like type 2 diabetes, dyslipidemia and cardiovascular disorders exerts potential health hazards in many facets. Enhanced production of reactive oxygen species (ROS) due to increased oxidative stress promotes the damage of many biologically important macromolecules. Hypochlorous acid (HOCl), a microbicidal agent is also known to be an important ROS sub-species. An enhanced generation of endogenous HOCl due to diseased condition therefore can be detrimental to health. In present work, a new quinoline-diaminomaleonitrile based probe (HQMN) has been designed for the selective detection of hypochlorite. The probe in hand shows a selective ratiometric emission change towards OCl^?. The probe behaves as a highly selective and sensitive tool for the detection of OCl^? over other analytes with a fast response time (within 100 s). Bioimaging study revealed that HQMN can detect endogenous OCl^? in human monocytes and an increase in endogenous HOCl concentration has been witnessed in diabetic condition compared to healthy control. Thus HQMN can be used as an excellent fluorescent probe for dynamic tracking of hypochorite in living biological cells especially to identify diabetic conditions.     

Fluorescent coumarinyldithiane as a selective chemodosimeter for mercury(II) ion in aqueous solution

A coumarin-based dithiane (1) was synthesized for the selective detection of Hg²⁺ with respect to dual chromo- and fluorogenic changing events in an aqueous solution by the mercury-promoted transformation of a dithiane group into an aldehyde functional unit. The Hg²⁺-selective response of the chemodosimeter was clearly observed in aqueous buffer as well as in human blood plasma medium.     

Ion chromatographic determination of sulfide and cyanide in real matrices by using pulsed amperometric detection on a silver electrode

The determination of free sulfide and cyanide by pulsed amperometric detection (PAD) at a silver-working electrode was improved through a deep de-oxygenation (at least 10 min) of both standard and real solutions containing the two analytes and adopting a two-potential waveform able to eliminate Ag working electrode fouling. The waveform stepped around the oxidation of Ag in the presence of 0.1-0.4 M hydroxyl ion, from -0.1 to 0.1 V versus saturated calomel electrode (SCE). The eluent composition (0.4 M NaOH plus 7.5 mM oxalate solution) allowed a very good column efficiency and selectivity. The presence of a polysulfide species was hypothesized in sulfide solutions that had not been de-oxygenated and aged. The polysulfide eluted just before sulfide and was confirmed by a chemical test with SO3(2-) producing the elimination of the polysulfide peak. Detection limits, according to the Hubaux-Vos method, were 1.0 and 2.0 microg/l for S2- and CN , respectively. We demonstrated good performance of the optimized method by repeatedly injecting standard solutions and by analyzing different real matrices. The method exhibited very good accuracy and repeatability (10 microg/l and a 500 microl injection loop, had a repeatability better than 3% for sulfide and 100 microg/l had a repeatability better than 1% for cyanide). The two-potential waveform ensured long-term stability of the electrode surface that required no manual polishing procedure for at least 1 month (20 analysis per day).