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.     

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.     

Unique Fluorogenic Ratiometric Fluorescent Chemodosimeter for Rapid Sensing of CN− in Water

A new benzimidazole‐spiropyran conjugate chemosensor molecule ( BISP ) has been synthesized and characterized by ¹H NMR spectroscopy, mass spectrometry (ESI‐MS), and elemental analysis. The two isomeric forms ( BISP ? BIMC ) were shown to be highly selective and sensitive to CN^? among the ten anions studied in aqueous HEPES buffer, as shown by fluorescence and absorption spectroscopy and even by visual color changes, with a detection limit of 1.7 μM for BIMC . The reaction of CN^? with BIMC was monitored by ¹H NMR spectroscopy, high‐resolution mass spectrometry (HRMS), UV/Vis measurements, and fluorescence spectroscopy in HEPES buffer of pH 7.4. TDDFT calculations were performed in order to correlate the electronic properties of the chemosensor with its cyanide complex. Further, titration against thiophilic metal ions like Au³⁺, Cu²⁺, Ag⁺, and Hg²⁺ with [ BIMC‐CN ] in situ showed that it acts as a secondary recognition ensemble toward Au³⁺ and Cu²⁺ by switch‐on fluorescence. In addition, a reversible logic‐gate property of BIMC has been demonstrated through a feedback loop in the presence of CN^? and Au³⁺ ions, respectively. Furthermore, the use of BIMC to detect CN^? in live cells by fluorescence imaging has also been demonstrated. Notably, test strips based on BIMC were fabricated, which could serve as convenient and efficient CN^? test kits.     

Reaction‐Based Ratiometric Chemosensor for Instant Detection of Cyanide in Water with High Selectivity and Sensitivity

A highly selective chemosensor 1 based on an acylhydrazone group as binding site and naphthalene group as the fluorescence signal group were described, which could instantly detect CN^? in water with specific selectivity and high sensitivity. The detection of cyanide was performed via the nucleophilic attack of cyanide anion on the carbonyl group, which could be confirmed by ¹H NMR, ¹³C NMR, ESI‐MS and DFT calculations. The addition of CN^? to sensor 1 induced a remarkable color change from colorless to yellow and generated a blue fluorescence, these sense procedure could not interfered by other coexistent competitive anions (F^?, Cl^?, Br^?, I^?, AcO^?, H₂PO₄^?, HSO₄^?, ClO₄^?, SCN^?, S^2?, NO₃^? and SO₄^2?). The detection limits were 5.0×10^?7 M and 2.0×10^?9 M of CN^? using the visual fluorescent color changes and fluorescence spectra changes respectively, which is far lower than the WHO guideline of 1.9×10^?6 M . Test strips based on sensor 1 were fabricated, which could act as a convenient and efficient CN^? test kit to detect CN^? in pure water for “in‐the‐field” measurement.     

Anion recognition based on phenolic hydroxyl group in competitive media

Two novel artificial receptors, one containing phenolic hydroxyl group and diamide (1), the other only containing diamide (2), were designed and synthesized. The binding ability evaluated by UV–vis and fluorescence titration experiments in dry DMSO revealed that compound 1 could selectively recognize AcO^?. In particular, the binding ability can also be detected in the DMSO/H₂O solution by UV–vis. The interference experiment result showed that the binding ability was not influenced by the existence of other anions. In contrast, there were no detectable interaction between receptor 2 and anions. The further insights to the nature of interaction between receptor 1 and AcO^? were investigated by ¹H NMR titration experiments and theoretical investigation, which demonstrated receptor 1 complexed AcO^? through the synergistic hydrogen bonding interaction of OH and NH.     

A highly selective fluorescent sensor for fluoride anion based on pyrazole derivative: Naked eye “no–yes” detection

A new pyrazole-based fluorescent sensor, 5-amino-3-(5-phenyl-1H-pyrrol-2-yl)-1H-pyrazole-4-carboxamide (compound 1), was studied for fluoride anion (F^?) detection in organic or water-containing solution. This compound displayed both changes in UV–vis absorption and fluorescence emission spectra upon addition of F^?. With increasing of F^?, blue emission intensity increases drastically and reaches saturation with 607-fold enhancement at 424 nm. The results indicate that compound 1 has highly selectivity for fluoride detection over other anions, such as Cl^?, Br^?, I^?, HSO₄^?, H₂PO₄^? and AcO^? in DMSO or aqueous DMSO solutions. ¹H NMR titration and other experiments confirm that the sensing process is mainly from the deprotonation of the pyrazole–NH in compound 1.     

Coumarin-based urea-amide scaffold in ratiometric fluorescence sensing of CN−

Coumarin-based urea and urea–amide scaffolds 1–3 have been designed and synthesized for the selective and naked eye detection of cyanide ion. Of the three, compound 3 exhibits ratiometric fluorescence change selectively in the presence of CN^? and validates the rationality in designing anion receptor. Upon interaction with CN^?, the color of the solution of 3 in CH₃CN under UV exposure becomes bright yellow, which is beneficial for its naked eye detection. Addition of CN^? of ～10^?4 M brings nice color change from colourless to yellow in ordinary light. The sensing event is supposed to be due to nucleophilic addition of CN^? to the coumarin unit enabling intramolecular charge transfer (ICT) mechanism.     

Novel fluorescent cyanide-selective chemosensor based on a functionalised pillar[5]arene copper(II) complex

As a novel macrocyclic host, pillar[5]arene can selectively recognise guest molecules in organic solvents. In this study, a fluorescent chemosensor composed of a functionalised-pillar[5]arene and Cu²⁺ metal complex (PN–Cu), which shows good selectivity for CN^? anions, has been designed and synthesised. Complexation between PN–Cu and anions has been probed by means of various fluorescence-based methods. PN–Cu, as a turn-on fluorescence chemosensor showed high selectivity towards CN^? ions in comparison to other anions, and its detection limit for CN^? was calculated as 9.03 × 10^?7 M. The PN–Cu sensor can serve as a recyclable component in sensing materials. Moreover, the interaction between the singly functionalised pillar[5]arene and Cu²⁺ has been probed through various tests. Based on the remarkable selectivity of the chemosensor PN–Cu, we propose that it might be used as a potential material for CN^? recognition.     

Novel multi-responsive fluorescence switch for Hg2+ and UV/vis lights based on diarylethene-rhodamine derivative

A new multi-responsive fluorescent switch DTE-Pip-Rho 1O has been designed and synthesized in this study. For this molecule, the reactive site of spirolactam ring is far away from the diarylethene unit through the intramolecular piperazine. It exhibited high selectivity and sensitivity to Hg²⁺ in addition to obvious color change (colorless-pink) and fluorescence “off-on” (dark-orange) during this process. It is believed that the color change is due to Hg²⁺-assisted hydrolysis of rhodamine hydrazide. Therefore, the new molecule can be used as colorimentric and fluorescent chemosensor for Hg²⁺ with high selectivity. The detection limits of absorbance and fluorescence for Hg²⁺ were calculated to be 1.15?μM and 1.16?μM, respectively. The resulting DTE-Pip-Rho 1O-Hg²⁺ could also function as a reversible fluorescence photo-switch in response to UV/vis light owing to FRET mechanism. Moreover, it has been demonstrated that the photo-switchable system displayed excellent fatigue resistance and remarkable anti-photobleaching capability.     

Triphenylamine-based simple chemosensor for selective fluorometric detection of fluoride, acetate and dihydrogenphosphate ions in different solvents

Triphenylamine-based new chemosensors 1 and 2 have been designed and synthesized for fluorometric detection of anions. The urea-amide conjugates in 1 and 2 are involved in binding of anions via hydrogen bonding. UV?Cvis and fluorescence titration experiments revealed that the sensor 1 has the selectivity for acetate (AcO^?), dihydrogenphosphate (H₂PO₄ ^?) and fluoride (F^?) over the other anions examined in the present study, in CHCl₃. In comparison, receptor 2 is non responsive for the same anions under similar conditions. In more polar solvent CH₃CN containing 0.1% DMSO, the receptor 1 shows a greater selectivity towards fluoride. The color of the solution of 1 is changed from colorless to light yellow and finally to yellowish brown only in the presence of fluoride in CH₃CN containing 10% DMSO. In pure DMSO and CH₃CN solvents, almost colorless solution of 1 is transformed into blood red and reddish brown in the presence of 30 equivalent amounts of F^?, respectively.     

Synthesis and electrochemical properties of calix[4]arene derivatives containing ferrocene units in the cone and 1,3-alternate conformation

Two novel calix[4]arene receptors containing ferrocene units in cone (L₁) and 1,3-alternate (L₂) conformations have been synthesized from 25,27-dihydroxy-26,28-bis[(3-aminopropyl)oxy]calix[4]arene 4 or 25,26,27,28-tetra[(3-aminopropyl)oxy]calix[4]arene 6 and ferrocenecarboxaldehyde via condensation, respectively. Their structures have been characterized by ¹H, ¹³C, APT, COSY NMR, FTIR, HSMR, and UV–vis spectral data. The electrochemical behavior of L₁ and L₂ has been investigated in the presence of F^?, Cl^?, Br^?, H₂PO₄^?, CH₃COO^? anions. Electrochemical studies show that these receptors electrochemically recognize CH₃COO^?, H₂PO₄^?, and Cl^?, anions. Using an UV–vis study, the selectivity to these anions in DMSO solution was confirmed.     

A coumarin based highly selective fluorescent chemosensor for sequential recognition of Cu2+ and PPi

In this study, we have successfully synthesized a new coumarin based fluorescent chemosensor 1, in which tren and quinolone are introduced as receptors for sequential recognition of Cu²⁺ and PPi. The structure of chemosensor 1 was characterized by ¹H NMR, ¹³C NMR and ESI-HR-MS. Sensor 1 showed an obvious “on-off” fluorescence quenching response toward Cu²⁺, and the quenching efficiency reached a maximum of 99.6% with the addition of 20 equiv. of Cu²⁺. The 1-Cu²⁺ complex showed an “off-on” fluorescence enhancement response toward PPi over many competitive anions, especially HPO₄^2? and H₂PO₄^?. The detection limit of sensor 1 was 1.9?×?10^?6?M to Cu²⁺ and 5.96?×?10^?8?M to PPi. In addition, sensor 1 showed a 1:1 binding stoichiometry to Cu²⁺ and sensor 1-Cu²⁺ showed a 2: 1 binding stoichiometry to PPi in CH₃CN/HEPES buffer medium (9:1 v/v, pH?=?7.4). The stable pH range of sensor 1 to Cu²⁺ and 1-Cu²⁺ to PPi was from 4 to 8.     

Synthesis of Novel Anionic Receptors with （Thio）urea and Amide Binding Sites and the Recognition Properties for Anions

IntroductionSincemoreandmoreanionsplayanimportantroleinbiologicalandchemicalprocesses ,thedesignandsynthe sisofreceptorsforon lineandrealtimedetectionofbio logicallyimportantanions ,andforenvironmentalmonitor ingofharmfulanionpollutantshaveattractedparticularat tentioninsupramolecularchemistry .1Thebasicstrategyfortheconstructionofanion bindingreceptorsistoexploitthereceptorsthathaveelectrostatic ,2 hydrogenbonding ,3orLewisacidiccentralinteraction .4 Amongavarietyofnon covalentinteractions ,h…     

A multi-responsive diarylethene-rhodamine 6G derivative for sequential detection of Cr3+ and CO32−

A new unsymmetrical diarylethene derivative (1o) with rhodamine 6G as a functional group has been designed and synthesized. It displayed good physicochemical properties induced by lights and chemical stimuli. 1o could sensitively detect towards Cr³⁺ with a 1:1 stoichiometry, and exhibit an obviously fluorescence (from dark to light cyan) and color (from colorless to pink) changes during the recognition process. The limit of detection was determined to be 27?nM and 8.5?nM via UV/vis and fluorescence methods, respectively. More importantly, the resulting complex 1o-Cr³⁺ (1o') could be served as a potential fluorescent probe to selectively and sensitively recognize toward CO₃^2?, the limit of detection was determined to be 0.88?μM and 0.26?μM via UV/vis and fluorescence methods, respectively. Moreover, the quenching of fluorescence intensity can reach 95% due to the perfect FRET processes between the excited open-ring rhodamine 6G moiety and the closed-ring diarylethene unit.     

A highly selective diarylethene chemosensor for dual channel recognition of CN− and Zn2+ and its application

A novel diarylethene chemosensor comprising 3-aminobenzofuran-2-carboxamide Schiff base (1O) was synthesized and the photophysical and sensing behaviors of 1O were further investigated. Importantly, the introduction of electron-withdrawing group to 1O made the sensor an efficient tool for detection of toxic cyanide even in the presence of other plausible interfering anions including fluoride and acetate. In particular, addition of CN^? to 1O visibly changes the color from colorless to orange-red, which can be observed by the naked eye. Apart from this, it also exhibited an outstanding fluorometric sensing toward Zn²⁺ with high selectivity and sensitivity. Moreover, the remarkable spectral responses of the devised sensor prompted us to fabricate molecular logic circuit. Furthermore, the sensor was successfully applied to the detection of CN^? on test strips and silica coated microslides, and the methods were very simple to operate without resorting to any spectroscopic instrumentation. In addition, the 1O can also effectively detect CN^? and Zn²⁺ in actual water samples.     

Electrofluorochromic Detection of Cyanide Anions Using a Nanoporous Polymer Electrode and the Detection Mechanism

An electrofluorochromic (EFC) conjugated copolymer ( P_EFC ) containing carbazole and benzothiadiazole (BTD) moieties is synthesized through Suzuki coupling followed by electrochemical polymerization, resulting in a nanoporous EFC polymer electrode. The electrode exhibits high sensitivity and selectivity in the EFC detection of cyanide anions (CN^?) in largely aqueous electrolyte (67 vol % water) because electrochemical oxidation of P_EFC leads to significant fluorescence quenching, and the presence of different concentrations (1 to 100 μM ) of CN^? in the electrolyte can weaken the oxidative quenching to substantially different extents. Although P_EFC is hydrophobic in the neutral state, it is converted to radical cation/dication states upon oxidation, rendering the P_EFC some hydrophilicity. Moreover, its nanoporous morphology provides a large surface area and short diffusion distance, facilitating the movement of CN^? in the electrolyte into the P_EFC film to interact with receptors. Density functional theory calculations show that the noncovalent interaction between electron‐deficient BTD and nucleophilic CN^? is energy favorable in the oxidized states in both aqueous and organic media, suggesting that the specific π^?–π⁺ interaction plays the main role in the CN^? detection.     

A novel naphthalimide–glutathione chemosensor for fluorescent detection of Fe3+ and Hg2+ in aqueous medium and its application

By rationally introducing glutathione functionalized 1, 8–naphthalimide, a novel fluorescent chemosensor (NG) was successfully synthesized. NG can high selectively and sensitively recognize Fe³⁺/Hg²⁺ ions through quenching of fluorescence among all kinds of common metal ions in aqueous medium. The binding stoichiometry ratio of NG–Fe³⁺ is verified as 2:1and NG–Hg²⁺ as 1:2 confirmed by Job's plot method, FT-IR, ¹H NMR and ESI–MS spectrum, and the possible sensing mechanism were also proposed. The chemosensor NG toward Fe³⁺ and Hg²⁺ displays the excellent advantages of high selectivity and sensitivity, low detection limits (7.92?×?10^?8 and 4.22?×?10^?8?M), high association constants (3.37?×?10⁸ and 8.14?×?10⁴?M^?2), instataneous response (about 10s) and wide pH response range (3.0–8.0). Importantly, the chemosensor NG was successfully applied to determine Hg²⁺ in tap water. Meanwhile, the test strips based on NG were prepared, which could conveniently and efficiently detect Fe³⁺ and Hg²⁺. Moreover, the complex of NG and Fe³⁺ (NG–Fe³⁺) showed high selectivity and sensitivity for H₂PO₄￣ over many other anions in the same medium.     

Colorimetric sensing of cyanide anion in aqueous media with a fluorescein–spiropyran conjugate

A fluorescein–spiropyran conjugate (2) behaves as a receptor for colorimetric sensing of cyanide anion (CN^?) in aqueous media under irradiation of UV light. The compound 2, which exists as a spirocycle-closed (SP) form in the dark condition, is isomerized to the spirocycle-opened merocyanine (MC) form upon irradiation of UV light and shows absorption bands at 467 and 568 nm. Addition of CN^? to the solution leads to a decrease in these bands and an appearance of new absorption band at 512 nm, via a nucleophilic interaction between CN^? and the spirocarbon of MC form. This absorption change occurs selectively with CN^? and enables ratiometric quantification of CN^? by absorption analysis.     

Study by fluorescence of calix[4]arenes bearing heterocycles with anions: highly selective detection of iodide

The present work describes a study of complexation efficiency of calix[4]arenes bearing benzoimidazolyl, benzothiazolyl, and benzoxazolyl heterocycles (5–7) towards several anions. The binding ability of calixarene derivatives 5–7 towards selected anions of different molecular geometries such as: F^?, HSO₄ ^?, I^?, N₃ ^?, NO₃ ^?, NO₂ ^?, SCN^?, ClO₄ ^?, Br^?, CN^?, Cl^?, CH₃COO^? CF₃SO₃ ^? in methanol, has been investigated by fluorescence spectroscopic techniques, all anions were used as tetrabutylammonium salts to avoid possible complexation of cationic species by the derivative calix[4]arenes. Fluorescent chemosensor ability of these three calixarene derivatives was highly selective for iodide in contrast with other anions studied. The best chemosensor found, corresponds to compound 7, with an association constant of 2.01 × 10⁴ mol^?1 L and a detection limits of 0.22 ppm for iodide.     

Bithiophene triarylborane dyad: An efficient material for the selective detection of CN− and F− ions

A new fluorescent chemosensor based on bithiophene coupled dimesitylborane (BMB-1) was synthesized and characterized. BMB-1 was used for colorimetric and turn-on fluorescent sensing of cyanide (CN⁻) and fluoride (F⁻) ions, in the presence of other competitive anions in an aqueous (CH₃CN–H₂O) medium. BMB-1 showed a hypsochromic shift (blue shift) with addition of CN⁻ and F⁻ ions in absorption studies. The lower detection level of CN⁻ and F⁻ ions is 1.37 × 10⁻⁹ and 1.75 × 10⁻⁹ M, respectively. The BMB-1 binding mechanism is based on the nucleophilic addition of CN⁻ and F⁻ ions in the internal charge transfer transition of bithio moiety to the boranylmesitylene unit, and the color changes were observed under UV light. This result is further confirmed by Fourier transform infrared spectroscopy, mass spectrometry and density functional theory calculations. Also, the BMB-1 probe is found to be a good adsorbent for the removal of F⁻ ions in real water samples using the adsorption technique.