Hg- and Cu-selective fluoroionophoric behaviors of a dioxocyclam derivative bearing anthrylacetamide moieties

New dioxocyclam derivatives bearing two anthracene fluorophores were prepared, and their fluoroionophoric properties toward transition metal ions were investigated. Chemosensor 2 having anthrylacetamide moieties exhibited pronounced Hg²⁺- and Cu²⁺-selective fluoroionophoric properties in aqueous acetonitrile solution over other representative transition metal ions, as well as alkali and alkaline earth metal ions. Chemosensor 2 also exhibited Hg²⁺ and Cu²⁺ selectivity under competitive conditions in the presence of physiologically and environmentally important metal ions. The detection limits for the sensing of Hg²⁺ and Cu²⁺ ions were 7.8 × 10⁻⁶ and 1.5 × 10⁻⁶ M, respectively, in aqueous 95% acetonitrile solution.     

Hg-selective fluoroionophore of p-tert-butylcalix[4]arene-diaza-crown ether having pyrenylacetamide subunits

A new ionophore having two pyrenylacetamide moieties based on the p-tert-butylcalix[4]arene-diaza-crown ether has been prepared and its fluoroionophoric properties were investigated. Bis(pyrenyl) derivative was found to exhibit selective ON-OFF type sensing behavior toward Hg²⁺ ions over other representative transition and heavy metal ions. The fluorescence quenching efficiency of larger than 20-fold was observed with 100 equiv of Hg²⁺ ions and the association constant was found to be 4.5 × 10⁴ M⁻¹ in methanol. The ionophore also exhibited a very efficient quenching of excimer fluorescence selectively upon treatment with Hg²⁺ ions in 50% aqueous methanol solution. The observed Hg²⁺-selective ON-OFF type fluorescence behavior could be utilized as efficient sensing and switching devices for the design of other supramolecular systems.     

A fluorescent chemosensor for Hg based on naphthalimide derivative by fluorescence enhancement in aqueous solution

Naphthalimide derivative (compound 1) containing hydrophilic hexanoic acid group was synthesized and used to recognize Hg²⁺ in aqueous solution. The fluorescence enhancement of 1 is attributed to the formation of a complex between 1 and Hg²⁺ by 1:1 complex ratio (K = 2.08 × 10⁵), which has been utilized as the basis of fabrication of the Hg²⁺-sensitive fluorescent chemosensor. The comparison of this method with some other fluorescence methods for the determination of Hg²⁺ indicated that the method can be applied in aqueous solution rather than organic solution. The analytical performance characteristics of the proposed Hg²⁺-sensitive chemosensor were investigated. The chemosensor can be applied to the quantification of Hg²⁺ with a linear range covering from 2.57 × 10⁻⁷ to 9.27 × 10⁻⁵ M and a detection limit of 4.93 × 10⁻⁸ M. The experiment results show that the response behavior of 1 toward Hg²⁺ is pH independent in medium condition (pH 4.0–8.0). Most importantly, the fluorescence changes of the chemosensor are remarkably specific for Hg²⁺ in the presence of other metal ions, which meet the selective requirements for practical application. Moreover, the response of the chemosensor toward Hg²⁺ is fast (response time less than 1 min). In addition, the chemosensor has been used for determination of Hg²⁺ in hair samples with satisfactory results, which further demonstrates its value of practical applications.     

Fabrication and application of a new modified electrochemical sensor using nano-silica and a newly synthesized Schiff base for simultaneous determination of Cd,Cu and Hg ions in water and some foodstuff samples

A new chemically modified carbon paste electrode was constructed and used for rapid, simple, accurate, selective and highly sensitive simultaneous determination of cadmium, copper and mercury using square wave anodic stripping voltammetry (SWASV). The carbon paste electrode was modified by N,N′-bis(3-(2-thenylidenimino)propyl)piperazine coated silica nanoparticles. Compared with carbon paste electrode, the stripping peak currents had a significant increase at the modified electrode. Under the optimized conditions (deposition potential, −1.100 V vs. Ag/AgCl; deposition time, 60 s; resting time, 10 s; SW frequency, 25 Hz; pulse amplitude, 0.15 V; dc voltage step height, 4.4 mV), the detection limit was 0.3, 0.1 and 0.05 ng mL⁻¹ for the determination of Cd²⁺, Cu²⁺ and Hg²⁺, respectively. The complexation reaction of the ligand with several metal cations in methanol was studied and the stability constants of the complexes were obtained. The effects of different cations and anions on the simultaneous determination of metal ions were studied and it was found that the electrode is highly selective for the simultaneous determination of Cd²⁺, Cu²⁺ and Hg²⁺. Furthermore, the present method was applied to the determination of Cd²⁺, Cu²⁺ and Hg²⁺ in water and some foodstuff samples.     

A new Hg-selective fluorescent sensor based on a dansyl amide-armed calix[4]-aza-crown

A new fluorescent chemosensor for Hg²⁺ based on a dansyl amide-armed calix[4]-aza-crown was reported. It exhibits high sensitivity and selectivity toward Hg²⁺ over a wide range of metal ions in MeCN-H₂O (4:1, v/v). The association constant of the 1:1 complex formation for 2-Hg²⁺ was calculated to be 1.31 × 10⁵ M⁻¹, and the detection limit for Hg²⁺ was found to be 4.1 × 10⁻⁶ mol L⁻¹.     

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.     

Hg-selective fluoroionophoric behavior of pyrene appended diazatetrathia-crown ether

Bis(pyrene) derivative of diazatetrathia-crown ether has been prepared and its Hg²⁺-selective fluoroionophoric properties were investigated. The compound showed a pronounced Hg²⁺-selectivity and other metal ions except for Cu²⁺ showed almost no discernible responses. The Hg²⁺-selectivity of the compound was also confirmed by the competitive experiments performed in the presence of physiologically important metal ions and the detection limit was found to be 1.6 × 10⁻⁶ M. The prominent selective and efficient fluorescence quenching behavior could be utilized as a new chemosensing system for the analysis of toxic Hg²⁺ ions in aqueous environment.     

A new fluorescent sensor bearing three dansyl fluorophores for highly sensitive and selective detection of mercury(II) ions

A novel fluorometric sensor bearing three dansyl moieties based on tris[2-(2-aminoethylthio)ethyl]amine was prepared by a simple approach using a conventional two-step synthesis. The sensor exhibits highly Hg²⁺-selective ON-OFF fluorescence quenching behavior in aqueous acetonitrile solutions and is shown to discriminate various competing metal ions, particularly Cu²⁺, Ag⁺, and Pb²⁺ as well as Ca²⁺, Cd²⁺, Co²⁺, Fe³⁺, Mn²⁺, Na⁺, Ni²⁺, and Zn²⁺, with a detection limit of 1.15 × 10⁻⁷ M or 23 ppb.     

Sodium polyacrylate as a binding agent in diffusive gradients in thin-films technique for the measurement of Cu and Cd in waters

An aqueous solution containing sodium polyacrylate (PA, 0.0030 M) was used in diffusive gradients in thin-films technique (DGT) to measure DGT-labile Cu²⁺ and Cd²⁺ concentrations. The DGT devices (PA DGT) were validated in four types of solutions, including synthetic river waters containing metal ions with or without complexing EDTA, natural river water (Hun River, Shenyang, China) spiked with Cu²⁺ and Cd²⁺, and an industrial wastewater (Shenyang, China). Results showed that only free metal ions were measured by PA DGT, recovery = 98.79% for Cu²⁺ and recovery = 97.80% for Cd²⁺ in solutions containing only free metal ions, recovery = 51.02% for Cu²⁺ and recovery = 51.92% for Cd²⁺ in solution with metal/EDTA molar ratio of 2:1 and recovery = 0 in solutions with metal/EDTA molar ratio of 1:1 and 1:2. These indicated that the complexes of Cu-EDTA and Cd-EDTA were DGT-inert or not DGT-labile. The DGT performance in spiked river water (recovery = 8.47% for Cu²⁺ and recovery = 27.48% for Cd²⁺) and in industrial wastewater (recovery = 14.16% for Cd²⁺) were also investigated. Conditional stability constants (log K) of PA-Cu and PA-Cd complexes were determined as 6.98 and 5.61, respectively, indicating strong interaction between PA and the metals.     

Rhodamine-labelled new architecture for dual sensing of Co and Hg ions

A new rhodamine-based chemosensor 1 has been designed and synthesized. The receptor selectively recognizes Co²⁺ and Hg²⁺ ions in CH₃CN/water (4:1, v/v; 10 μM tris HCl buffer, pH 6.8) by showing different extents of change in emission. The disappearance of colour of mercury-ensemble of 1 followed by appearance of distinct bluish colour under UV illumination upon addition of l-cysteine distinguishes Hg²⁺ from Co²⁺ ions. The receptor shows in vitro detection of both the ions in human cervical cancer (HeLa) cells.     

A novel colorimetric and fluorescent chemosensor: synthesis and selective detection for Cu and Hg

A novel two-channel metal ion sensor has been synthesized from macrocyclic dioxotetraamine and 1,8-naphthalimide derivative. The metal ion-selective signaling behaviors of the sensor were investigated. The sensor presented the selective coloration for Cu²⁺ and Hg²⁺ that can be detected by the naked-eye, respectively. Besides, the addition of Cu²⁺ and Hg²⁺ quenched the fluorescence of 1 obviously and the detection limit was found to be 3 × 10⁻⁷ M for Cu²⁺ and 7 × 10⁻⁷ M for Hg²⁺. This sensor can be utilized for the visual and spectroscopic detection of Cu²⁺ or Hg²⁺ in the presence of the other competing metal ions.     

Photoactive chemosensors 4: a Cu protein cavity mimicking fluorescent chemosensor for selective Cu recognition

Fluorescent chemosensor 3 can sense Cu²⁺ ions (1-8 μM) even in the presence of elevated levels of Ni²⁺, Cd²⁺, Zn²⁺, Hg²⁺, Ag⁺ and Pb²⁺ (5000 μM). 3 can also analyze for Ag⁺ ions (50-500 μM) in the presence of Ni²⁺, Cd²⁺, Zn²⁺, Hg²⁺ and Pb²⁺ (5000 μM) but Cu²⁺ strongly interferes.     

Naphthalene and pyrrole substituted guanidine in selective sensing of Cu2+, Hg2+, Pb2+ and CN− ions under different conditions

Naphthalene and pyrrole substituted guanidine 1 has been designed and synthesised. Compound 1 efficiently distinguishes Cu²⁺, Hg²⁺ and Pb²⁺ ions by exhibiting different responses in fluorescence. While compound 1 exhibited turn-on emission selectively in the presence of Hg²⁺ and Pb²⁺ ions in CH₃CN and CH₃CN–H₂O (1:1, v/v), respectively, it showed decrease in emission upon interaction with Cu²⁺ ion in CH₃CN. Furthermore, the Cu-1 ensemble has been established as a potential probe for selective detection of CN^? ion over a series of other anions involving colour change (in ordinary light: colourless to light yellow and under UV light: colourless to sky blue). Theoretical insight has been invoked to understand the mode of metal–ligand interaction.     

Azo 8-hydroxyquinoline benzoate as selective chromogenic chemosensor for Hg and Cu

Azo 8-hydroxyquinoline benzoate (2) was synthesized and studied to detect metal ions. Distinct color change was found for compound 2 in the presence of transition metal ions Hg²⁺ or Cu²⁺ in CH₃CN, respectively, which makes it possible for distinguishing Hg²⁺ and Cu²⁺ from other metal ions by the ‘naked eye’.     

Dual optical detection of a novel selective mercury sensor based on 7-nitrobenzo-2-oxa-1,3-diazolyl subunits

A novel macromolecule based on 2-[3-(2-aminoethylthio)propylthio]ethanamine covalently bound to two 7-nitrobenzo-2-oxa-1,3-diazolyl moieties was prepared as a fluoroionophore and a chromophore for the selective optical detection of Hg²⁺. The sensor was prepared in two steps and its fluoroionophoric and chromophoric properties toward various transition metal, alkali, and alkali earth cations were investigated. Compound 4 selectively binds Hg²⁺, and the binding is indicated by both fluorescence quenching and a chromogenic change which can be detected by the naked eye. In an 80:20 acetonitrile/water solvent mixture, 4 acts as an ON-OFF fluorescence switch upon Hg²⁺ binding, exhibiting efficient quenching and a detection limit of 10⁻⁷ M or 20 ppb.     

Highly selective detection of Hg ion by push–pull-type purine nucleoside-based fluorescent sensor

Highly selective detection of Hg²⁺ ion has been achieved using the push–pull-type purine nucleoside-based fluorescent sensor L1. The sensor L1 incorporating aza-18-crown-6 at C6 position of purine nucleoside, is highly sensitive and selective toward Hg²⁺ ion in CH₃CN–H₂O mixture (92/8, v/v). The detection limit for the fluorescent sensor L1 toward Hg²⁺ ion is 7.8 × 10⁻⁸.     

Ratiometric and turn-on monitoring for heavy and transition metal ions in aqueous solution with a fluorescent peptide sensor

A novel fluorescent peptide sensor containing tryptophan (donor) and dansyl fluorophore (acceptor) was synthesized for monitoring heavy and transition metal (HTM) ions on the basis of metal ion binding motif (Cys-X-X-X-Cys). The peptide probe successfully exhibited a turn on and ratiometric response for several heavy metal ions such as Hg²⁺, Cd²⁺, Pb²⁺, Zn²⁺, and Ag⁺ in aqueous solution. The enhancements of emission intensity were achieved in the presence of the HTM ions by fluorescent resonance energy transfer (FRET) and chelation enhanced fluorescence (CHEF) effects. The detection limits of the sensor for Cd²⁺, Pb²⁺, Zn²⁺, and Ag⁺ were lower than the EPA's drinking water maximum contaminant levels (MCL). We described the fluorescent enhancement, binding affinity, and detection limit of the peptide probe for HTM ions.     

An efficient and selective flourescent chemical sensor based on 5-(8-hydroxy-2-quinolinylmethyl)-2,8-dithia-5-aza-2,6-pyridinophane as a new fluoroionophore for determination of iron(III) ions. A novel probe for iron speciation

A novel fluorescent chemical sensor for the highly sensitive and selective determination of Fe³⁺ ions in aqueous solutions is prepared. The iron sensing system was prepared by incorporating 5-(8-hydroxy-2-quinolinylmethyl)-2,8-dithia-5-aza-2,6-pyridinophane (L) as a neutral Fe³⁺-selective fluoroionophore in the plasticized PVC membrane containing sodium tetraphenylborate as a liphophilic anionic additive. The response of the sensor is based on the strong fluorescence quenching of L by Fe³⁺ ions. At pH 5.5, the proposed sensor displays a calibration curve over a wide concentration range from 6.0 × 10⁻⁴ to 1.0 × 10⁻⁷ M, with a relatively fast response time of less than 2 min. In addition to a high stability and reproducibility, the sensor shows a unique selectivity toward Fe³⁺ ion with respect to common coexisting cations. The proposed fluorescence optode was applied to the determination of iron(III) content of straw of rice, spinach and different water samples. The fluorescent sensor was also used as a novel probe for Fe³⁺/Fe²⁺ speciation in aqueous solution.     

Exploiting the deprotonation mechanism for the design of ratiometric and colorimetric Zn fluorescent chemosensor with a large red-shift in emission

The design, synthesis, and photophysical evaluation of a new naphthalimide-based fluorescent chemosensor, N-butyl-4-[di-(2-picolyl)amino]-5-(2-picolyl)amino-1,8-naphthalimide (1), were described for the detection of Zn²⁺ in aqueous acetonitrile solution at pH 7.0. Probe 1 showed absorption at 451 nm and a strong fluorescence emission at 537 nm (Φ_F=0.33). The capture of Zn²⁺ by the receptor resulted in the deprotonation of the secondary amine conjugated to 1,8-naphthalimide so that the electron-donating ability of the N atom would be greatly enhanced; thus probe 1 showed a 56 nm red-shift in absorption (507 nm) and fluorescence spectra (593 nm, Φ_F=0.14), respectively, from which one could sense Zn²⁺ ratiometrically and colorimetrically. The deprotonated complex, [(1-H)/Zn]⁺, was calculated at m/z 619.1800 and measured at m/z 618.9890. In contrast to these results, the emission of 1 was thoroughly quenched by Cu²⁺, Co²⁺, and Ni²⁺. The addition of other metal ions such as Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Fe³⁺, Mn²⁺, Al³⁺, Cd²⁺, Hg²⁺, Ag⁺, and Pb²⁺ produced a nominal change in the optical properties of 1 due to their low affinity to probe 1. This means that probe 1 has a very high fluorescent imaging selectivity to Zn²⁺ among metal ions.     

Determination of Hg on poly(vinylferrocenium) (PVF)-modified platinum electrode

A new surface based on poly(vinylferrocenium) (PVF⁺)-modified platinum electrode was developed for determination of Hg²⁺ ions in aqueous solutions. The polymer was electrodeposited on platinum electrode by constant potential electrolysis as PVF⁺ClO₄⁻. Cl⁻ ions were then attached to the polymer matrix by anion exchange and the modified electrode was dipped into Hg²⁺ solution. Hg²⁺ was preconcentrated at the polymer matrix by adsorption and also complexation reaction with Cl⁻. Detection of Hg²⁺ was carried out by differential pulse anodic stripping voltammetry (DPASV) after reduction of Hg²⁺. Mercury ions as low as 5 × 10⁻¹⁰ M could be detected with the prepared electrode and the relative standard deviation was calculated as 6.35% at 1 × 10⁻⁶ M concentration (n = 6). Interferences of Ag⁺, Pb²⁺ and Fe³⁺ ions were also studied at two different concentration ratios with respect to Hg²⁺. The developed electrode was applied to the determination of Hg²⁺ in water samples.