Characterization of rhodamine B hydroxylamide as a highly selective and sensitive fluorescence probe for copper(II)

Rhodamine B hydroxylamide (1) is characterized as a highly selective and sensitive fluorescence probe for Cu²⁺. Under the optimized conditions, the probe exhibits specific absorbance-on and fluorescence-on responses to Cu²⁺ only. This remarkable property may allow Cu²⁺ to be detected directly in the presence of the other transition metal ions, and such an application has been demonstrated to human serum. The reaction mechanism is also investigated and proposed as that the hydroxylamide group of 1 binds Cu²⁺, and the subsequent complexation of Cu²⁺ displays a high catalytic activity for the hydrolytic cleavage of the amide bond, causing the release of fluorophore (rhodamine B) and thereby the retrievement of absorbance and fluorescence. The recovered fluorescence intensity is proportional to the concentration of Cu²⁺ in the range 1-20 μM. The detection limit for Cu²⁺ is 33 nM (k = 3). The reaction mechanism described here may be useful for developing excellent spectroscopic probes with cleavable active bonds for other analytes.     

A highly selective and ratiometric fluorescence probe for the detection of Hg and pH change based on coumarin in aqueous solution

A simple but highly selective coumarin-based fluorescence probe 1, 8-(1,3-dithiane)-7-hydroxycoumarin was designed and synthesized for both the ratiometric detection of Hg²⁺ and the on–off response to pH change in aqueous solution. The sensor detected Hg²⁺ selectively via Hg²⁺-promoted thioacetal deprotection reaction within five minutes and reflected pH in the range from 7.8 to 11.9 as a result of the equilibrium between weak-fluorescent acid form and strong-fluorescent base form. In addition, the probe has an excellent selectivity towards Hg²⁺ over other competitive metal ions for biomedical and environmental applications. The sensing behavior of our probe was studied by UV–visible absorption spectra and fluorescence spectra.     

Novel fluorimetric bulk optode membrane based on 5,8-bis((5′-chloro-8′-hydroxy-7′-quinolinyl)methyl)-2,11-dithia-5,8-diaza-2,6-pyridinophane for selective detection of lead(II) ions

A novel fluorescence chemical sensor for the highly sensitive and selective determination of Pb²⁺ ions in aqueous solutions is described. The preliminary potentiometric and spectrofluorimetric complexation studies in solution revealed that the lipophilic ligand 5,8-bis((5′-chloro-8′-hydroxy-7′-quinolinyl)methyl)-2,11-dithia-5,8-diaza-2,6-pyridinophane (L2) forms a highly stable and selective [PbL2]²⁺ and [Pb(L2)₂]²⁺ complexes which results in a strong fluorescence quenching of the ligand. Thus, a novel fluorescence Pb²⁺ sensing system was prepared by incorporating L2 as a neutral lead-selective fluoroionophore in the plasticized PVC membrane containing tetrakis(p-chlorophenyl) borate as a liphophilic anionic additive. The response of the sensor is based on the strong selective fluorescence quenching of L2 by Pb²⁺ ions. At pH 5.5, the proposed sensor displays a calibration curve over a wide concentration range of 3.0 × 10⁻⁷ to 2.5 × 10⁻² M with a relatively fast response time of less than 5 min. In addition to high stability, reversibility and reproducibility, the sensor shows a unique selectivity towards Pb²⁺ ion with respect to common coexisting cations. The proposed fluorescence optode was successfully applied to the determination of lead in plastic toys and tap water samples.     

A highly selective molecularly imprinted electrochemiluminescence sensor for ultra-trace beryllium detection

A new molecularly imprinted electrochemiluminescence (ECL) sensor was proposed for highly sensitive and selective determination of ultratrace Be²⁺ determination. The complex of Be²⁺ with 4-(2-pyridylazo)-resorcinol (PAR) was chosen as the template molecule for the molecularly imprinted polymer (MIP). In this assay, the complex molecule could be eluted from the MIP, and the cavities formed could then selectively recognize the complex molecules. The cavities formed could also work as the tunnel for the transfer of probe molecules to produce sound responsive signal. The determination was based on the intensity of the signal, which was proportional to the concentrations of the complex molecule in the sample solution, and the Be²⁺ concentration could then be determined indirectly. The results showed that in the range of 7 × 10⁻¹¹ mol L⁻¹ to 8.0 × 10⁻⁹ mol L⁻¹, the ECL intensity had a linear relationship with the Be²⁺ concentrations, with the limit of detection of 2.35 × 10⁻¹¹ mol L⁻¹. This method was successfully used to detect Be²⁺ in real water samples.     

A simple click generated probe for highly selective sequential recognition of Cu(II) and pyrophosphate

A click generated quinoline derivative (1) has been synthesized and used as a fluorescent probe for sequential recognition of Cu²⁺ and pyrophosphate (PPi) in DMSO/H₂O (1:1, v/v, HEPES 20 mM, pH = 7.4) solution. Probe 1 displays high selectivity to Cu²⁺ ions, and the in-situ prepared probe 1-Cu²⁺ exhibits high selectivity toward pyrophosphate (PPi) with emission recovery of probe 1. Therefore, 1-Cu²⁺ complex can be applied as a fluorescence turn-on probe for PPi with high selectivity and sensitivity.     

A stoichiometric imprinted chelating resin for selective recognition of copper(II) ions in aqueous media

This work reports the preparation of a new copper(II) ion-imprinted polymer (IIP) material, using 5,6;14,15-dibenzo-1,4-dioxa-8,12-diazacyclopentadecane-5,14-diene (DBDA15C4) and 2-vinylpyridine (VP) as a non-vinylated chelating agent and a functional vinyl monomer, respectively. The Cu²⁺ ion can form stable complexes with DBDA15C4 and VP. The stoichiometries of Cu²⁺-DBDA15C4 and ternary Cu²⁺-DBDA15C4-VP complexes were elucidated using conductometric and spectrophotometric methods, and found to be Cu²⁺(DBDA15C4), Cu²⁺(DBDA15C4)₂ and Cu²⁺(DBDA15C4)(VP)₂. The results obtained from solution studies were also supported by ab initio theoretical calculations. The resulting ternary complex Cu²⁺(DBDA15C4)(VP)₂ was copolymerized with ethyleneglycoldimethacrylate, as a cross-linking monomer, via bulk polymerization method. The imprinted copper ion was removed from the polymeric matrix by 0.1 M HNO₃. The Cu²⁺-imprinted polymer particles were characterized by IR spectroscopy and elemental analysis. Optimum pH range for rebinding of Cu²⁺ on the IIP and equilibrium binding time were 7.0-7.5 and 45 min, respectively. Sorbent capacity and enrichment factor for Cu²⁺ were obtained as 75.3 ± 1.9 μmol g⁻¹ and 100, respectively. In selectivity study, it was found that imprinting results in increased affinity of the material toward Cu²⁺ ion over other competitor metal ions with the same charge and close ionic radius. The prepared IIPs were repeatedly used and regenerated for five times without a significant decrease in polymer binding affinities.     

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.     

Colorimetric and fluorescent chemosensor for citrate based on a rhodamine and Pb complex in aqueous solution

In this paper we unveil a novel rhodamine compound based fluorescent chemosensor (1-Pb²⁺) for colormetric and fluorescent detection of citrate in aqueous solution. This is the first fluorescent chemosensor for citrate based on rhodamine compound. The comparison of this method with some other fluorescence methods for citrate indicates that the method can detect citrate in aqueous solution by both color changes and fluorescent changes with long emission wavelength. In the new developed sensing system, 1-Pb²⁺ is fluorescent due to Pb²⁺-induced fluorescence enhancement of 1. However, the addition of citrate may release 1 into the solution with quenching of fluorescence. The chemosensor can be applied to the quantification of citrate with a linear range covering from 1.0 × 10⁻⁷ to 5.0 × 10⁻⁵ M and a detection limit of 2.5 × 10⁻⁸ M. The experiment results show that the response behavior of 1-Pb²⁺ towards citrate is pH independent in medium condition (pH 6.0–8.0). Most importantly, the fluorescence changes of the chemosensor are remarkably specific for citrate in the presence of other anions (even those that exist in high concentration), which meet the selective requirements for practical application. Moreover, the response of the chemosensor toward citrate is fast (response time less than 1 min). In addition, the chemosensor has been used for determination of citrate in urine samples with satisfactory results.     

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.     

Removal of copper(II) from aqueous solution with rape stalk modified by citric acid

In this paper, rape stalk was modified with citric acid (CA) to prepare copper ion biosorbent. The modified rape stalk (MRS) was characterized by Fourier transforms infrared (FTIR), zeta potential, and thermogravimetric analysis (TGA). The effects of various parameters like initial Cu²⁺ concentration, contact time, initial pH, and temperature on adsorption capacity were studied. The adsorption capacity of MRS at 298 K was 69.84 mg/g, far higher than 18.24 mg/g for native rape stalk (NRS). The adsorption mechanism was also evaluated in terms of kinetics and thermodynamics. The adsorption equilibrium data was well described by the Langmuir isotherm model. The adsorption process followed the pseudo-second-order rate kinetics. Thermodynamic study showed spontaneous and endothermic nature of the adsorption process. The ion exchange of the adsorption mechanism was affirmed. MRS could be a potentially low-cost and green adsorbent for removal of Cu²⁺ from aqueous solution.     

Synthesis and characterization of novel ion-imprinted polymeric nanoparticles for very fast and highly selective recognition of copper(II) ions

This work reports the preparation of new Cu²⁺ ion-imprinted polymeric nanoparticles using 1-hydroxy-4-(prop-2′-enyloxy)-9,10-anthraquinone (AQ) as a vinylated chelating agent. The Cu²⁺ ion found to form a stable 1:1 complex with AQ in methanol solution. The resulting Cu²⁺-AQ complex was copolymerized with ethyleneglycol dimethacrylate, as a cross-linking monomer, via precipitation polymerization method. The imprint copper ion was removed from the polymeric matrix using a 0.1 mol L⁻¹ HNO₃ solution. The Cu²⁺-imprinted polymeric nanoparticles were characterized by IR spectroscopy, scanning electron microscopy (SEM) and N₂ adsorption-desorption isotherms. The SEM micrographs showed colloidal nanoparticles of 60-100 nm in diameter and slightly irregular in shape. Optimum pH for maximum sorption was 7.0. Sorption and desorption of Cu²⁺ ion on the IIP nanoparticles were quite fast and achieved completely over entire investigated time periods of 2-30 min. Maximum sorbent capacity and enrichment factor of the prepared IIP for Cu²⁺ were 73.8 μmol g⁻¹ and 56.5, respectively. The relative standard deviation and limit of detection (C_LOD = 3S_b/m) of the method were evaluated as 2.6% and 0.1 ng mL⁻¹, using inductively coupled plasma-atomic emission spectrometry, respectively. It was found that the imprinting technology results in increased affinity of the prepared material toward Cu²⁺ ion over other metal ions with the same charge and close ionic radius. The relative standard deviations for six and twenty replicates with the same nanoparticles were found to be 1.7% and 2.1%, respectively.     

A highly selective visual and fluorescent sensor for Pb2+ and Zn2+ and crystal structure of Cu2+ complex based-on a novel single-armed Salamo-type bisoxime

A novel single-armed Salamo-type bisoximes (H₄L) has been designed and synthesised. An obvious colour change from yellow (H₄L) to pale pink (HL-Pb²⁺) which can be visually observed by the naked eye in visible light. H₄L can act as a fluorescent sensor for ratiometric recognition of Zn²⁺ with high selectivity and sensitivity. Crystallographic data of the [Cu(HL)(μ-OAc)Cu] reveals that the two Cu²⁺ ions are both penta-coordinated with square pyramidal geometries, and forms a 2D supramolecular plane structure by hydrogen bonding interactions.     

Magnetic Nitrogen-Doped Porous Carbon Nanocomposite for Pb(II) Adsorption from Aqueous Solution

We report in the present study the in situ formation of magnetic nanoparticles (Fe₃O₄ or Fe) within porous N-doped carbon (Fe₃O₄/N@C) via simple impregnation, polymerization, and calcination sequentially. The synthesized nanocomposite structural properties were investigated using different techniques showing its good construction. The formed nanocomposite showed a saturation magnetization (M_s) of 23.0 emu g⁻¹ due to the implanted magnetic nanoparticles and high surface area from the porous N-doped carbon. The nanocomposite was formed as graphite-type layers. The well-synthesized nanocomposite showed a high adsorption affinity toward Pb²⁺ toxic ions. The nanosorbent showed a maximum adsorption capacity of 250.0 mg/g toward the Pb²⁺ metallic ions at pH of 5.5, initial Pb²⁺ concentration of 180.0 mg/L, and room temperature. Due to its superparamagnetic characteristics, an external magnet was used for the fast separation of the nanocomposite. This enabled the study of the nanocomposite reusability toward Pb²⁺ ions, showing good chemical stability even after six cycles. Subsequently, Fe₃O₄/N@C nanocomposite was shown to have excellent efficiency for the removal of toxic Pb²⁺ ions from water.     

Poly(vinyl chloride)-membrane ion-selective bulk optode based on 1,10-dibenzyl-1,10-diaza-18-crown-6 and 1-(2-pyridylazo)-2-naphthol for Cu and Pb ions

An ion-selective bulk optode (ISBO) for sensing Cu²⁺ and Pb²⁺ ions based on plasticized poly(vinyl chloride) containing 1,10-dibenzyl-1,10-diaza-18-crown-6 (DBzDA18C6) as ionophore and 1-(2-pyridylazo)-2-naphthol (PAN) as chromoionophore was prepared. The effects of DBzDA18C6/PAN and NaTPB/PAN mole ratios on the response behavior of the ISBO were investigated. The ISBO membrane shows enhanced selectivities for Cu²⁺ (at 530 nm) and Pb²⁺ (at 467 nm) over alkali, alkaline earth and other transition metal ions. The optical selectivity coefficients were measured using the separate solution method (SSM) in the two corresponding wavelengths at pH=5. The detection limit for Cu²⁺ and Pb²⁺ are 3.2×10⁻⁷ and 1.0×10⁻⁸ M, respectively.     

A highly selective pyrene based fluorescent sensor toward Hg detection

A new pyrene-containing fluorescent sensor has been synthesized from 2,3,3-trimethylindolenine. Spectroscopic and photophysical properties of sensor are presented. The large change in fluorescence intensity (I/I₀ = 0.13) at 381 nm and affinity to Hg²⁺ over other cations such as K⁺, Na⁺, Ca²⁺, Mg²⁺, Pb²⁺, and Cu²⁺ make this compound a useful chemosensor for Hg²⁺ detection in hydrophilic media. The sensor (6.0 × 10⁻⁶ M) displays significant fluorescence quenching upon addition of Hg²⁺ in pH 7.4 HEPES buffer without excimer formation. Job’s plot analysis shows the binding stoichiometry to be 2:1 (host/guest).     

Fluorescence turn-on chemodosimeter for rapid detection of mercury (II) ions in aqueous solution and blood from mice with toxicosis

The heavy metal mercury (Hg) is a threat to the health of people and wildlife in many environments. Among various chemical forms, Hg²⁺ salts are usually more toxic than their counterparts because of their greater solubility in water; thus, they are more readily absorbed from the gastrointestinal tract into circulation. Therefore, new chemical receptors for detecting Hg²⁺ ions in circulation are needed. In this study, we developed a rhodamine-based turn-on fluorescence probe to monitor Hg²⁺ in aqueous solution and in blood of mice with toxicosis. The chemodosimeter responds to Hg²⁺ ions stoichiometrically, rapidly, and irreversibly at room temperature as a result of a chemical reaction that produces strongly fluorescent oxadiazole. The new fluorescent probe shows good fluorescence response, with high sensitivity and selectivity, toward Hg²⁺ ions in aqueous solution and in blood from mice with toxicosis and facilitates the naked-eye detection of Hg²⁺ ions.     

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.     

Cobalt(II), nickel(II) and zinc(II) coordination compounds derived from aromatic amines

The structural and spectroscopic characterization of coordination compounds of four aromatic amines derived from benzimidazole, 2-aminobenzimidazole (L1), 1-(S-methylcarbodithioate)-2-aminobenzimidazole (L2), 2-(2-aminophenyl)-1H-benzimidazole (L3) and 6,6-dimethyl-5H-benzimidazolyl[1,2-c]quinazoline (L4) are reported. Cobalt(II) [Co(L1)₂(CH₃COO)₂] (1) and nickel(II) [Ni(L1)₂(CH₃COO)₂] (2) acetate coordination compounds of L1 are discussed. The synthesis and the X-ray crystal structure of the new 1-(S-methylcarbodithioate)-2-aminobenzimidazole (L2) is informed, together with its cobalt(II) [Co(L2)₂Cl₂] (3), [Co(L2)₂Br₂] (4) and zinc(II) [Co(L2)₂Cl₂] (5), [Zn(L2)₂Br₂] (6) coordination compounds. In these compounds the imidazolic nitrogen is coordinated to the metal center, while the ArNH₂ and the S-methylcarbodithioate groups do not participate as coordination sites. A co-crystal of L1 and L2 is analyzed. Structural analyses of the coordination compounds of L3 showed that this ligand behaves as a bidentate ligand through the aniline and the imidazole groups forming six membered rings in the cobalt(II) [Co(L3)Cl₂] (7) and zinc(II) [Zn(L3)Cl₂] (8) compounds, as well as the nickel(II) nitrate [Ni(L3)₂(H₂O)₂](NO₃)₂ (9). The quinazoline L4 was produced by insertion of one acetone molecule and water elimination in L3, its X-ray crystal diffraction analysis, as well as that of its zinc(II) coordination compound [Zn(L4)₂Cl₂] (10), are discussed.     

A chemosensor showing discriminating fluorescent response for highly selective and nanomolar detection of Cu and Zn and its application in molecular logic gate

A fluorescent based receptor (4Z)-4-(4-diethylamino)-2-hydroxybenzylidene amino)-1,2dihydro-1,5-dimethyl-2-phenylpyrazol-3-one (receptor 3) was developed for the highly selective and sensitive detection of Cu²⁺ and Zn²⁺ in semi-aqueous system. The fluorescence of receptor 3 was enhanced and quenched, respectively, with the addition of Zn²⁺ and Cu²⁺ ions over other surveyed cations. The receptor formed host-guest complexes in 1:1 stoichiometry with the detection limit of 5 nM and 15 nM for Cu²⁺ and Zn²⁺ ions, respectively. Further, we have effectively utilized the two metal ions (Cu²⁺ and Zn²⁺) as chemical inputs for the manufacture of INHIBIT type logic gate at molecular level using the fluorescence responses of receptor 3 at 450 nm.