Synthesis and ion sensing properties of new colorimetric and fluorimetric chemosensors based on bithienyl-imidazo-anthraquinone chromophores

Novel colorimetric receptors for fluoride ion sensing containing anthraquinone as a chromogenic signaling unit and imidazo-2,2'-bithiophene binding sites are reported. Well-defined color change was observed upon addition of fluoride ions to acetonitrile solutions of receptors 2. Compounds 2a-c, deprotonated after fluoride ion addition, were studied as metal ion chemosensors in the presence of Zn(II), Hg(II), and Cu(II) in acetonitrile solutions, especially compound 2a which displayed a marked change from pink to yellow-gold colors upon complexation.     

Rhodamine-based chemosensing monolayers on glass as a facile fluorescent “turn-on” sensing film for selective detection of Pb

Rhodamine-based chemosensors 1 and 2 were synthesized and self-assembled onto glass surfaces for the selective fluorescent sensing of Pb²⁺. The immobilized chemosensors showed fluorescent responses that were turned-on with Pb²⁺ in CH₃CN, selectively over various metal ions. The Pb²⁺-selective fluorescent switch of the immobilized chemosensors was also reversible, allowing for repeated use for Pb²⁺ detection.     

A Chemical Recognition Element for Lithium Ions Based on Optical Electronic Absorption

Xerogel samples with entrapped series of four optical absorption chemosensors were prepared by sol-gel process. These materials are proposed as chemical recognition elements of an optical chemical sensor. The roles of the chemosensors play proton-dissociable chromogenic azocrown ethers bearing phenol and two azo groups as parts of macrocycles. Occurrence of the alkali ion—receptor interaction is signalled by the chemosensors changing their electronic absorption spectra. By this way chemosensor 4O-CH₃ is able to distinguish Li⁺ ions from other alkali metal ions present in aqueous solution, if the chemosensor is entrapped in Glymo-silica (1:1) xerogel matrix. The proposed recognition element for Li⁺ has been exposed to the cycles chemisorption—desorption many times. Besides DRIFT spectra of the used xerogel matrices were analyzed.     

A ‘turn-on’ fluorescent sensor for the selective detection of cobalt and nickel ions in aqueous media

Two newly designed turn-on fluorescein-based chemosensors are highly sensitive and selective for Co²⁺ and Ni²⁺ in both absorption and emission modes, normally difficult to achieve with these paramagnetic ions. Binding to both ions is reversible, as indicated by the bleaching of the color when the metal is extracted with EDTA. Given the difficulty of designing enhanced fluorescent sensors for paramagnetic Co²⁺ and Ni²⁺ ions, the fluorescein compounds may inspire the further development of more sophisticated sensing constructs for the detection of these ions.     

Chemosensor properties of 7-hydroxycoumarin substituted cyclotriphosphazenes

The newly synthesized cyclotriphosphazene cored coumarin chemosensors 5, 6, and 7 were successfully characterized by ¹ H NMR, ³¹ P NMR, and MALDI-TOF mass spectrometry. Additionally, the photophysical and metal sensing properties of the targeted compounds were determined by fluorescence spectroscopy in the presence of various metals (Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ , Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Cr ³⁺ , Mn ²⁺ , Fe ³⁺ , Co ²⁺ , Al ³⁺ , Hg ⁺ , Cu ²⁺ , Zn ²⁺ , Ag ⁺ , and Cd ²⁺ ) . The fluorescence titration results showed that compounds 5, 6, and 7 could be employed as fluorescent chemosensors for Fe ³⁺ ions with high sensitivity. The complex stoichiometry between final cyclotriphosphazene chemosensors and Fe ³⁺ ions was also determined by Job’s plots.     

Fluorescent and colourimetric 1, 8-naphthalimide-appended chemosensors for the tracking of metal ions: selected examples from the year 2010 to 2017

The global sensing science in the past couple of years has seen brilliant successes in the designs and syntheses of diverse fluorescent and colourimetric chemosensors of ultra-high selectivities and sensitivities for the tracking of metal ions in environmental and biological systems. Amongst the most widely employed fluorophores for the development of fluorescent and colourimetric chemosensors is the 1, 8-naphthalimide fluorophore, which is distinctive due to its possession of outstanding photophysical properties unequalled by other fluorophores. Many reported literatures are replete with employment of 1, 8-naphthalimide as a unique fluorophore for the construction of chemosensors for the monitoring of metal ions (such as Cu²⁺, Hg²⁺, Cr³⁺, Fe³⁺, Zn²⁺, Ag⁺, Pd²⁺, Al³⁺, Ba²⁺, Au³⁺, and Bi²⁺, and/or a combination of any of them) with remarkable results documented from various labs. This review summarises recent advances in the development of representative fluorescent and colourimetric 1, 8-naphthalimide-based chemosensors reported within the past 7 years. It is believed that gaining insights into the various highlighted examples would help to refine our knowledge of the field and pave the way for further advancement in the constructions of fluorescent and colourimetric 1, 8-naphthalimide-based chemosensors of improved sensing parameters and practical application values.     

Functionalized hexagonal mesoporous silica monoliths with hydrophobic azo-chromophore for enhanced Co(II) ion monitoring

We introduce here new optical strips for the colorimetric monitoring of Co(II) ions in an aqueous solution. The optical nanosensors were designed by direct immobilizing azo-chromophore with long hydrophobic tails onto hexagonal mesoporous silica monoliths (HOM-2). Although, azo-dye probe was used as signaling reporter for selective detection of the Co(II) analyte up to 10⁻⁶ mol/dm³ in solution, the tailoring of the Co(II) ion-sensing functionality was successfully manipulated up to 10⁻⁹ mol/dm³ with the incorporation of azo-chromophore into hexagonal mesoporous silica monoliths (HOM-2), which led to small, easy-to-use optical sensor strips. However, our simple design of colorimetric sensors is based on a physical adsorption of chemically responsive dyes onto HOM materials followed by stronger dye-analyte interactions in aqueous sensing systems. No elution of the probe molecules was evident with the addition of Co(II) analyte ions during the sensing process. The binding of Co(II) ions with probes led to the color change of nanosensors corresponding to the formation of the metal-chelate [Co(II)-Probe] ⁿ⁺ complexes. Results indicated that hexagonal nanosensors offer one-step and simple sensing procedures for both quantification and visual detection of Co(II) ions without the need for sophisticated instruments. However, the solid HOM-2 materials immobilized by the these indicator dyes, in principle, could be used as preconcentrators to yield high adsorption capacity and preconcentration efficiency, leading to simultaneously visual inspection and simple detection over a wide, adjustable range of Co(II) ions even at trace levels. For Co(II) ion selectivity assays, negligible changes in either the developed color or the reflectance intensities of the [Co-Probe] ⁿ⁺ complex were observed, despite the addition of competitive cations. Moreover, the hexagonal nanosensors are reversible and have the efficient potential to serve for multiple analyses. Hexagonal optical strips for the colorimetric monitoring of Co(II) ions in an aqueous solution was successfully fabricated. This strip enabled to create ion-sensitive responses with revisable, selective and sensitive recognitions of a wide range of detectable Co(II) ions down to sub-nanomolar (∼15×10⁻⁹ M) in rapid sensing responses (in the order of minutes) This special Festschrift for Professor Jaroniec.     

Fluorescent ion-imprinted polymers for selective Cu(II) optosensing

This paper describes the synthesis and characterization of a fluorescent ion-imprinted polymer (IIP) for selective determination of copper ions in aqueous samples. The IIP has been prepared using a novel functional monomer, 4-[(E)-2-(4′-methyl-2,2′-bipyridin-4-yl)vinyl]phenyl methacrylate (abbreviated as BSOMe) that has been spectroscopically characterized in methanolic solution, in the absence and in the presence of several metal ions, including Cd(II), Cu(II), Hg(II), Ni(II), Pb(II), and Zn(II). The stability constant (2.04 × 10⁸ mol⁻² l²) and stoichiometry (L₂M) of the BSOMe complex with Cu(II) were extracted thereof. Cu(II)-IIPs were prepared by radical polymerization using stoichiometric amounts of the fluorescent monomer and the template metal ion. The resulting cross-linked network did not show any leaching of the immobilized ligand allowing determination of Cu(II) in aqueous samples by fluorescence quenching measurements. Several parameters affecting optosensor performance have been optimized, including sample pH, ionic strength, or polymer regeneration for online analysis of water samples. The synthesized Cu(II)-IIP exhibits a detection limit of 0.04 μmol l⁻¹ for the determination of Cu(II) in water samples with a reproducibility of 3%, exhibiting an excellent selectivity towards the template ion over other metal ions with the same charge and close ionic radius. The IIP-based optosensor has been repeatedly used and regenerated for more than 50 cycles without a significant decrease in the luminescent properties and binding affinity of the sensing phase.     

Multimodal Use of New Coumarin‐Based Fluorescent Chemosensors: Towards Highly Selective Optical Sensors for Hg2+ Probing

Despite several types of fluorescent sensing molecules have been proposed and examined to signal Hg²⁺ ion binding, the development of fluorescence‐based devices for in‐field Hg²⁺ detection and screening in environmental and industrial samples is still a challenging task. Herein, we report the synthesis and characterization of three new coumarin‐based fluorescent chemosensors featuring mixed thia/aza macrocyclic framework as receptors units, that is, ligands L1 – L3 . These probes revealed an OFF–ON selective response to the presence of Hg²⁺ ions in MeCN/H₂O 4:1 (v/v), which allowed imaging of this metal ion in Cos‐7 cells in vitro. Once included in silica core–polyethylene glycol (PEG) shell nanoparticles or supported on polyvinyl chloride (PVC)‐based polymeric membranes, ligands L1 – L3 can also selectively sense Hg²⁺ ions in pure water. In particular we have developed an optical sensing array tacking advantage of the fluorescent properties of ligand L3 and based on the computer screen photo assisted technique (CSPT). In the device ligand L3 is dispersed into PVC membranes and it quantitatively responds to Hg²⁺ ions in natural water samples.     

Thermal Lens Spectroscopy for Quantitative Determination of a Cu(II) Complex With an 8-Aminoquinoline Derivative in Tap Water and Mining Wastewater Samples Using a Dual Beam Technique

Abstract

This article describes the quantitative determination of Cu(II) using thermal lens spectrometry. The chromogenic reaction involving Cu(II) and 5-(4-sulphophenylazo)-8-aminoquinoline in alkaline solution was studied in different experimental conditions such as pH, ligand concentration, methanol volume, and presence of interfering ions. A collinear dual beam set-up has been used for direct quantitation in water samples without a pre-concentration step. The optimized conditions provided a linear calibration in the concentration range from 3.0 to 15.0?×?10^?7?mol L^?1. The detection and quantitation limits were 6.13?×?10^?8? and 2.04?×?10^?7?mol L^?1, respectively. Resultantly, an application to Cu(II) determination in tap water (recovery 99.8–103.3%) and mining (synthetic) wastewater (95.3–98.0%) shows relative SDs ≤ 3.1%. The method is presented as a new alternative for the direct Cu(II) determination in real samples.     

Luminescent hexanuclear Cu(I)-cluster for the selective determination of copper

For the first time, the formation of a luminescent hexanuclear cluster has been used for the selective determination of copper. In aqueous solutions, the non-luminescent ligand N-ethyl-N′-methylsulfonylthiourea (EMT) forms an intensely red luminescent hexanuclear Cu(I)-cluster with an emission maximum at 663 nm only with Cu(II) ions. The intensity of the luminescence is proportional to the Cu(II) concentration and allows for selective Cu determinations in the μg l⁻¹-range. Ubiquitous metal ions such as Fe(III), Al(III), Ca(II), Mg(II), and alkaline metal ions, as well as other heavy metal ions, e.g. Co(II), Ni(II), Zn(II), Cd(II), Hg(II), and Pb(II) are tolerated in concentrations up to 50 mg l⁻¹. The detection limit for Cu(II) in aqueous solution, calculated according to Funk et al. [Qualitätssicherung in der Analytischen Chemie, Verlag Chemie, Weinheim, 1992], is 113 μg l⁻¹. The cluster formation has been used for the quantitative analysis of copper in tap water and in industrial water, as well as for the localization of copper adsorbed by activated-sludge flocs.     

Spectrophotometric determination of trace copper(II) in biological samples with 2,4-bis(4-phenylazophenylaminodiazo)phenol

A highly sensitive and selective chromogenic reagent 2,4-bis(4-phenylazophenylaminodiazo)phenol (BPPAAP) reacted with copper(II) to form a highly stable complex in the ethanolic solution at pH range of 9.0–12.0. The Cu(II)-BPPAAP complex showed maximum absorbance at 540 nm, with molar absorptivity being 1.86 × 10⁵ L/mol cm. Beer’s law was obeyed over the range 0–0.2 μg/100 mL of copper(II) and variation coefficient is found to be 2.4–4.8%. The detection and quantification limit of the method are 2.0 and 6.5 ng/mL, respectively. To eliminate the interference of foreign ions, a convenient and efficient method using a column packed with sulfhydryl dextrose gel as a solid-phase extractant was utilized with satifactory reults. The developed method has been successfully employed for the determination of copper(II) in the biological samples.     

Response Characteristics of Copper‐Selective Polymer Membrane Electrodes Based on a Newly Synthesized Macrocyclic Calix[4]arene Derivative as a Neutral Carrier Ionophore

A novel macrocyclic calix[4]arene derivative was examined as an ionophore for ion‐selective polymeric membrane electrode toward Cu⁺² ions. The sensor showed a near Nernstian response for Cu(II) ions over a concentration range from 8.1×10^?6 to 1.0×10^?2 mol L^?1 with a slope of 34.2±0.4 mV per concentration decade in an acidic solution (pH 5). The limit of detection was 0.47 µg mL^?1. It had a response time of <20 s and can be used for at least 3 months without any divergence in potentials. The influence of plasticizer as well as the amount of lipophilic anionic site additive in the sensing membrane was discussed. It was shown that membrane electrodes formulated with the ionophore and appropriate anionic additive exhibited enhanced potentiometric response toward Cu²⁺ over all other cations tested. Since selectivity toward Cu²⁺ ions is decreased in the presence of high amount of the anionic additive, the ionophore can function as neutral carriers within the organic membrane phase. Validation of the assay method revealed good performance characteristics, including long life span, good selectivity for Cu²⁺ ions over a wide variety of other metal ions, long term response stability, and high reproducibility. The sensors were used for direct measurement of copper content in different rocks collected from different geological zones. The results agreed fairly well with data obtained using atomic absorption spectrometry.     

Copper(II) ion-selective microelectrochemical transistor

A device has been developed for the measurement of copper(II) ions (Cu²⁺) in aqueous medium. The device reported here is an electrochemical transistor which consists of two platinum electrodes separated by 100 μm spacing and bridged with an anodically grown film of polycarbazole. Polycarbazole film (undoped form) is observed to be highly selective for the Cu(II) ions. In a completed device, the conductivity of the polycarbazole film changes on addition of Cu(II) ions. The change in conductivity is attributed to the conformational changes in the polymer phase on occupation of the Cu(II) ions, without affecting electron/proton transfer. The device turns on by adding 2.5 × 10⁻⁶ M Cu(II) ions and reaches a saturation region beyond 10⁻⁴ M Cu(II) ion concentrations. In the above concentration range, the device response [I _D vs. log Cu(II) ion concentration] is linear. The selectivity of the device for other metal ions such as Cu(I), Ni(II), Co(II), Fe(II), Fe(III), Zn(II) and Pb(II) is also studied. Received: 6 April 1999 / Accepted: 20 August 1999     

Spectrophotometric determination of trace cadmium in vegetables with 3,5-bis(4-phenylazophenylaminodiazo)benzoic acid

A new highly sensitive and selective chromogenic reagent, 3,5-bis(4-phenylazophenylaminodiazo)benzoic acid (BPPABA) has been synthesized and applied to the determination of trace cadmium(II) in vegetables. The method is based on the color reaction between BPPABA and cadmium (II). In the presence of Triton X-100, cadmium(II) reacts with BPPABA in Na₂B₄O₇-NaOH buffer solution (pH 10.5), forming red complex with maximum absorption at 530 nm. Under the optimal conditions, Beer’s law is obeyed within 0–12 μg of cadmium within 25 mL of solution, and the apparent molar absorptive coefficient of the complex is 2.8 × 10⁵ L/mol cm. The detection limit and the relative standard deviation were found to be 0.92 μg/L and 1.0%, respectively. Interference of foreign ions was also investigated. Most of the metal ions are tolerated in considerable amounts except for Hg(II), Cu(II) and Ni(II). To eliminate the interference of foreign ions, metal ion imprinted polymer technique was utilized.     

Catalytic Hydrogenation of Halosteroidal Derivatives by Bipyridine or Phenanthroline Complexes of Copper(II) in Hydrazine Aqueous Media

We report two synthetic systems, Cu(Bpy)²⁺ and Cu(Phen)²⁺, for catalytic hydrogenation of steroidal haloalkenes in the presence of hydrazine and air. Thesestudies demonstrated that the selective hydrogenation is faster for the 1,10‐phenanthroline–Cu(II) system because forming more stable copper complex are formed, leaving fewer free copper ions in solution. Evidence also supports that the catalytic power of Cu(II) ions can be tuned moderately through the addition of bidentate ligand, Bpy or Phen.     

Tuning the selectivity of two chemosensors to Fe(III) and Cr(III)

Two rhodamine-based chemosensors (1 and 2) were designed, and their sensing behavior toward metal ions was investigated by fluorescence spectroscopies. 1 and 2 achieved tuning the selectivity to Fe(III) and Cr(III) in 100% aqueous solution, whereas other ions including Cd(II), Co(II), Cu(II), Ni(II), Zn(II), Mg(II), Ba(II), Pb(II), Na(I), and K(I) induced basically no spectral change, which constituted a Fe(III)-selective and a Cr(III)-selective fluorescent chemosensor, respectively.     

Theoretical study of thiazole derivatives as chemosensors for fluoride anion

The interactions between chemosensor, 2-(2′-hydroxyphenyl)-4-phenylthiazole (1), and different halides (F⁻, Cl⁻, and Br⁻) and NO₃⁻ anions have been theoretically investigated at the B3LYP/6-31G(d) level with the BSSE correction. It turned out that the unique selectivity of 1 for F⁻ is ascribed to its ability of deprotonating the hydroxy group of host sensor. The intermolecular proton transfer (IPT) causes the colorimetric and fluorescent signaling of 1 for F⁻. The deprotonated complex 1⁻·HF is formed for the deprotonation process of chemosensor. The study of substituent effects suggest that the electron-donating –CH₃ and –OCH₃ substituted derivatives are expected to be promising candidates for ratiometric fluorescent F⁻ chemosensors as well as chromogenic chemosensors, while electron-donating –N(CH₃)₂ substituted derivative can serve as chromogenic F⁻ chemosensors only. Furthermore, the electron-withdrawing (–NO₂ and –Br) substituted derivatives can serve as chromogenic F⁻/CH₃COO⁻ chemosensors.     

Fabrication of new solid state phosphate selective electrodes for environmental monitoring

A highly selective and sensitive phosphate sensor has been fabricated by constructing a crystal disk consisting of variable mixtures of aluminium powder (Al), aluminium phosphate (AlPO₄) and powdered copper (Cu). The membrane sensor exhibits linear potential response in the concentration range of 1.0 × 10⁻¹ to 1.0 × 10⁻⁶ mol L⁻¹. The proposed sensor also exhibits a fast response time of <60 s. Its detection limit is lower than 1.0 × 10⁻⁶ mol L⁻¹. The electrode has a long lifetime and can be stored in air when not in use. The selectivity of the sensor with respect to other common ions is excellent.     

Fabrication of an optical sensor based on the immobilization of Qsal on the plasticized PVC membrane for the determination of copper(II)

A novel optical sensor has been proposed for sensitive determination of Cu(II) ion in aqueous solutions. The copper sensing membrane was prepared by incorporating Qsal (2-(2-hydroxyphenyl)-3H-anthra[2,1-d]imidazole-6,11-dione) as ionophore in the plasticized PVC membrane containing tributyl phosphate (TBP) as plasticizer. The membrane responds to Cu(II) ion by changing color reversibly from yellow to dark red in acetate buffer solution at pH 4.0. The proposed sensor displays a linear range of 6.3 × 10^?7?1.00 × 10^?4 M with a limit of detection of 3.3 × 10^?7 M. The response time of the optical sensor was about 3?C5 min, depending on the concentration of Cu(II) ions. The selectivity of the optical sensor to Cu(II) ions in acetate buffer is good. The sensor can readily be regenerated by hydrochloric acid (0.1 M). The optical sensor is fully reversible. The proposed optical sensor was applied to the determination of Cu(II) in environmental water samples.