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.     

Phenylethylidene-3,4-dihydro-1H-quinoxalin-2-ones: promising building blocks for Cu recognition

A series of sulfonamido-substituted phenylethylidene-3,4-dihydro-1H-quinoxalin-2-one derivatives in which both of the fluorophore and ionophore are integrated into one structural unit, have been investigated. They all exhibit high selectivity toward Cu²⁺ in ethanol in the presence of other metallic ions (Zn²⁺, Mg²⁺, Co²⁺, Ni²⁺, Mn²⁺, Ca²⁺, and Ag⁺), as well as fast, stable, and reversible binding, as is evidenced by the observation of a red shift in the UV-vis spectrum, ‘ON-OFF’ fluorescence response. In addition, titration and MALDI-TOF measurements indicated that a 1:1 (and possibly also 2:1 (organic ligand: Cu²⁺) complexes were formed, depending on the relative amount of Cu²⁺ added to the solution of the organic ligand. It was also found that the binding constant could be tuned by modifying the nature and position of the substituents attached to the central benzene ring in the quinoxalone derivative. In acetonitrile, unlike in ethanol, these ligands undergo oxidation-decomposition by Cu²⁺ and therefore, no UV-vVis absorption bands could be observed. However, due to color change (from yellow to transparent) they could be useful as dosimeters in this solvent.     

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’.     

Highly selective ratiometric fluorescent sensor for Cu(II) with two urea groups

A new Naphthalene derivative with two urea groups, 1,8-bis[N-(o-methoxyphenyl)ureido]naphthalene (BMPUN), was synthesized for detecting Cu(II) ratiometrically. Complexation between urea groups of BMPUN and Cu(II) with high selectivity gives rise to a great red-shift from 380 to 440 nm in the emission spectra. The introduction of electron donating groups is helpful to increase the electron density of the nitrogen atom of urea groups and then enhance the ability of complexation for Cu(II).     

A selective and sensitive chemosensor for Cu based on 8-hydroxyquinoline

A novel 8-hydroxyquinoline derivative 3 was synthesized. Significant fluorescent quenching was found in the presence of Cu²⁺ and Hg²⁺ with notably higher selectivity for Cu²⁺ than Hg²⁺.     

Novel naphthalene-based fluorescent chemosensors for Cu2+ and Fe3+ in aqueous media

Three novel compounds bearing 2,7-dihydroxylnaphthalene capable of detecting Cu²⁺ or Fe³⁺ have been synthesised based on photoinduced electron transfer. The ability of these compounds for complex transition metal ions has been studied, and complex stoichiometry for Cu²⁺ and Fe³⁺ complex has been determined in the Tris–HCl (0.01 M DMSO/H₂O (v/v) 1:1, buffer, pH 7.4) solution system by fluorescence titration experiments. These chemosensors form a 1:1 complex with Cu²⁺ or Fe³⁺ and show a fluorescent quenching with a binding constant of (4.46 ± 0.29) × 10³ and (8.04 ± 0.26) × 10⁴, respectively.     

Imidazo-benzo-15-crown-5 ethers bearing arylthienyl and bithienyl moieties as novel fluorescent chemosensors for Pd and Cu

Novel fluorescent ionophores bearing imidazo-arylthienyl or imidazo-bithienyl π-conjugated bridges functionalized with one or two fused benzo-15-crown-5 ethers as receptor units are reported. The sensing ability of the compounds in the presence of metallic cations (Li⁺, Na⁺, K⁺, Ca²⁺, Zn²⁺, Cu²⁺, Ni²⁺, Pd²⁺, and Hg²⁺) and fluoride ion was studied in MeCN/DMSO solutions by absorption and emission spectroscopy. The experimental results indicate that all compounds could act as selective fluorimetric sensors for Cu²⁺ and Pd²⁺ and also for the fluoride ion, in the case of the bis-substituted crown ether derivatives.     

Design and synthesis of a new coumarin-based ‘turn-on’ fluorescent probe selective for Cu

The novel coumarin-based ‘turn-on’ fluorescent probe (E)-3-(2,5-dimethoxybenzylideneamino)-7-hydroxy-2H-chromen-2-one (MGM) was designed, synthesized, and characterized. This compound shows high selectivity for Cu⁺², combined with a large fluorescence enhancement upon binding to Cu²⁺. Benesi-Hildebrand and Job plots demonstrate that the stoichiometry of the Cu²⁺ complex formed is 2:1. Preliminary studies employing epifluorescence microscopy demonstrated that Cu⁺² could be imaged in human neuroblastoma SH-SY5Y cells treated with MGM.     

A coumarin-based fluorescent probe for selective detection of Cu2+ in water

Fluorescent Red GK, a commercially available coumarin-based dye, was developed as a “turn-off” fluorescent probe for detection of Cu²⁺ in aqueous solution. It exhibited high selectivity and sensitivity at room temperature. Upon addition of Cu²⁺, the strong fluorescence of Fluorescent Red GK was severely quenched and its color changed from orange to colorless under illumination with a UV lamp; the color of the solution also changed from pink to colorless. So, it can be used as a specific colorimetric and fluorescent probe for Cu²⁺ with a detection limit as low as 0.0634?μM.     

Hg and Cu selective detection using a dual channel receptor based on thiopyrylium scaffoldings

2,4,6-Triphenylthiopyrylium functionalized with an aza-oxa-thia macrocycle is able to selectively recognize Hg²⁺ cation by a color change and Cu²⁺ cation by a remarkable significant emission enhancement.     

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 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.     

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.     

"Off-On" based fluorescent chemosensor for Cu2+ in aqueous media and living cells

A novel Cu²⁺-specific “off-on” fluorescent chemosensor of naphthalimide modified rhodamine B (naphthalimide modified rhodamine B chemosensor, NRC) was designed and synthesized, based on the equilibrium between the spirolactam (non-fluorescence) and the ring-opened amide (fluorescence). The chemosensor NRC showed high Cu²⁺-selective fluorescence enhancement over commonly coexistent metal ions or anions in neutral aqueous media. The limit of detection (LOD) based on 3 × δ_blank/k was obtained as low as 0.18 μM of Cu²⁺, as well as an excellent linearity of 0.05-4.5 μM (R = 0.999), indicating the chemosensor of high sensitivity and wide quantitation range. And also the coordination mode with 1:1 stoichiometry was proposed between NRC and Cu²⁺. In addition, the effects of pH, co-existing metal ions and anions, and the reversibility were investigated in detail. It was also demonstrated that the NRC could be used as an excellent “off-on” fluorescent chemosensor for the measurement of Cu²⁺ in living cells with satisfying results, which further displayed its valuable applications in biological systems.     

Bifunctional fluorescent thiacalix[4]arene based chemosensor for Cu and F ions

A new thiacalix[4]arene based fluorescent sensor bearing two dansyl groups has been synthesized in cone conformation. In CH₃CN:CH₂Cl₂ (1:1), the presence of Cu (II) induces the formation of a 1:1 metal:ligand complex, which exhibits increasing emission at 433 nm at the expense of the fluorescent emission of 1 centered at 504 nm. The detection limit of the sensor for Cu²⁺ is 2×10⁻⁷ mol L⁻¹. For anion sensing, 1 shows a high selectivity for fluoride ions over other anions tested.     

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 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.     

Study on the synthesis of novel fluorescent macrocyclic sensors and their sensitive properties for Cu2+ and Fe3+ in aqueous solution

In this work, we synthesised and characterised three novel fluorescence macrocyclic sensors containing optically active dansyl groups. The studies for the interaction of the synthesised compounds with various mental ions (Li⁺, Na⁺, K⁺, Ag⁺, Mg²⁺, Ca²⁺, Ba²⁺, Pb²⁺, Zn²⁺, Co²⁺, Cd²⁺, Hg²⁺, Ni²⁺, Cu²⁺, Mn²⁺, Cr³⁺, Al³⁺, Fe³⁺) were performed by fluorescence titration, Job’s plot, ESI-MS and DFT calculations. The results showed that the sensors 1a–1c displayed selective recognition for Cu²⁺ and Fe³⁺ ions and formed stoichiometry 1:1 complex through PET mechanism in DMSO/H₂O solution (1:1, v/v, pH 7.4 of HEPES). The binding constant (K) and detection limit were calculated.     

Organic heterocyclic-based colorimetric and fluorimetric chemosensors for the detection of different analytes: a review (from 2015 to 2022)

Heterocyclic organic compounds, also called heterocycles, are any major class of organic compounds having at least one atom other than carbon in the ring. Due to their excellent electronic and structural features, these compounds exhibit a wide range of biological and nonbiological applications. Among these, indole, benzimidazole, benzothiazole, and benzoxazole are versatile organic heterocyclic compounds widely used in different fields. They show a wide range of applications in polymer, coordination chemistry, pharmacy, dyes, food packages, medicine, and industries. These compounds contain heteroatoms like S-, N-, and O-, through which they interact with metal ions, anions, and neutral species, giving measurable analytical signals that can be used as fluorimetric and colorimetric chemosensors for detecting different analytes in biological, agricultural and environmental samples. This review summarizes indole, benzimidazole, benzothiazole, and benzoxazole-based fluorimetric and colorimetric chemosensors for detecting metal ions, anions, and neutral species. Furthermore, the recognition mechanisms have been discussed in detail, which could help researchers to design efficient, highly selective, and sensitive chemosensors to recognize and determine heavy metal cations.