A new fluorescent chemosensor for Hg2+ in aqueous solution

We prepared an aminothiourea‐derived Schiff base (DA) as a fluorescent chemosensor for Hg²⁺ ions. Addition of 1 equiv of Hg²⁺ ions to the aqueous solution of DA gave rise to an obvious fluorescence enhancement and the subsequent addition of more Hg²⁺ induced gradual fluorescence quenching. Other competing ions, including Pb²⁺, Cd²⁺, Cr³⁺, Zn²⁺, Fe²⁺, Co³⁺, Ni²⁺, Ca²⁺, Mg²⁺, K⁺ and Na⁺, did not induce any distinct fluorescence changes, indicating that DA can selectively detect Hg²⁺ ions in aqueous solution. Copyright © 2012 John Wiley & Sons, Ltd.     

A novel chromone Schiff base as Zn2+ turn-on fluorescent chemosensor in a mixed solution

In this study, a novel fluorescent chemosensor 1 based on chromone-3-carboxaldehyde Schiff base was synthesized and featured through nuclear magnetic resonance (NMR) and mass spectra. Spectroscopic investigation indicated that the fluorescent sensor showed high selectivity toward Zn²⁺ over other metal ions and that the detection limit of 1 could reach 10⁻⁷ M. These indicated that 1 acted as a highly selective and sensitive fluorescence chemosensor for Zn²⁺.     

A tricorn‐rhodamine fluorescent chemosensor for detection of Co2+ ions

A novel chemosensor TrisRh based on tris(2‐aminoethyl)amine and rhodamine 6G is designed and synthesized as a fluorescence turn‐on probe for Co²⁺ ions that is paramagnetic with a property of quenching fluorescence. Rhodamine spirolactam forms are nonfluorescent, whereas, ring‐opening of corresponding spirocyclic induced by Co²⁺ results in strong fluorescence emission. Upon the addition of Co²⁺ ions, TrisRh can display significant enhancements in absorbance and fluorescence intensity as well as evident colorific transformation, which can be perceived by the naked eye. The association stoichiometry of TrisRh to Co²⁺ ions was inferred to be 1:1 through Job's plot and electrospray ionization mass spectrometry analysis. The binding model was speculated from Fourier transform infrared spectra and ¹H–nuclear magnetic resonance technologies. Significantly, the limit of detection was determined to be as low as 1.22 nmol. Furthermore, TrisRh can exhibit robust anti‐jamming ability against other interference metal ions.     

‘Turn‐on’ fluorescent chemosensors based on naphthaldehyde‐2‐pyridinehydrazone compounds for the detection of zinc ion in water at neutral pH

A series of naphthaldehyde‐2‐pyridinehydrazone derivatives were discovered to display interesting ‘turn‐on’ fluorescence response to Zn²⁺ in 99% water/DMSO (v/v) at pH 7.0. Mechanism study indicated that different substituent groups in the naphthaldehyde moiety exhibited significant influence on the detection of Zn²⁺. The electron rich group resulted in longer fluorescence wavelengths but smaller fluorescence enhancement for Zn²⁺. Among these compounds, 1 showed the highest fluorescence enhancement of 19‐fold with the lowest detection limit of 0.17 μmol/L toward Zn²⁺. The corresponding linear range was at least from 0.6 to 6.0 μmol/L. Significantly, 1 showed an excellent selectivity toward Zn²⁺ over other metal ions including Cd²⁺.     

A ‘turn‐on’ fluorescent chemosensor for quantification of serum albumin in aqueous solution at neutral pH

A fluorescent chemosensor 1 (4‐diethylamino‐2′‐hydroxychalcone) for detecting serum albumin with long‐wavelength emission, good selectivity and facile synthesis was reported. Upon the addition of bovine serum albumin (BSA) to an aqueous solution of 1 at neutral pH, a ‘turn‐on’ fluorescence response was observed at 596 nm based on a hydrophobic binding mode between 1 and BSA. A linear range of 0.10–1.00 mg/mL and a detection limit of 9.1 µg/mL for BSA were obtained, respectively. Moreover, 1 was successfully applied to detect BSA in real bovine serum samples with satisfied recovery and accuracy, which suggested that 1 could serve as a valid and effective fluorescent chemosensor for quantification of BSA. Copyright © 2015 John Wiley & Sons, Ltd.     

A Schiff‐based sensor with turn‐on fluorescence for selective detection of Hg2+

A simple Schiff‐base colorimetric receptor 1 was prepared. It exhibits an ‘off–on‐type’ mode with high sensitivity in the presence of Hg²⁺. The change in color is very easily observed by the naked eye in the presence of Hg²⁺, whereas other metal cations do not induce such a change. A Job plot indicated a 1 : 1 complexation stoichiometry between receptor 1 and Hg²⁺. The association constant for 1–Hg²⁺ in Tetrahydrofuran (THF) was determined to be 1.3 × 10⁹ M^‐1 using a Hill plot. Copyright © 2013 John Wiley & Sons, Ltd.     

A chalcone-based fluorescent chemosensor for detecting Mg2+ and Cd2+

SBOD (sodium (E)-2-(3-[5-bromothiophen-2-yl]-3-oxoprop-1-en-1-yl)-4,6-dichlorophenolate) was designed and synthesized as a chalcone-based fluorescent turn-on chemosensor for Mg²⁺ and Cd²⁺. SBOD selectively detected Mg²⁺ and Cd²⁺ through the increase in effective fluorescence. Detection limits of SBOD for Mg²⁺ and Cd²⁺ were calculated to be 3.8 μM and 2.9 μM, respectively. The binding modes of SBOD for Mg²⁺ and Cd²⁺ were determined to be 1:1 by ESI-MS and Job plot. Association mechanisms for SBOD to Mg²⁺ and Cd²⁺ were illustrated by ESI-MS, UV–vis, fluorescence spectroscopy, and calculations.     

Tetrasubstituted cyclopentenone‐based fluorescent chemosensors for the selective detection of Fe3+ and Cu2+ ions

Fluorescent chemosensors based on 4‐hydroxy cyclopentenones were synthesized by the base catalyzed reaction of 1,5‐diphenyl‐pentane‐1,3,5‐trione with benzil and thenil. The molecule obtained by the benzil reaction was found to be useful for the selective detection of Fe³⁺ by fluorescence turn‐off, while the molecule synthesized by the thenil reaction was useful for selective detection of Cu²⁺ by fluorescent turn‐on. Details of the synthesis, complexation mode, nature of binding, reversibility, and pH studies of the two sensors are discussed. The studies revealed that the sensors were suitable for determining Fe³⁺ and Cu²⁺ content in real water samples.     

A turn‐on indole‐based sensor for hydrogen sulfate ion

A simple indole‐based receptor 1 was prepared by a simple Schiff‐base reaction of 1H‐indole‐3‐carbaldehyde with ethane 1,2‐diamine and its fluoroionophoric properties toward anions were investigated. Indole‐based receptor 1 acts as a selective turn‐on fluorescent sensor for HSO₄^? in methanol among a series of tested anions. Fluorescence spectroscopy, ultraviolet and nuclear magnetic resonance imaging support that the HSO₄^– indeed interacted with imine nitrogen and the proton of nitrogen in indole ring. Copyright © 2013 John Wiley & Sons, Ltd.     

A ratiometric fluorescent chemosensor for the detection of cysteine in aqueous solution at neutral pH

A ratiometric fluorescent chemosensor 2‐(2′‐hydroxy‐3′‐formyl‐5′‐methoxyphenyl)benzothiazole ( 1 ) was developed for the detection of cysteine (Cys). In aqueous solution at neutral pH, 1 exhibited a ratiometric fluorescent response to Cys with a remarkable red‐to‐green shift in the emission wavelength. This fluorescence change was attributed to the cyclization reaction between the formyl group in 1 and the amino and sulfhydryl group in Cys in a stoichiometry of 1: 1 according to the proposed mechanism. At neutral pH, 1 displayed a significant fluorescence ratio signal enhancement with the addition of Cys. Furthermore, 1 showed good selectivity toward Cys. The detection limit and linear range were 5.6 and 0–100 μmol/L, respectively, which demonstrated that 1 could recognize relatively low concentrations of Cys and is a good candidate for applications in detecting Cys.     

A new Schiff base as a turn‐off fluorescent sensor for Cu2+ and its photophysical properties

A new Schiff base receptor 1 was synthesized and its photophysical properties were investigated by absorption, emission and excitation techniques. Furthermore, its chromogenic and fluorogenic sensing abilities towards various metal ions were examined. Receptor 1 selectively detects Cu²⁺ ion through fluorescence quenching and detection was not inhibited in the presence of other metal ions. From fluorescence titration, the limit of detection of receptor 1 as a fluorescent ‘turn‐off’ sensor for the analysis of Cu²⁺ was estimated to be 0.35 μM.     

Development of highly selective fluorescent ferrocenyl-iminopyridine chemosensor for biologically relevant Fe3+

Design, synthesis, characterization, and ion detection studies of two ferrocene-appended Schiff bases namely N-(2-[ferrocenylamino]ethyl)-5-nitropyridin-2-amine ( 1 ) and ferrocenylamino-1H-imidazole-4-carboxamide ( 2 ) been reported. Both the chemosensors have been thoroughly characterized using Fourier transfer infrared, ¹H and ¹³C nuclear magnetic resonance, high resolution mass spectrometry, and ultraviolet/visible (UV/visible) and fluorescence spectral techniques. Probes 1 and 2 were designed with the aim of appending the ferrocenyl group with pyridine ring having an amine substitution (for 1 ) and imidazole ring with an amide substitution (for 2 ). Interaction of these probes with a series of cations and anions was examined through UV/vis and fluorescence spectral techniques. Probe 2 exhibited an insignificant response towards anions and loss of selectivity for cations, whereas 1 displayed highly selective detection towards biologically important Fe³⁺ in 2:1 (probe:cation) stoichiometry. Notably, none of the cations and anions could interfere the selectivity of Fe³⁺ ensured by 1 in aqueous medium. The limit of detection for Fe³⁺ detection using 1 was determined to be 0.2 ppm. The results strongly suggest that 1 could find promising future application as a chemosensor for Fe³⁺ in biological systems for quantification and qualitative analysis.     

Heterocyclic fluorescent Schiff base chemosensors for the detection of Fe(III) and Cu(II) ions

Two new Schiff bases were synthesized from 1-(2,4-dihydroxyphenyl)ethanone and pyridine derivatives. Both compounds were characterized using infrared, UV–Vis., ¹H NMR, ¹³C NMR and mass spectral studies. Density functional theory (DFT) calculations were performed for both the Schiff bases with 6-31G(d, p) as the basis set. Vibrational frequencies calculated using the theoretical method were in good agreement with the experimental values. Both the Schiff bases were highly fluorescent in nature. The cation-recognizing profile of the compounds was investigated in aqueous methanol medium. The Schiff base 4-(1-(pyridin-4-ylimino)ethyl)benzene-1,3-diol (PYEB) was found to interact with Fe(III) and Cu(II) ions, whereas the Schiff base 4,4′-((pyridine-2,3-diylbis(azanylylidene))bis(ethan-1-yl-1-ylidene))bis(benzene-1,3-diol) (PDEB) was found to detect Cu(II) ions. The mechanism of recognition was established as combined excited state intramolecular proton transfer (ESIPT)–chelation-enhanced fluorescence (CHEF) effect and chelation-enhanced quenching (CHEQ) process for the detection of Fe(III) and Cu(II) ions, respectively. The stability constant of the metal complexes formed during the sensing process was determined. The limit of detection for Fe(III) and Cu(II) ions with respect to Schiff base PYEB was found to be 1.64 × 10⁻⁶ and 2.16 × 10⁻⁷ M, respectively. With respect to Schiff base PDEB, the limit of detection for Cu(II) ion was found to be 4.54 × 10⁻⁴ M. The Cu(II) ion sensing property of the Schiff base PDEB was applied in bioimaging studies for the detection of HeLa cells.     

A novel colorimetric fluorescence sensor for Fe3+ based on quinoline Schiff base

A novel fluorescent sensor bearing a quinoline and an anisidine moiety has been developed for highly selective detection of Fe³⁺, which shows photo‐induced electron transfer (PET) behavior induced by Fe³⁺. Binding of Fe³⁺ to the sensor induced the electron of C = N group transfer from quinoline to iron, the result exhibits fluorescent enhancement. With the features of easy synthesis, simple structural skeleton and excellent sensing ability, the newly synthesized chemosensor also applied as a highly selective fluorescent probe in complex samples containing various competitive metal ions. The probe could fulfill various needs in biological and environmental fields.     

Facile synthesis,cytotoxicity and bioimaging of Fe3+ selective fluorescent chemosensor

The designing and development of fluorescent chemosensors have recently been intensively explored for sensitive and specific detection of environmentally and biologically relevant metal ions in aqueous solution and living cells. Herein, we report the photophysical results of alanine substituted rhodamine B derivative 3 having specific binding affinity toward Fe³⁺ with micro molar concentration level. Through fluorescence titration at 599 nm, we were confirmed that ligand 3 exhibited ratiometric fluorescence response with remarkable enhancement in emission intensity by complexation between 3 and Fe³⁺ while it appeared no emission in case of the competitive ions (Sc³⁺, Yb³⁺, In³⁺, Ce³⁺, Sm³⁺, Cr³⁺, Sn²⁺, Pb²⁺, Ni²⁺, Co²⁺, Cu²⁺, Ba²⁺, Ca²⁺, Mg²⁺, Ag⁺, Cs⁺, Cu⁺, K⁺) in aqueous/methanol (60:40, v/v) at neutral pH. However, the fluorescence as well as colorimetric response of ligand–iron complex solution was quenched by addition of KCN which snatches the Fe³⁺ from complex and turn off the sensor confirming the recognition process was reversible. Furthermore, bioimaging studies against L-929 cells (mouse fibroblast cells) and BHK-21 (hamster kidney fibroblast), through confocal fluorescence microscopic experiment indicated that ligand showed good permeability and minimum toxicity against the tested cell lines.     

A colorimetric and fluorescent chemosensor for selective detection of Cu2+ based on a new diarylethene with a benzophenone hydrazone unit

A new photochromic diarylethene based on benzophenone hydrazone has been synthesized. Its photochromic and fluorescent properties changed upon alternating irradiation with UV /Vis light and adding Cu²⁺/EDTA in methanol, which showed that the diarylethene could be served as a colorimetric and fluorescent chemosensor for selective detection of Cu²⁺ based on internal charge transfer processes. The colorimetric and turn‐off fluorescent selective detection of Cu²⁺ was attributed to the 2:1 complex of the diarylethene and Cu²⁺. The binding constant (Ka ) was 1.53 × 10⁴ L mol^?1 and the limit of detection of the diarylethene for Cu²⁺ was calculated to be 1.45 × 10^?6 mol L^?1. In addition, the metal‐responsive photochromic behavior of diarylethene was applied successfully to the construction of a molecular logic circuit.     

A highly sensitive and reversible chemosensor for Hg2+ detection based on porphyrin‐thymine conjugates

In this study, we demonstrated a highly sensitive, selective, and reversible chemosensor for Hg²⁺ determination. This chemosensor was synthesized by direct condensation of thymin‐1‐ylacetic acid with zinc tetraaminoporphyrin, which has a porphyrin core as the fluorophore and four thymine (T) moieties as the specific interaction sites for Hg²⁺. The probe (4T‐ZnP) exhibited split Soret bands with a small peak at 408 nm and a strong band at 429 nm in a dimethylformamide/H₂O (7/3, v/v) mixed solvent as well as a strong emission band at 614 nm. Upon the addition of Hg²⁺, the probe displayed strong fluorescence quenching due to the formation of T‐Hg²⁺‐T complexes. With the aid of the fluorescence spectrometer, the chemosensor in the dimethylformamide/H₂O (7/3, v/v) mixed solvent (0.3 μM) exhibited a detection limit of 6.7 nM. Interferences from other common cations, such as Co²⁺, K⁺, Sn²⁺, Zn²⁺, Cu²⁺, Ni²⁺, Mn²⁺, Na⁺, Ca²⁺, Mg²⁺, Pb²⁺, and Cd²⁺, associated with Hg²⁺ analysis were effectively inhibited. Copyright © 2015 John Wiley & Sons, Ltd.     

Fluorene‐based boronic acids as fluorescent chemosensor for monosaccharides at physiological pH

Two fluorene‐based boronic acids, 9,9‐dimethyl‐9H‐fluoren‐2‐yl‐2‐boronic acid (1) and 9,9‐dimethyl‐9H‐fluoren‐2,7‐diyl‐2,7‐diboronic acid (2), were synthesized and their sensing abilities for detection of D ‐monosaccharides were investigated by fluorescence at physiological pH. It was found that both boronic acids 1 and 2 have high selectivity and sensitivity for D ‐fructose with stability constant of 47.2 and 412.9, respectively. The sensor 2 showed a linear response toward D ‐fructose in the concentration range from 5 × 10^–5 to 10^–1 mol L^–1 with the detection limit of 2 × 10^–5 mol L^–1. Copyright © 2014 John Wiley & Sons, Ltd.     

A simple Chalcone‐based ratiometric chemosensor for silver ion

Herein, we report the selective binding of Ag⁺ ion by the anthracene‐based chalcone receptor 1. Receptor 1 behaves as a selective and sensitive chemosensor for the recognition of Ag⁺ over other heavy and transition metal ions without any interference and is capable of detecting the metal ion down to 0.15 × 10^?6 M. Receptor 1 on binding with Ag⁺ ions exhibits a ratiometric fluorescence enhancement, which is due to the inhibition of photoinduced electron transfer along with the intramolecular charge transfer mechanism. Copyright © 2015 John Wiley & Sons, Ltd.     

Fluorescent salicylaldehyde hydrazone as selective chemosensor for Zn2+ in aqueous ethanol: a ratiometric approach

4‐N,N‐diethylaminosalicylaldehyde hydrazone Schiff base ( 1 ) and its analogues ( 2 - 6 ) were synthesized and characterized by NMR, MS and elemental analysis. Compound 1 exhibited ratiometric fluorescent response to Zn²⁺ over other metal ions in aqueous ethanol solution with neutral buffer. The complexation ratio, site and constant and the effect of pH value and water fraction on its fluorescent response to Zn²⁺ were investigated. Copyright © 2009 John Wiley & Sons, Ltd.