A new rhodamine‐based fluorescent chemodosimeter for mercuric ions in water media

A new rhodamine–ethylenediamine–nitrothiourea conjugate (RT) was synthesized and its sensing property as a fluorescent chemodosimeter toward metal ions was explored in water media. Analytical results from absorption and fluorescence spectra revealed that the addition of Hg²⁺ ions to the aqueous solution of the chemodosimeter RT caused a distinct fluorescence OFF–ON response with a remarkable visual color change from colorless to pink; however, no clear spectral and color changes were observed from other metal ions including: Zn²⁺, Cu²⁺, Cd²⁺, Pb²⁺, Ag⁺, Fe²⁺, Cr³⁺, Co³⁺, Ni²⁺, Ca²⁺, Mg²⁺, K⁺ and Na⁺. The sensing results and the molecular structure suggested that a Hg²⁺‐induced a desulfurization reaction and cyclic guanylation of the thiourea moiety followed by ring‐opening of the rhodamine spirolactam in RT are responsible for a distinct fluorescence turn‐on signal, indicating that RT is a remarkably sensitive and selective chemodosimeter for Hg²⁺ ions in aqueous solution. Hg²⁺ within a concentration range from 0.1 to 25 μM can be determined using RT as a chemodosimeter and a detection limit of 0.04 μM is achieved. Copyright © 2014 John Wiley & Sons, Ltd.     

A rhodamine‐based fluorescent probe for Cu(II) determination in aqueous solution

An ‘off–on’ rhodamine‐based fluorescence probe for the selective detection of Cu(II) has been designed, exploiting the guest‐induced structure transform mechanism. This system shows a sharp Cu(II)‐selective fluorescence enhancement response in an aqueous system under physiological pH, and possesses high selectivity against a background of environmentally and biologically relevant metal ions. Under optimum conditions, the fluorescence intensity enhancement of this system is linearly proportional to the Cu(II) concentration from 50 nM to 6.0 μM with a detection limit of 29 nM. Copyright © 2014 John Wiley & Sons, Ltd.     

A highly selective and sensitive turn‐on fluorescent probe for the detection of Al3+ and its bioimaging

A novel fluorescent sensor, 1‐((2‐hydroxynaphthalen‐1‐yl)methylene)urea (ocn) has been designed and applied as a highly selective and sensitive fluorescent probe for recognition of Al³⁺ in Tris–HCl (pH = 7.20) solution. The probe ocn exhibits an excellent selectivity to Al³⁺ over other examined metal ions, anions and amino acids with a prominent fluorescence ‘turn‐on’ at 438 nm. ocn binds to Al³⁺ with a 2:1 binding stoichiometry and the detection limit was 0.3 μM. Furthermore, its capability of biological application was evaluated and the results showed that the sensor could be used to detect Al³⁺ in living cells.     

A N‐(2‐hydroxyethyl)piperazine dangled 2,5‐diphenyl‐1,3,4‐oxadiazole‐based fluorescent sensor for selective relay recognition of Cu2+ and sulfide in water

A new 2,5‐diphenyl‐1,3,4‐oxadiazole‐based derivative (L) was synthesized and applied as a highly selective and sensitive fluorescent sensor for relay recognition of Cu²⁺ and S^2? in water (Tris–HCl 10 mM, pH = 7.0) solution. L exhibits an excellent selectivity to Cu²⁺ over other examined metal ions with a prominent fluorescence ‘turn‐off’ at 392 nm. L interacts with Cu²⁺ through a 1:2 binding stoichiometry with a detection limit of 4.8 × 10^–7 M. The on‐site formed L–2Cu²⁺ complex exhibits excellent selectivity to S^2? with a fluorescence ‘off–on’ response via a Cu²⁺ displacement approach. Copyright © 2016 John Wiley & Sons, Ltd.     

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.     

Ratiometric fluorescent detection of Cu2+ based on dual‐emission ZIF‐8@rhodamine‐B nanocomposites

Zeolitic imidazolate framework‐8 (ZIF‐8) loading rhodamine‐B (ZIF‐8@rhodamine‐B) nanocomposites was proposed and used as ratiometric fluorescent sensor to detect copper(II) ion (Cu²⁺). Scanning electron microscopy, Fourier transform infrared spectroscopy, X‐ray powder diffraction, nitrogen adsorption/desorption isotherms and fluorescence emission spectroscopy were employed to characterize the ZIF‐8@rhodamine‐B nanocomposites. The results showed the rhodamine‐B was successfully assembled on ZIF‐8 based on the π‐π interaction and the hydrogen bond between the nitrogen atom of ZIF‐8 and –COOH of rhodamine‐B. The as‐obtained ZIF‐8@rhodamine‐B nanocomposites were octahedron with size about 150–200 nm, had good water dispersion, and exhibited the characteristic fluorescence emission of ZIF‐8 at 335 nm and rhodamine‐B at 575 nm. The Cu²⁺ could quench fluorescence of ZIF‐8 rather than rhodamine‐B. The ZIF‐8 not only acted as the template to assemble rhodamine‐B, but also was employed as the signal fluorescence together with the fluorescence of rhodamine‐B as the reference to construct a novel ratiometric fluorescent sensor to detect Cu²⁺. The resulted ZIF‐8@rhodamine‐B nanocomposite fluorescence probe showed good linear range (68.4 nM to 125 μM) with a low detection limit (22.8 nM) for Cu²⁺ combined with good sensitivity and selectivity. The work also provides a better way to design ratiometric fluorescent sensors from ZIF‐8 and other fluorescent molecules.     

Two new rhodamine‐based fluorescent chemosensors for Fe3+ in aqueous solution

Two new rhodamine‐based fluorescent probes were synthesized and characterized by NMR, high resolution mass spectrometer (HR‐MS) and IR. The probes displayed a high selectivity for Fe³⁺ among environmentally and biologically relevant metal ions in aqueous solution (CH₃OH–H₂O = 3 : 2, v/v). The significant changes in the fluorescence color could be used for naked‐eye detection. Job's plot, IR and ¹H NMR indicated the formation of 1: 1 complexes between sensor 1 and Fe³⁺. The reversibility establishes the potential of both probes as chemosensors for Fe³⁺ detection. The probe showed highly selectivity in aqueous solution and could be used over the pH range between 5 and 9. A simple paper test‐strip system for the rapid monitoring of Fe³⁺ was developed, indicating its convenient use in environmental samples. Copyright © 2014 John Wiley & Sons, Ltd.     

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 rhodamine-based "turn-on" fluorescent chemodosimeter for Cu2+ and its application in living cell imaging

A new fluorescent probe 1, N-(Rhodamine-6G)lactam-hydrazinecarbothioamide, was synthesized as a fluorescent and colorimetric chemodosimeter in aqueous solution for Cu²⁺. Following Cu²⁺-promoted ring opening, redox and hydrolysis reactions, comparable amplifications of absorption and fluorescence signals were observed upon addition of Cu²⁺; this suggests that chemodosimeter 1 effectively avoided the fluorescence quenching caused by the paramagnetic nature of Cu²⁺. Importantly, 1 can selectively recognize Cu²⁺ in aqueous media in the presence of other trace metal ions in organisms, abundant cellular cations and the prevalent toxic metal ions in the environment with high sensitivity (detection limit < 3 ppb) and a rapid response time (< 2 min). In addition, the biological imaging study has demonstrated that 1 can detect Cu²⁺ in the living cells.     

A colorimetric probe for detection of Cu2+ by the naked eye and application in test paper

A novel colorimetric probe RP1 was synthesized using rhodamine derivatives and heterocyclic compounds for the purpose of detecting Cu²⁺. RP1 showed good selectivity, high sensitivity and affinity toward Cu²⁺ over other competing ions in CH₃OH–H₂O (1/1, v/v) solution. Absorbance intensity showed a good linear fit between probe R1 and Cu²⁺ over the concentration range 1–8 μM and the association constant was also calculated to be 1.145 × 10⁵ M^?1. The sensing mechanism was deduced using Job's plot, Fourier transform infrared spectroscopy, and density functional theory studies. In addition, the colorimetric experiment indicated that probe RP1 could be made into test paper to detect Cu²⁺ with a colour change from colourless to pink.     

A triazole‐based fluorescence probe for detecting Hg2+ ions and its biological application

A new compound, ethyl 5‐phenyl‐2‐(p‐tolyl)‐2H‐1,2,3‐triazole‐4‐carboxylate was successfully introduced and synthesized as a novel rhodamine B derivative named REPPC, and characterized by ¹H nuclear magnetic resonance (NMR), ¹³C NMR, and high resolution mass spectrometry (HRMS). It showed an obvious fluorescence and UV–visible light absorption enhancement towards Hg²⁺ ion without interference from common metal ions in N,N‐dimethylformamide–H₂O (pH 7.4). The spirolactam ring moiety of rhodamine in REPPC was converted to the open‐ring form generating a 1:1 complex with the intervention of a mercury ion, verified by electrospray ionization‐mass spectroscopy testing and density functional theory calculation. REPPC was used to visualize the level of mercury ions in living HeLa cells with encouraging results.     

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.     

Highly selective and sensitive coumarin–triazole‐based fluorometric ‘turn‐off’ sensor for detection of Pb2+ ions

Exposure to even very low concentrations of Pb²⁺ is known to cause cardiovascular, neurological, developmental, and reproductive disorders, and affects children in particular more severely. Consequently, much effort has been dedicated to the development of colorimetric and fluorescent sensors that can selectively detect Pb²⁺ ions. Here, we describe the development of a triazole‐based fluorescent sensor L5 for Pb²⁺ ion detection. The fluorescence intensity of chemosensor L5 was selectively quenched by Pb²⁺ ions and a clear color change from colorless to yellow could be observed by the naked eye. Chemosensor L5 exhibited high sensitivity and selectivity towards Pb²⁺ ions in phosphate‐buffered solution [20 mM, 1:9 DMSO/H₂O (v/v), pH 8.0] with a 1:1 binding stoichiometry, a detection limit of 1.9 nM and a 6.76 × 10⁶ M^?1 binding constant. Additionally, low‐cost and easy‐to‐prepare test strips impregnated with chemosensor L5 were also produced for efficient of Pb²⁺ detection and proved the practical use of this test.     

Chromogenic and fluorescent ‘turn‐on’ chemodosimeter for fluoride based on a F–‐triggered cascade reaction

We developed a new chromogenic and fluorescent ‘turn‐on’ chemodosimeter 1 based on a F^–‐triggered cascade reaction. This system displayed significant changes in UV/vis absorption and fluorescence emission intensities selectively for F^– over other anions in a mixture of CH₃CN/H₂O (95 : 5, v/v) and in acetonitrile. Copyright © 2014 John Wiley & Sons, Ltd.     

A simple rhodamine hydrazide‐based turn‐on fluorescent probe for HOCl detection

Hypochlorous acid (HOCl) plays a crucial role in daily life and mediates a variety of physiological processes, however, abnormal levels of HOCl have been associated with numerous human diseases. It is therefore of significant interest to establish a simple, selective, rapid and sensitive fluorogenic method for the detection of HOCl in environmental and biological samples. A hydrazide‐containing fluorescent probe based on a rhodamine scaffold was facilely developed that could selectively detect HOCl over other biologically relevant reactive oxygen species, reactive nitrogen species and most common metal ions in vitro. Via an irreversible oxidation–hydrolysis mechanism, and upon HOCl‐triggered opening of the intramolecular spirocyclic ring during detection, the rhodamine hydrazide‐based probe exhibited large fluorescence enhancement in the emission spectra with a fast response, low detection limit and comparatively wide pH detection range in aqueous media. The probe was further successfully applied to monitoring trace HOCl in tap water and imaging both exogenous and endogenous HOCl within living cells. It is anticipated that this simple and useful probe might be an efficient tool with which to facilitate more HOCl‐related chemical and biological research. Copyright © 2015 John Wiley & Sons, Ltd.     

Core–shell structured CdTe/CdS@SiO2@CdTe@SiO2 composite fluorescent spheres: Synthesis and application for Cd2+ detection

Core–shell structured quantum dot (QD)–silica fluorescent nanoparticles have attracted a great deal of attention due to the excellent optical properties of QDs and the stability of silica. In this study, core–shell structured CdTe/CdS@SiO₂@CdTe@SiO₂ fluorescent nanospheres were synthesized based on the Stöber method using multistep silica encapsulation. The second silica layer on the CdTe QDs maintained the optical stability of nanospheres and decreased adverse influences on the probe during subsequent processing. Red‐emissive CdTe/CdS QDs (630 nm) were used as a built‐in reference signal and green‐emissive CdTe QDs (550 nm) were used as a responding probe. The fluorescence of CdTe QDs was greatly quenched by added S^2?, owing to a S^2?‐induced change in the CdTe QDs surface state in the shell. Upon addition of Cd²⁺ to the S^2?‐quenched CdTe/CdS@SiO₂@CdTe@SiO₂ system, the responding signal at 550 nm was dramatically restored, whereas the emission at 630 nm remained almost unchanged; this response could be used as a ratiometric ‘off–on’ fluorescent probe for the detection of Cd²⁺. The sensing mechanism was suggested to be: the newly formed CdS‐like cluster with a higher band gap facilitated exciton/hole recombination and effectively enhanced the fluorescence of the CdTe QDs. The proposed probe shows a highly sensitive and selective response to Cd²⁺ and has potential application in the detection of Cd²⁺ in environmental or biological samples.     

Synthesis and photophysical investigation of Schiff base as a Mg2+ and Zn2+ fluorescent chemosensor and its application

In view of the fluorescent switching properties and anti-fatigue properties of diarylethene, a diarylethene fluorescent chemosensor for the immediate detection of zinc ion (Zn²⁺) and magnesium ion (Mg²⁺) in acetonitrile was synthesized in this article. The structure of 1o was determined by performing spectroscopy and elemental analysis. The presence of Zn²⁺ or Mg²⁺ made the chemosensor 1o show an obvious “turn-on” fluorescent signal (bright yellow-green for Mg²⁺ and bright cyan for Zn²⁺). The fluorescent change caused by the 1:1 binding of 1o and Zn²⁺ or Mg²⁺ might be due to hindering the excited-state intramolecular proton transfer (ESIPT) process, which were bolstered by Benesi–Hildebrand analysis, Job's plot curves, proton nuclear magnetic resonance (¹H-NMR) titration and mass spectrometry. The limits of detection were acquired from the standard curve plots for Mg²⁺ at 44.6 nM and for Zn²⁺ at 14 nM. Based on the fluorescent behaviors, a logic gate was constructed with the emission intensity at 528/518 nm as output signal, the ultraviolet-visible (UV-vis) lights, Mg²⁺/Zn²⁺ and EDTA as input signals. Exogenous Zn²⁺ and Mg²⁺ fluorescent bioimaging were performed on Hela cells with 1o , indicating its potential application in biodiagnostic analysis. In particular, 1o was manufactured into test paper, and Zn²⁺ or Mg²⁺ can be conveniently, efficiently and qualitatively identified by the fluorescent color variation of the test strips.     

Highly fluorescent au nanoclusters: Electrostatically induced phase transfer synthesis for Cu2+ sensing

This paper reports a convenient method for the synthesis of highly fluorescent Au nanoclusters (NCs) via electrostatically induced phase transfer. Furthermore, on the basis of an aggregation‐induced fluorescence quenching mechanism, the potential application for Cu²⁺ sensing on the fluorescence emission of the Au NCs is discussed. These prepared fluorescent Au NCs offer acceptable sensitivity, high selectivity, and a limit of quantitation of 0.02 μM for the measurement of Cu²⁺, which is lower than the maximum level (1 ppm, equals to 15.6 μM) of Cu²⁺ permitted in drinking water in China. This study contributes to the further development of practical applications with fluorescent NCs.     

Naphthalimide-based fluorescent probe for Hg2+ detection and imaging in living cells and zebrafish

A simple naphthalimide-based fluorescent probe was designed and synthesized for the determination of mercury ion (Hg²⁺). The probe showed a noticeable fluorescence quenching response for Hg²⁺. When added with Hg²⁺, the fluorescence intensity of the probe at 560 nm was remarkably decreased with the color changed from yellow to colorless under ultraviolet (UV) light. The probe had a notable selectivity and sensitivity for Hg²⁺ and displayed an excellent sensing performance when detecting Hg²⁺ at low concentration (19.5 nM). The binding phenomenon between the probe and Hg²⁺ was identified by Job's method and high-resolution mass spectrometry (HRMS). Moreover, the probe was not only utilized to identify Hg²⁺ in real samples with satisfactory results (92.00%–110.00%) but also was successfully used for bioimaging in cells and zebrafish. The recognition mechanism has been verified by transmission electron microscopy (TEM) for the first time. All the results showed that the probe could be used as a potent useful tool for detection of Hg²⁺.     

Ligand reaction-based fluorescent peptide probes for the detection of Cu2+ and glutathione

Copper is a critical element in both human and animal metabolic processes. Its role includes supporting connective tissue cross-linking, as well as iron and lipid metabolism; at the same time, copper is also a toxic heavy metal that can cause harm to both the environment and human health. Glutathione (GSH) is a tripeptide composed of glutamic acid, cysteine, and glycine combined with sulfhydryl groups. Its properties include acting as an antioxidant and facilitating integrative detoxification. GSH is present in both plant and animal cells and has a fundamental role in maintaining living organisms. GSH is the most abundant thiol antioxidant in the human body. It exists in reduced and oxidized forms within cells and provides significant biochemical functions, such as regulating vitamins such as vitamins D, E, and C, and facilitating detoxification. A fluorescent probe has been developed to detect copper ions selectively, sensitively, and rapidly. This report outlines the successful work on creating a peptide probe, TGN (TPE-Trp-Pro-Gly-Cln-His-NH₂), with specific Cu²⁺ detection capabilities, and a significant fluorescence recovery occurred with the addition of GSH. This indicates that the probe can detect Cu²⁺ and GSH concurrently. The detection limit for Cu²⁺ in the buffer solution was 264 nM (R² = 0.9992), and the detection limit for GSH using the TGN-Cu²⁺ complex was 919 nM (R² = 0.9917). The probe exhibits high cell permeability and low biotoxicity that make it ideal for live cell imaging in biological conditions. This peptide probe has the capability to detect Cu²⁺ and GSH in biological cells.