A carbonothioate‐based highly selective fluorescent probe with a large Stokes shift for detection of Hg2+

Mercury (Hg) is one of the heavy metal pollutants in the environment. Even a very small amount of mercury can cause serious harm to human beings. Herein, we reported a new carbonothioate‐based fluorescent probe for the detection of Hg²⁺ without interference from other metal ions. This probe possessed a very large Stokes shift (192 nm), which could improve the detection sensitivity by minimizing the interferences resulted from self‐absorption or auto‐fluorescence. With the addition of Hg²⁺ to the probe solution, considerable fluorescence enhancement was observed. Additionally, the Hg²⁺ concentration of 0–16 μM and fluorescence intensity showed a good linear relationship (y = 22106× + 53108, R² = 0.9955). Finally, the proposed probe was used to detect Hg²⁺ in real water samples, and its result was satisfactory. Therefore, our proposed probe would provide a promising method for the determination of Hg²⁺ in the environment.     

Multifunctional peptide‐based fluorescent chemosensor for detection of Hg2+, Cu2+ and S2− ions

A novel multifunctional fluorescent peptide sensor based on pentapeptide dansyl‐Gly‐His‐Gly‐Gly‐Trp‐COOH (D‐P5) was designed and synthesized efficiently using Fmoc solid‐phase peptide synthesis (SPPS). This fluorescent peptide sensor shows selective and sensitive responses to Hg²⁺ and Cu²⁺ among 17 metal ions and six anions studied in N‐2‐hydroxyethylpiperazine‐N‐2‐ethane sulfonic acid (HEPES) buffer solution. The peptide probe differentiates Hg²⁺ and Cu²⁺ ions by a ‘turn‐on’ response to Hg²⁺ and a ‘turn‐off’ response to Cu²⁺. Upon addition of Hg²⁺ or Cu²⁺ ions, the sensor displayed an apparent color change that was visible under an ultraviolet lamp to the naked eye. The limits of detection (LOD) of DP‐5 were 25.0 nM for Hg²⁺ and 85.0 nM for Cu²⁺; the detection limits for Cu²⁺ were much lower than the drinking water maximum contaminant levels set out by the United States Environmental Protection Agency (USEPA). It is noteworthy that both D‐P5‐Hg and D‐P5‐Cu systems were also used to detect S^2? successfully based on the formation of ternary complexes. The LODs of D‐P5‐Hg and D‐P5‐Cu systems for S^2? were 217.0 nM and 380.0 nM, respectively. Furthermore, the binding stoichiometry, binding affinity and pH sensitivity of the probe for Hg²⁺ and Cu²⁺ were investigated. This study gives new possibilities for using a short fluorescent peptide sensor for multifunctional detection, especially for anions.     

A coumarin‐based fluorescent probe for Hg2+ and its application in living cells and zebrafish

Mercury (Hg) is a heavy metal with high toxicity and easy migration; it can be enriched through the food chain, and cause serious threats to the natural environment and human health. So, the development of a method that can be used to detect mercury ions (Hg²⁺) in the environment, in cells, and in organisms is very important. Here, a new 7‐hydroxycoumarin‐derived carbonothioate‐based probe ( CC‐Hg ) was designed and synthesized for detection of Hg²⁺. After addition of Hg²⁺, a large fluorescence enhancement was observed due to the formation of 7‐hydroxyl, which reinforced the intramolecular charge transfer process. The CC‐Hg probe had good water solubility and selectivity. Moreover, the probe was able to detect Hg²⁺ quantitatively over the concentration range 0–2 μM and with a detection limit of 7.9 nM. Importantly, we successfully applied the probe to detect Hg²⁺ in water samples, in living cells, and in zebrafish. The experimental results demonstrated its potential value in practical applications.     

Two new reversible naphthalimide‐based fluorescent chemosensors for Hg2+

Naphthalimide‐based fluorescent probes 1 and 2 were synthesized, and were designed to form probe–Hg complexes through Hg²⁺ ions coordinated to the amide group and imidazole group. They showed high sensitivity and were selective ‘naked‐eye’ chemosensors for Hg²⁺ in phosphate buffer. The fluorescence of compounds 1 and 2 could be quenched up to 90% by the addition of Hg²⁺. Reversible probes can detect Hg²⁺ ions over a wide pH range (7.0–10.0). Copyright © 2015 John Wiley & Sons, Ltd.     

Nitrogen-rich silicon quantum dots: facile synthesis and application as a fluorescent ‘on–off–on’ probe for sensitive detection of Hg2+ and cyanide ions

The sensitive and reliable detection of Hg²⁺ and CN⁻ as harsh environmental contaminants are of great importance. In view of this, a novel ‘on–off–on’ fluorescent probe based on nitrogen-rich silicon quantum dots (NR-SiQDs) has been designed for sensitive detection of Hg²⁺ and CN⁻ ions in aqueous medium. NR-SiQDs were synthesized using a facile, one-step, and environment friendly procedure in the presence of 3-aminopropyl trimethoxysilane (APTMS) and ascorbic acid (AA) as precursors, with l -asparagine as a nitrogen source for surface modification. The NR-SiQDs exhibited strong fluorescence emission at 450 nm with 42.34% quantum yield, satisfactory salt tolerance, and superior photostability and pH stability. The fluorescence emission was effectively quenched using Hg²⁺ (turn-off) due to the formation of a nonfluorescent stable NR-SiQDs/Hg²⁺ complex, whereas after the addition of cyanide ions (CN⁻), Hg²⁺ ions could be leached from the surface of the NR-SiQDs and the fluorescence emission intensity of the quenched NR-SiQDs fully recovered (turn-on) due to the formation of highly stable [Hg(CN)₄]²⁻ species. After optimizing the response conditions, the obtained limits of detection were found to be 53 nM and 0.46 μM for Hg²⁺ and CN⁻, respectively. Finally, the NR-SiQD-based fluorescence probe was utilized to detect Hg²⁺ and CN⁻ ions in water samples and satisfactory results were obtained, suggesting its potential application for environmental monitoring.     

A colorimetric fluorescent probe for rapid and specific detection of nitrite

The method of fluorescent probes has been an important technique for detection of nitrite (NO₂^?). As an important inorganic salt, excessive nitrite would threaten humans and the environment. In this paper, a colorimetric fluorescent probe P‐N (1,2‐diaminoanthraquinone) with rapid response and high selectivity, which could detect NO₂^? by visual colour changes and fluorescence spectroscopy is presented. The probe P‐N solution (pH 1) changed from pink to colourless with the addition of NO₂^? and fluorescence intensity at 639 nm clearly decreased. Good linear exists between fluorescence intensities and NO₂^? concentrations for the range 0–16 μM, and the detection limit was 54 nM (based on a 3σ/slope). Moreover, probe P‐N could also detect NO₂^? in real water samples, and results were all satisfactory. Probe P‐N shows great practical application value for detecting NO₂^? in the environment.     

Discriminative detection of mercury (II) and hydrazine using a dual‐function fluorescent probe

A dual‐function fluorescent probe (Probe 1 ) was developed for discriminative detection of Hg²⁺ and N₂H₄. Probe 1 could discriminatively detect Hg²⁺ and N₂H₄ through two different reaction sites, with the mechanism for Probe 1 for Hg²⁺ depending on a desulfurization reaction and for N₂H₄ depending on the Schiff‐base reaction. N₂H₄ had minimal effect on Hg²⁺ detection in dimethyl sulfoxide (DMSO)/H₂O solution, but Hg²⁺ could interfere with N₂H₄ detection in DMSO/buffer solution. Different concentrations of Hg²⁺ and N₂H₄ resulted in different blue shades of Probe 1 test strips, and the shade of blue was different with the same concentration of Hg²⁺ or N₂H₄, as observed under ultraviolet light at 365 nm wavelength.     

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.     

Detection of mercury(II) by DNA templated gold nanoclusters based on forming thymidine–Hg2+–thymidine duplexes

We have successfully synthesized gold nanoclusters (AuNCs) templated with DNA (5′‐CCCCCCCCCCCCTTTTTT‐3′), and subsequently employed the fluorescent DNA‐AuNCs as a novel probe for sensitive detections of mercury ions (Hg²⁺). Basically, the procedure is due to the formation of thymidine–Hg²⁺–thymidine duplexes between DNA‐AuNCs and Hg²⁺, thus leading to aggregations of DNA‐AuNCs described here occurring, and facilitating their fluorescence decrease. Significantly, this decrease of fluorescent signals permitted sensitive detection of Hg²⁺ in a linear range of 0.1–100 µmol L^?1, with a detection limit of 0.083 µmol L^?1 at a signal‐to‐noise ratio of 3. Additionally, the practicality of this probe for assaying Hg²⁺ in human urine and lake water samples was further validated, and showed various advantages including simplicity, selectivity, sensitivity and low cost, demonstrating its potential to broaden ways for assaying Hg²⁺ in real samples. Copyright © 2014 John Wiley & Sons, Ltd.     

A highly efficient and selective turn‐on fluorescent sensor for Hg2+, Ag+ and Ag nanoparticles based on a coumarin dithioate derivative

Based on chelation‐enhanced fluorescence, a new fluorescent coumarin derivative probe 3(1‐(7‐hydroxy‐4‐methylcoumarin)ethylidene)hydrazinecarbodithioate for Hg²⁺, Ag⁺ and Ag nanoparticles is reported. Fluorescent probe acts as a rapid and highly selective “off–on” fluorescent probe and fluorescence enhancement by factors 5 to12 times was observed upon selective complexation with Hg²⁺, Ag⁺ and Ag nanoparticles. The molar ratio plots indicated the formation of 1:1 complexes between Hg²⁺ and Ag⁺ with the probe. The linear response range covers a concentration range 0.1 × 10^–5–1.9 × 10^–5 mol/L, 0.1 × 10^–5–2.3 × 10^–5 mol/L and 0.146 × 10^–12–2.63 × 10^–12 mol/L for Hg²⁺, Ag⁺ and Ag nanoparticles, respectively. The interference effect of some anions and cations was also tested. Copyright © 2013 John Wiley & Sons, Ltd.     

An aqueous fluorescent probe for Hg2+ detection with high selectivity and sensitivity

An aqueous fluorescent probe, 1, was developed for the rapid detection of Hg²⁺ with high sensitivity and excellent selectivity. Upon the addition of Hg²⁺ in pure aqueous media, the Hg²⁺‐mediated hydrolysis of vinyl ether and subsequent cyclization reactions converted probe 1 into the corresponding iminocoumarin dye, which is strongly fluorescent when excited. The application of this probe for the detection of intracellular Hg²⁺ was successfully demonstrated in living cells. Copyright © 2015 John Wiley & Sons, Ltd.     

‘Naked-eye’ quinoline-based ‘reactive’ sensor for recognition of Hg2+ ion in aqueous solution

A new ‘naked-eye’ quinoline-based ‘reactive’ ratiometric fluorescent probe was prepared. The reactive stoichiometry of the probe with Hg²⁺ ion was 2:1. The probe exhibited high selectivity towards Hg²⁺ ion to other metal ions with a 410-fold increase in absorbance intensity ratio (A₄₀₂/A₃₄₀) in aqueous solution over a wide-range pH value (2–12), accompanied by a resonance color change from colorless to pale yellow visible to naked-eye.     

A novel optical probe based on d‐penicillamine‐functionalized graphene quantum dots: Preparation and application as signal amplification element to minoring of ions in human biofluid

In this study, d ‐penicillamine‐functionalized graphene quantum dots (DPA‐GQD) has been synthesized, which significantly increases the fluorescence intensity of GQD. We used this simple fluorescent probe for metal ions detection in human plasma samples. Designed DPA‐GQD respond to Hg²⁺, Cu²⁺, Au²⁺, Ag⁺, Co²⁺, Zn²⁺, and Pb²⁺ with high sensitivity. The fluorescence intensity of this probe decreased significantly in the presence of metal ions such as, Hg²⁺, Cu²⁺, Au²⁺, Ag⁺, Co²⁺, Zn²⁺, and Pb²⁺. In this work, a promising probe for ions monitoring was introduced. Moreover, DPA‐GQD probe has been tested in plasma samples. The functionalized DPA‐GQDs exhibits great promise as an alternative to previous fluorescent probes for bio‐labeling, sensing, and other biomedical applications in aqueous solution.     

DNA‐based chemiluminescent nanoprobes for highly sensitive and selective detection of mercury(II) ion

A simple and sensitive DNA‐stablized gold nanoparticle (AuNP)‐based chemiluminescent (CL) probe for detecting mercury ion (Hg²⁺) in aqueous solution has been developed. The CL strategy relies upon the catalytic activity of unmodified AuNPs on the luminol–H₂O₂ CL reaction, and the interaction of unmodified AuNPs with DNA. The unmodified AuNPs can effectively differentiate unstructured and folded DNA. The DNA desorbs from AuNPs in the presence of Hg²⁺, leading to the increase in CL signal. By rationally varying the number of thymine in single‐strand oligonucleotides, the detection range could be tuned. Employing single‐strand oligonucleotides with 14 thymine in the detecting system, a sensitive linear range for Hg²⁺ ions from 5.0 × 10^–10 to 1.0 × 10^–7 mol/L and a detection limit of 2.1 × 10^–10 mol/L are obtained. Changing the number of thymine to 10 and 6, it leads to a narrow detection range but a high sensitivity. Besides, DNA‐based CL nanoprobes exhibit a remarkable selectivity for Hg²⁺ ions over a variety of competing metal ions. Copyright © 2012 John Wiley & Sons, Ltd.     

Fluorescent sensors based on quinoline‐containing styrylcyanine: determination of ferric ions,hydrogen peroxide,and glucose,pH‐sensitive properties and bioimaging

A novel styrylcyanine‐based fluorescent probe 1 was designed and synthesized via facile methods. Ferric ions quenched the fluorescence of probe 1, whereas the addition of ferrous ions led to only small changes in the fluorescence signal. When hydrogen peroxide was introduced into the solution containing probe 1 and Fe²⁺, Fe²⁺ was oxidized to Fe³⁺, resulting in the quenching of the fluorescence. The probe 1/Fe²⁺ solution fluorescence could also be quenched by H₂O₂ released from glucose oxidation by glucose oxidase (GOD), which means that probe 1/Fe²⁺ platform could be used to detect glucose. Probe 1 is fluorescent in basic and neutral media but almost non‐fluorescent in strong acidic environments. Such behaviour enables it to work as a fluorescent pH sensor in both the solution and solid states and as a chemosensor for detecting volatile organic compounds with high acidity and basicity. Subsequently, the fluorescence microscopic images of probe 1 in live cells and in zebrafish were achieved successfully, suggesting that the probe has good cell membrane permeability and a potential application for imaging in living cells and living organisms. Copyright © 2014 John Wiley & Sons, Ltd.     

A novel fluorescent probe based on rhodamine hydrazone derivatives bearing a thiophene group for Al3+

In the present work, a novel 5‐methyl‐thiophene‐carbaldehyde‐functionalized rhodamine 6G Schiff base (RA) was designed and easily prepared as an Al³⁺ fluorescent and colorimetric probe, which could selectively and sensitively detect Al³⁺ by showing enhanced fluorescence emission. Meanwhile distinct color variation from colorless to pink also provided ‘naked eye’ detection of Al³⁺, due to the ring spirolactam opening of the rhodamine derivative. Other metal ions (including K⁺, Mg²⁺, Na⁺, Ba²⁺, Mn²⁺, Cd²⁺, Fe²⁺, Ni²⁺, Pb²⁺, Zn²⁺, Hg²⁺, Co²⁺, Li⁺, Sr²⁺ and Cu²⁺) could only induce limited interference. The detection limit of the fluorescent probe was estimated to be 4.17 × 10^?6 M, the binding constant of the RA–Al³⁺ complex was 1.4 × 10⁶ M^?1. Moreover, this fluorescent probe RA possessed high reversibility. As aluminum is a ubiquitous metal in nature and plays vital roles in many biological processes, this chemosensor could be explored for biological study applications. Copyright © 2015 John Wiley & Sons, Ltd.     

Naked eye sensing of toxic metal ions in aqueous medium using thiophene‐based ligands and its application in living cells

Thiophene‐based diimine (R1) and monoimine (R2) were synthesized in a single step, and their cation binding affinity was tested using colorimetric and UV–vis spectral studies. R1 selectively shows a colorimetric turn‐on response for Pb²⁺, Hg²⁺ ions and colorimetric turn‐off with Sn²⁺ ions, and R2 shows visual response for Cu²⁺ and Hg²⁺ over other examined metal ions in aqueous medium. R1 forms 1:1 complex with Pb²⁺, Hg²⁺, and Sn²⁺ and exhibits fluorescence quenching, whereas R2 shows 2:1 complex with Hg²⁺, Cu²⁺ and shows fluorescence enhancement. The structural and electronic properties of the sensors and their metal complexes were also investigated using Density Functional Theory calculations. R2 was also successfully demonstrated as a fluorescent probe for detecting Cu²⁺ ions in living cells. Copyright © 2014 John Wiley & Sons, Ltd.     

A highly selective and simple fluorescent sensor for mercury (II) ion detection based on cysteamine‐capped CdTe quantum dots synthesized by the reflux method

Cysteamine (CA)‐capped CdTe quantum dots (QDs) (CA–CdTe QDs) were prepared by the reflux method and utilized as an efficient nano‐sized fluorescent sensor to detect mercury (II) ions (Hg²⁺). Under optimum conditions, the fluorescence quenching effect of CA–CdTe QDs was linear at Hg²⁺ concentrations in the range of 6.0–450 nmol/L. The detection limit was calculated to be 4.0 nmol/L according to the 3σ IUPAC criteria. The influence of 10‐fold Pb²⁺, Cu²⁺ and Ag⁺ on the determination of Hg²⁺ was < 7% (superior to other reports based on crude QDs). Furthermore, the detection sensitivity and selectivity were much improved relative to a sensor based on the CA–CdTe QDs probe, which was prepared using a one‐pot synthetic method. This CA–CdTe QDs sensor system represents a new feasibility to improve the detection performance of a QDs sensor by changing the synthesis method. Copyright © 2014 John Wiley & Sons, Ltd.     

Application of 2,4,5-tris(2-pyridyl)imidazole as ‘turn-off’ fluorescence sensor for Cu(II) and Hg(II) ions and in vitro cell imaging

The 2,4,5-tris(2-pyridyl)imidazole ( L ) molecule has been evaluated as a probe for dual sensing of Hg²⁺ and Cu²⁺ ions in EtOH/HEPES buffer medium (5 mM, pH = 7.34, 1:1, v/v). Probe L shows a good sensitive and selective turn-off response in the presence of both Hg²⁺ and Cu²⁺ ions, which is comprehensible under long UV light. The probe can detect Cu²⁺ ion in the pH range 3–11 and Hg²⁺ ion in pH 6–8. The limit of detection for Cu²⁺ (0.77 μM) is well under the allowable limit prescribed by the United States Environmental Protection Agency. Two metal (Cu²⁺/Hg²⁺) ions are needed per L for complete fluorescence quenching. The probe shows marked reversibility on treatment with Na₂EDTA, making the protocol more economical for practical purposes. Paper strip coated with the L solution of EtOH can detect the presence of Cu²⁺ and Hg²⁺ ions in the sample using visible quenching of the fluorescence intensity. Density functional theory–time-dependent density functional theory (DFT–TDDFT) calculations support experimental observations, and d-orbitals of Cu²⁺/Hg²⁺ provide a nonradiative decay pathway. Cell imaging study using HDF and MDA-MB-231 cells also supported the viability of L in detecting Cu²⁺ and Hg²⁺ ions in living cells.     

A simple gold nanoplasmonic SERS method for trace Hg2+ based on aptamer‐regulating graphene oxide catalysis

The as‐prepared graphene oxide (GO) exhibited a strong catalytic effect on reduction of HAuCl₄ by trisodium citrate to form gold nanoplasmons (AuNPs) with a strong surface‐enhanced Raman scattering (SERS) effect at 1615 cm^?1 in the presence of molecular probe Victoria blue 4R (VB4r). SERS intensity increased with nanocatalyst GO concentration due to the formation of more AuNP substrates. The aptamer (Apt) of Hg²⁺ can bind to GO to form Apt–GO complexes, which can strongly inhibit nanocatalysis. When target Hg²⁺ is present, the formed stable Hg²⁺–Apt complexes are separated from the GO surface, which leads to GO catalysis recovery. The enhanced SERS signal was linear to Hg²⁺ concentration in the range 0.25–10 nmol/L, with a detection limit of 0.08 nmol/L Hg²⁺. Thus, a new gold nanoplasmon molecular spectral analysis platform was established for detecting Hg²⁺, based on Apt regulation of GO nanocatalysis.