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 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.     

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⁺.     

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.     

‘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 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.     

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.     

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.     

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.     

An amplified surface plasmon resonance "turn-on" sensor for mercury ion using gold nanoparticles

Inorganic mercury ion (Hg²⁺) has been shown to coordinate to DNA duplexes that feature thymine–thymine (T–T) base pair mismatches. This observation suggests that an Hg²⁺-induced conformational change in a single-stranded DNA molecule can be used to detect aqueous Hg²⁺. Here, we have developed an analytical method using surface plasmon resonance (SPR) to develop a highly selective and sensitive detection technique for Hg²⁺ that takes advantage of T–Hg²⁺–T coordination chemistry. The general concept used in this approach is that the “turn-on” reaction of a hairpin probe via coordination of Hg²⁺ by the T–T base pair results in a substantial increase in the SPR response, followed by specific hybridization with a gold nanoparticle probe to amplify the sensor performance. Meanwhile, the limit of detection is 1 nM, which is lower than other recently developed techniques. A linear correlation is observed between the measured SPR reflectivity and the logarithm of the Hg²⁺ concentration over the concentration range of 5–5000 nM. Additionally, the SPR system provides high selectivity for Hg²⁺ in the presence of other divalent metal ions up to micromolar concentration levels. The proposed approach is also successfully utilized for the determination of Hg²⁺ in water samples.     

Fluorescence ‘on-off-on’ chemosensor for sequential recognition of Fe3+ and Hg2+ in water based on tetraphenylethylene motif

A novel selective and sensitive fluorescence ‘on-off-on’ probe based on tetraphenylethylene (TPE) motif for sequential recognition of Fe³⁺ and Hg²⁺ in water has been developed. Especially the complex 6-Fe³⁺ could behave as a ‘turn on’ fluorescent sensor over a wide-range pH value for detection of Hg²⁺. The selectivity of this complex for Hg²⁺ over other heavy and transition metal ions is excellent, and its sensitivity for Hg²⁺ is at 2 ppb in water.     

A highly selective colorimetric and long‐wavelength fluorescent probe for the detection of Hg2+

Currently, the fluorescent probe is an important method for detecting heavy metal ions, especially mercury ion (Hg²⁺), which is harmful to the health of humans and the environment due to its toxicity and extensive use. In this paper, we designed and synthesized a colorimetric and long‐wavelength fluorescent probe Hg‐P with high sensitivity and excellent selectivity, which could detect Hg²⁺ by the changes of visual color, fluorescence and absorption spectroscopy. With the addition of Hg²⁺ to probe Hg‐P solution, its color changed from yellow to pink, and showed a 171 nm red‐shifted absorption spectrum. Probe Hg‐P was used in real water and soil solution samples to detect Hg²⁺, and the result is satisfactory. Therefore, this new probe shows great value and application in detecting Hg²⁺ in the environment.     

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.     

A Highly Selective and Non-Reaction Based Chemosensor for the Detection of Hg2+ Ions Using a Luminescent Iridium(III) Complex

We report herein a novel luminescent iridium(III) complex with two hydrophobic carbon chains as a non-reaction based chemosensor for the detection of Hg²⁺ ions in aqueous solution (<0.002% of organic solvent attributed to the probe solution). Upon the addition of Hg²⁺ ions, the emission intensity of the complex was significantly enhanced and this change could be monitored by the naked eye under UV irradiation. The iridium(III) complex shows high specificity for Hg²⁺ ions over eighteen other cations. The system is capable of detecting micromolar levels of Hg²⁺ ions, which is within the range of many chemical systems.     

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.     

Water‐soluble polymeric chemosensor for selective detection of Hg2+ in aqueous solution using rhodamine‐based modified poly(acrylamide–acrylic acid)

We report the fabrication of a novel easily available turn‐on fluorescent water‐soluble polymeric chemosensor for Hg²⁺ ions that was simply prepared by micellar free radical polymerization of a water‐insoluble organic rhodamine‐based Hg²⁺‐recognizing monomer (GR6GH), with hydrophilic monomers acrylamide (AM) and acrylic acid (AA). The chemical structure of the polymeric sensor was characterized by FT‐IR and ¹H NMR spectroscopy. The apparent viscosity average molecular weight M_η of poly(acrylamide–acrylic acid) [poly(AM–NaAA)] and the water‐soluble polymeric chemosensor poly(AM–NaAA–GR6GH) were 1.76 × 10⁶ and 6.84 × 10⁴ g/mol, respectively. Because of its amphiphilic property, the water‐soluble polymeric chemosensor can be used as a chemosensor in aqueous media. Upon addition of Hg²⁺ ions to an aqueous solution of poly(AM–NaAA–GR6GH), fluorescence enhancements were observed instantly. Moreover, other metal ions did not induce obvious changes to the fluorescence spectra. This approach may provide an easily measurable and inherently sensitive method for Hg²⁺ ion detection in environmental and biological applications. Copyright © 2015 John Wiley & Sons, Ltd.     

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.     

Glutathione‐stabilized Cu nanocluster‐based fluorescent probe for sensitive and selective detection of Hg2+ in water

In this paper, an innovative and facile one‐pot method for synthesizing water‐soluble and stable fluorescent Cu nanoclusters (CuNCs), in which glutathione (GSH) served as protecting ligand and ascorbic acid (AA) as reducing agent was reported. The resultant CuNCs emitted blue‐green fluorescence at 440 nm, with a quantum yield (QD) of about 3.08%. In addition, the prepared CuNCs exhibited excellent properties such as good water solubility, photostability and high stability toward high ionic strength. On the basis of the selective quenching of Hg²⁺ on CuNCs fluorescence, which may be the result of Hg²⁺ ion‐induced aggregation of the CuNCs, the CuNCs was used for the selective and sensitive determination of Hg²⁺ in aqueous solution. The proposed analytical strategy permitted detection of Hg²⁺ in a linear range of 4 × 10^?8 to 6 × 10^?5 M, with a detection limit of 2.2 × 10^?8 M. Eventually, the practicability of this sensing approach was confirmed by its successful application to assay Hg²⁺ in tap water, Lotus lake water and river water samples with the quantitative spike recoveries ranging from 96.9% to 105.4%.     

Phenanthroimidazole-based thiobenzamide as an effective sensor for highly selective detection of mercury(II)

Based on highly selective and irreversible Hg²⁺-promoted desulfurization reaction, a new and simple phenanthroimidazole-type sensor was prepared and exhibited high selectivity towards Hg²⁺ ion over other metal ions, accompanied by transformation of a weakly fluorescent thioamide moiety (colorless) to a highly fluorescent amide one (blue), with a 136-fold increase in fluorescent intensity in aqueous solution with a pH span 2.57–9.12.     

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.