A Schiff base‐grafted nanoporous silica material as a reversible optical probe for Hg2+ ion in water

A novel organic–inorganic silica‐based fluorescent probe was designed, synthesized and characterized by different techniques such as XRD, BET, TGA, and FT‐IR. The fluorescence properties of the probe were studied in the presence of a variety of metal‐ions in water. The results revealed that various metal‐ions negligibly vary the emission intensity of the probe except for Hg²⁺, which quenched the intensity dramatically. The selectivity of the probe toward Hg²⁺ ion was further investigated in the presence of common competing metal‐ions and the results demonstrated the high selectivity of the probe toward Hg²⁺ ion. The fluorescence emission of the probe was also studied as a function of the concentration of Hg²⁺ ion. A nanomolar limit of detection was estimated for Hg²⁺, indicating a high sensitivity. Furthermore, the probe showed INHIBIT‐type logic behavior with Hg²⁺ and H⁺ as inputs. Also, the optimum pH range was studied in addition to reversibility and real world applicability of the probe.     

Lighting‐Up of the Dye Malachite Green with Mercury(II)–DNA and Its Application for Fluorescence Turn‐Off Detection of Cysteine and Glutathione

This work describes a novel strategy for the highly sensitive and selective detection of cysteine (Cys) and glutathione (GSH) based on the Hg²⁺–AGRO100–malachite green (MG) complex system. The dye MG, which has a very low quantum yield in aqueous solution by itself, can bind with the thymine‐rich DNA AGRO100 in the presence of Hg²⁺ ions to generate a striking fluorescence intensity enhancement of 1000‐fold. As sulfur‐containing amino acids, Cys and GSH effectively sequester Hg²⁺ ions from the Hg²⁺–AGRO100–MG complex structure to switch the ‘lit‐up’ chemosensor to the ‘off’ state (about a 50‐fold fluorescence intensity decrease), thus providing a facile, but effective, method to probe for Cys/GSH. The fluorescence titration, UV absorption, CD, and Raman spectra provide some insight into the structural and chemical basis for the enhancement effect. The formation of the Hg²⁺–AGRO100–MG complex significantly affects the electronic structure and conformation of the MG molecule by leading to an extended π system, which is the likely origin of the observed striking fluorescence intensity enhancement. Notably, the proposed sensing platform exhibits exquisite selectivity and sensitivity toward Cys/GSH with limits of detection of 5 nM for Cys and 10 nM for GSH, respectively. Furthermore, the straightforward assay design avoids labeling of the probe, uses only commercially available materials, and still displays comparable sensitivity and excellent selectivity.     

An Aurone‐derived Low‐molecular‐weight Fluorescence Probe for the Detection of Hg2+ in Aqueous Solution and Living Cells

A low‐molecular‐weight fluorescent probe 1 (M.W. = 238.24) based on aurone was synthesized, and its application in fluorescent detection of Hg²⁺ in aqueous solution and living cells was reported. It exhibited an “on–off” fluorescent response toward Hg²⁺ in aqueous solution. Both the color and fluorescence changes of the probe were remarkably specific for Hg²⁺ in the presence of other common metal ions, satisfying the selective requirements for biomedical and environmental monitoring application. The probe has been applied in direct measurement of Hg²⁺ content in river water samples and imaging of Hg²⁺ in living cells, which further indicates the potential application values in environmental and biological systems.     

A Novel Fluorescent Probe Based on Perylene Derivative for Hg2+ Ions and Biological Thiols and its Application in Live Cell Imaging and Theoretical Calculations

The selective and sensitive detection of biothiols; cysteine (Cys), homocysteine (Hcy) and glutathione (GSH) in aqueous solutions is of considerable importance because of their pivotal roles in maintaining the reducing environment in the cells. This study describes a strategy for the determination of biothiols based on the PDI/Met‐Hg²⁺complex platform. We designed and fabricated methionine modified perylene diimide molecule as a selective sensing probe for Hg²⁺ ions in aqueous solutions ( PDI/Met‐Hg ²⁺). The complex between perylene bisimide derivative ( PDI/Met) and Hg²⁺ was investigated and it demonstrated turn‐on fluorescence response for the detection of the biological thiols. Besides, PDI/Met displayed fluorescence quenching response in the presence of mercury ions and the emission intensity of PDI/Met‐Hg²⁺ was recovered after transferring biothiols (Cys, Hcy, and GSH). Thus, PDI/Met could be utilized as a fluorescent chemosensor for the sequential recognition of mercury ions and biological thiols.     

Probing the mechanism of the interaction between l‐cysteine‐capped‐CdTe quantum dots and Hg2+ using capillary electrophoresis with ensemble techniques

A good understanding of the mechanism of interaction between quantum dots (QDs) and heavy metal ions is essential for the design of more effective sensor systems. In this work, CE was introduced to explore how l ‐cysteine‐capped‐CdTe QDs (l ‐cys‐CdTe QDs) interacts with Hg²⁺. The change in electrophoretic mobility can synchronously reflect the change in the composition and property of QDs. The effects of the free and capping ligands on the system are discussed in detail. ESI‐MS, dynamic light scattering (DLS), zeta potential, and fluorescence (FL) were also applied as cooperative tools to study the interaction mechanism. Furthermore, the interaction mechanism, which principally depended on the concentration of Hg²⁺, was proposed reasonably. At the low concentration of Hg²⁺, the formation of a static complex between Hg²⁺ and the carboxyl and amino groups of l ‐cys‐CdTe QDs surface was responsible for the FL quenching. With the increase of Hg²⁺ concentration, the capping l ‐cys was stripped from the surface of l ‐cys‐CdTe QDs due to the high affinity of Hg²⁺ to the thiol group of l ‐cys. Our study demonstrates that CE can reveal the mechanism of the interaction between QDs and heavy metal ions, such as FL quenching.     

基于四丹磺酰胺杯[4]芳烃的汞离子荧光化学传感器

我们方便地合成了上沿修饰四丹磺酰胺基团的杯[4]芳烃衍生物1,发现该化合物在含50％水的乙腈中显示出对汞离子高选择性和灵敏性的识别作用,竞争实验表明多数金属离子对其检测干扰较小。机理研究结果表明荧光萃灭源于由丹磺酰胺基团到汞离子的光致电子转移过程。另外,通过研究1和1-Hg2+的荧光衰减实验,以及对比双丹磺酰胺杯[4]芳烃2和单丹磺酰胺杯[4]芳烃3对汞离子的识别作用,发现化合物1的四丹磺酰胺基团具有很好的预组织和协同作用。化合物1对汞离子的检测限为3.41×10-6 mol·L-1,这可以使1成为一个潜在的汞离子荧光化学传感器。     

Fluorescence turn-on chemodosimeter for rapid detection of mercury (II) ions in aqueous solution and blood from mice with toxicosis

The heavy metal mercury (Hg) is a threat to the health of people and wildlife in many environments. Among various chemical forms, Hg²⁺ salts are usually more toxic than their counterparts because of their greater solubility in water; thus, they are more readily absorbed from the gastrointestinal tract into circulation. Therefore, new chemical receptors for detecting Hg²⁺ ions in circulation are needed. In this study, we developed a rhodamine-based turn-on fluorescence probe to monitor Hg²⁺ in aqueous solution and in blood of mice with toxicosis. The chemodosimeter responds to Hg²⁺ ions stoichiometrically, rapidly, and irreversibly at room temperature as a result of a chemical reaction that produces strongly fluorescent oxadiazole. The new fluorescent probe shows good fluorescence response, with high sensitivity and selectivity, toward Hg²⁺ ions in aqueous solution and in blood from mice with toxicosis and facilitates the naked-eye detection of Hg²⁺ ions.     

Highly selective detection of mercury (II) using a G-rich oligonucleotide-based fluorescence quenching method

We provide a highly sensitive and selective assay to detect Hg²⁺ in aqueous solutions using single fluorescence-labeled G-quadruplex at room temperature. The mechanism is that AS1411 converted to G-quadruplex in the presence of potassium ion, and then, by this technique utilizing the high binding capacity of T–Hg²⁺–T makes the fluorescence dye come closer to GGG of AS1411 to causing fluorescence signal quenching by photoinduced electron transfer energy transfer. At physiological pH, the detection limit can be as low as 10 nM, with high selectivity toward Hg²⁺ ions over a lot of metal ions. The linear correlation existed between the fluorescence intensity and the concentration of Hg²⁺ over the range of 0–250 nM (R = 0.9920) in real sample. Accordingly, we expect this G-quadruplex-based sensor will be a potential application for detection of environmentally toxic mercury.     

Molecular Assembly Directed by Metal–Aromatic Interactions: Control of the Aggregation and Photophysical Properties of Zn–Salen Complexes by Aromatic Mercuration

There is widespread interest in non‐covalent bonding and weak interactions, such as electrostatic interactions, hydrogen bonding, solvophobic/hydrophobic interactions, metal–metal interactions, and π–π stacking, to tune the molecular assembly of planar π‐conjugated organic and inorganic molecules. Inspired by the roles of metal–aromatic interaction in biological systems, such as in ion channels and metalloproteins, herein, we report the first example of the use of Hg²⁺–aromatic interactions to selectively control the assembly and disassembly of zinc–salen complexes in aqueous media; moreover, this process exhibited significant “turn on” fluorescent properties. UV/Vis and fluorescence spectroscopic analysis of the titration of Hg²⁺ ions versus complex ZnL¹ revealed that the higher binding affinity of Hg²⁺ ions (compared to 13 other metal ions) was ascribed to specific interactions between the Hg²⁺ ions and the phenyl rings of ZnL¹ ; this result was also confirmed by ¹H NMR spectroscopy and HRMS (ESI). Further evidence for this type of interaction was obtained from the reaction of small‐molecule analogue L¹ with Hg²⁺ ions, which demonstrates the proximity of the N‐alkyl group to the aromatic protons during Hg²⁺‐ion binding, which led to the consequential H/D exchange reaction with D₂O. DFT modeling of such interactions between the Hg²⁺ ions and the phenyl rings afforded calculated distances between the C and Hg atoms (2.29 Å) that were indicative of C? Hg bond‐formation, under the direction of the N atom of the morpholine ring. The unusual coordination of Hg²⁺ ions to the phenyl ring of the metallosalen complexes not only strengthened the binding ability but also increased the steric effect to promote the disassembly of ZnL¹ in aqueous media.     

Ultrasensitive Silicon Nanoparticle Ratiometric Fluorescence Determination of Mercury(II)

A novel ratiometric fluorescence sensing system for the ultrasensitive detection of Hg²⁺ was developed. It used aminofunctionalized silicon nanoparticles and rhodamine B, which exhibit two distinct fluorescence emission peaks at 449 and 581?nm, respectively, under a single excitation wavelength (350?nm). The fluorescence of the amino-functionalized silicon nanoparticles was selectively quenched by Hg²⁺, while that of rhodamine B was insensitive to Hg²⁺. The ratio of fluorescence intensities at 449–581?nm linearly decreased with increasing concentrations of Hg²⁺ from 0.005–0.1 and 0.1–7?µM within 0.5?min, and a detection limit as low as 3.3?nM was achieved. Moreover, the ratiometric fluorescence sensing system exhibited good selectivity toward Hg²⁺ over other metal ions with relatively low background interference, even in a complex matrix such as lake water. Most importantly, the practical use of this sensing system for Hg²⁺ detection in real water samples was also demonstrated.     

Highly selective and sensitive visualizable detection of Hg2+ based on anti-aggregation of gold nanoparticles

For the widely used gold nanoparticles (AuNPs)-based colorimetric probes, AuNPs generally change from dispersion to aggregation state accompanying with corresponding color turning from red to blue. Although colorimetric probes based on the anti-aggregation of AuNPs show exceptional selectivity and sensitivity, few examples have been reported in literature. A facile but highly sensitive and selective colorimetric probe based on the anti-aggregation of AuNPs transferred from the deactivation of aggregation agent 4,4′-dipyridyl by Hg²⁺ was developed in this work. This reported probe is suitable for real-time detection of Hg²⁺ in water with a detection limit of 3.0 ppb for Hg²⁺, and exhibits a selectivity toward Hg²⁺ by two orders of magnitude over other metal ions. The dynamic range of this probe can be conveniently tuned by adjusting the amount of 4,4′-dipyridyl used.     

Chemosensing hybrid materials: Chalcones‐functionalized cage‐like mesoporous SBA‐16 material for highly selective detection of toxic metal ions

Highly selective and low‐cost optical nanosensors of organic–inorganic hybrid materials for heavy metal ions detection have been prepared via the functionalization of mesoporous silica (SBA‐16) with chalcone fluorescent chromophores. The successful attachment of organic chalcone moieties and preservation of original structure of SBA‐16 after the anchoring process were confirmed by extensive characterizations using various techniques like Fourier transform infrared and UV–visible spectroscopies, transmission electron microscopy, nitrogen adsorption–desorption isotherms, low‐angle X‐ray diffraction and thermogravimetric analysis. The colorimetric behaviour, selectivity and sensitivity were also investigated. The optical nanosensors respond selectively to heavy metal ions, such as Mn²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺ and Hg²⁺, with observable colour changes in 0.01 M Tris–HCl aqueous buffer solution. Also, the optical sensing ability of the investigated nanosensors to the mentioned metal ions was investigated using steady‐state absorption and emission techniques. Significant increase in the absorption spectra and a static quenching in the emission spectra are observed upon adding various concentrations of the studied metal ions. The spectral changes as well as the observable colour changes suggest that the investigated nanosensors are suitable for simple, economic, online analysis and remote design of these toxic metal ions with fast kinetic responses. Finally, the low detection limits for all the studied metals are in good agreement with those recommended by both the US Environmental Protection Agency and World Health Organization, except for Hg²⁺ and Cd²⁺, indicating that the investigated nanosensors have hypersensitivity, selectivity and better recognition for all the studied metal ions.     

A highly selective and ratiometric fluorescence probe for the detection of Hg and pH change based on coumarin in aqueous solution

A simple but highly selective coumarin-based fluorescence probe 1, 8-(1,3-dithiane)-7-hydroxycoumarin was designed and synthesized for both the ratiometric detection of Hg²⁺ and the on–off response to pH change in aqueous solution. The sensor detected Hg²⁺ selectively via Hg²⁺-promoted thioacetal deprotection reaction within five minutes and reflected pH in the range from 7.8 to 11.9 as a result of the equilibrium between weak-fluorescent acid form and strong-fluorescent base form. In addition, the probe has an excellent selectivity towards Hg²⁺ over other competitive metal ions for biomedical and environmental applications. The sensing behavior of our probe was studied by UV–visible absorption spectra and fluorescence spectra.     

Highly Sensitive Electrochemical Bioassay for Hg(II) Detection Based on Plasma-Polymerized Propargylamine and Three-Dimensional Reduced Graphene Oxide Nanocomposite

In this study, a nanocomposite consisting of three-dimensional reduced graphene oxide (3D-rGO) and plasma-polymerized propargylamine (3D-rGO@PpPG) was prepared and used as a highly sensitive and selective DNA sensor for detecting Hg²⁺. Given the high density of amino groups in the resultant 3D-rGO@PpPG nanocomposite, thymine-rich and Hg²⁺-targeted DNA was preferentially immobilized on the fabricated sensor surface via the strong electrostatic interaction between DNA strands and the amino-functionalized nanocomposites, followed by detecting Hg²⁺ through T–Hg²⁺–T coordination chemistry between DNA and Hg²⁺. The results of electrochemical measurements revealed that the anchored amount of DNA strands anchored on the 3D-rGO@PpPG nanofilm surface affects the determination of Hg²⁺ in aqueous solution. It showed high sensitivity and selectivity toward Hg²⁺ within concentrations ranging from 0.1 to 200 nM and displayed a low detection limit of 0.02 nM. The new strategy proposed also provides high selectivity of Hg²⁺ against other interfering metal ions, good stability, and repeatability. The excellent applicability of the developed sensor confirms the potential use of plasma-modified nanofilms for the detection of heavy metal ions in real environmental samples and water.     

Development of [(2E,6E)-2,6-bis(4-(dimethylamino)benzylidene)cyclohexanone] as fluorescence-on probe for Hg2+ ion detection: Computational aided experimental studies

Selective metal ion detection is highly desired in fluorometric analysis. In the current study a curcumin-based fluorescence-on probe/[(2E,6E)-2,6-bis(4-(dimethylamino) benzylidene) cyclohexanone]/probe was designed for the removal of one of the most toxic heavy metal ion i.e. Hg²⁺. The structure of the probe was confirmed by FTIR and ¹H NMR spectroscopic analysis displaying distinctive peaks. The complex formation between probe and Hg²⁺ ion was also studied by density functional theory to support the experimental results. Chelation enhanced fluorescence was observed upon interaction with Hg²⁺ ion. Different parameters like pH, effect of mercury ion concentration, contact time, interference study and effect of probe concentration on the fluorescence enhancement were also investigated. A rapid response was detected for Hg²⁺ ion with limit of detection and quantification as 2.7 nM and 3 nM respectively with association constant of 1 × 10¹¹ M^?2. The probe displayed maximum fluorescence intensity at physiological pH. The results showed that the synthesized probe can be employed as an excellent probe for the detection and quantification of Hg²⁺ ions in aqueous samples with high selectivity and sensitivity due to its higher binding energy and larger charge transferring ability.     

Oligonucleotide‐mediated aggregation of a cationic conjugated polymer for fluorescent detection of mercury ions in an aqueous medium

A cationically charged conjugated polymer ( P2 ) functionalized with quaternary ammonium salt was newly synthesized via Suzuki cross‐coupling polymerization. The functionalized P2 features different fluorescence colors according to its phases (blue emission in solution and green emission as asolid) which is caused by intramolecular and intermolecular exciton migration, respectively. The use of P2 as a novel fluorescent sensing platform is demonstrated for mercury ion detection. The detection of mercury ions is accomplished in two steps: (1) the cationic, blue‐emitting P2 absorbs an anionic oligonucleotide, polythymidine ( PT ) via electrostatic interaction to form a complex with green emission due to aggregation between the two species; (2) the addition of mercury ions to the complex produces a new complex of PT ‐Hg²⁺ via more favorable specific interaction, resulting in the isolation of P2 and the consequent recovery of blue fluorescence of P2 . It suggests that this detection system has high selectivity and sensitivity down to the ～10^?7 M level, even in mixtures of metal ions. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2393–2400     

Hg- and Cu-selective fluoroionophoric behaviors of a dioxocyclam derivative bearing anthrylacetamide moieties

New dioxocyclam derivatives bearing two anthracene fluorophores were prepared, and their fluoroionophoric properties toward transition metal ions were investigated. Chemosensor 2 having anthrylacetamide moieties exhibited pronounced Hg²⁺- and Cu²⁺-selective fluoroionophoric properties in aqueous acetonitrile solution over other representative transition metal ions, as well as alkali and alkaline earth metal ions. Chemosensor 2 also exhibited Hg²⁺ and Cu²⁺ selectivity under competitive conditions in the presence of physiologically and environmentally important metal ions. The detection limits for the sensing of Hg²⁺ and Cu²⁺ ions were 7.8 × 10⁻⁶ and 1.5 × 10⁻⁶ M, respectively, in aqueous 95% acetonitrile solution.     

Water‐soluble hyperbranched polyelectrolytes with high fluorescence quantum yield: Facile synthesis and selective chemosensor for Hg2+ and Cu2+ ions

New water‐soluble hyperbranched polyfluorenes bearing carboxylate side chains have been synthesized by the simple “A2 + B2 + C3” protocol based on Suzuki coupling polymerization. The linear polyfluorene analogue LPFA was also synthesized for comparative investigation. The optical properties of the neutral precursory polymers in CHCl₃ and final carboxylic‐anionic conjugated polyelectrolytes in buffer solution were investigated. The obtained hyperbranched polyelectrolyte HPFA2 with lower content of branch unit (2%) showed excellent solubility and high fluorescence quantum yield (?_F = 89%) in aqueous solution. Fluorescence quenching of HPFA2 by different metal ions was also investigated, the polyelectrolyte showed high selectivity for Hg²⁺ and Cu²⁺ ions relative to other various metal ions in buffer solution. The Stern‐Volmer constant K_sv was determined to be 0.80 × 10⁶ M^?1 for Hg²⁺ and 3.11 × 10⁶ M^?1 for Cu²⁺, respectively, indicating the potential application of HPFA2 as a highly selective and sensitive chemosensor for Hg²⁺ and Cu²⁺ ions in aqueous solution. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3431–3439, 2010     

Two thieno[3,4b]pyrazine‐containing copolymers: synthesis,characterization, and application in mercury ions detection

Two alternative copolymers of thieno[3,4b]pyrazine (TPZ) and triphenylamine (TPA) or phenylene (Ph), P(TPA‐TPZ) and P(Ph‐TPZ), were synthesized by Wittig–Horner polycondensation and characterized by ¹H NMR, elemental analysis, GPC, TGA, cyclic voltammetry, UV–Vis absorption, and photoluminescence (PL) spectroscopy. The polymers are soluble in common organic solvents and possess good thermal stability. Both of them shows strong solvatochromism phenomenon when dissolved in different solvents. The fluorescence of the copolymer solutions is efficiently quenched upon the addition of Hg²⁺, indicating that the two copolymers could be good Hg²⁺ detectors. More interestingly, the copolymers show high selectivity for the Hg²⁺ detection and P(TPA‐TPZ) shows higher sensitivity and selectivity toward the Hg²⁺ detection than P(Ph‐TPZ) does in the presence of other competing metal ions. The results imply that the conjugated polymers (CPs) containing the thieno[3,4b]pyrazine moiety are promising materials for chemosensors. Copyright © 2009 John Wiley & Sons, Ltd.     

Direct colorimetric visualization of mercury (Hg) based on the formation of gold nanoparticles

It is critical to be able to detect and quantify Hg²⁺ ions under aqueous conditions with high sensitivity and selectivity. The technique presented herein provides a direct way for simple colorimetric visualization of Hg²⁺ ions in aqueous solution, based on the formation of gold nanoparticles through the Hg²⁺ catalyzed HAuCl₄/NH₂OH reaction. The outstanding selectivity and sensitivity result from the well-known amalgamation process that occurs between mercury and gold. The entire procedure takes less than 20 min. The limit of detection (2 ppb) shows excellent potential for monitoring ultralow levels of mercury in water samples.