Rhodamine-Appended Bipyridine: XOR and OR Logic Operations Integrated in an Example of Controlled Metal Migration

A new bipyridyl derivative 1 bearing rhodamine B as visible fluorophore was designed, synthesized and characterized as a fluorescent and colorimetric sensor for metal ions. Interaction with Cu²⁺, Zn²⁺, Cd²⁺, Hg⁺, and Hg²⁺ ions was followed by UV/Vis and emission spectroscopy. Upon addition of these metal ions, different colorimetric and fluorescent responses were observed. “Off-on-off” (Cu²⁺, Zn²⁺, and Hg²⁺) and “off-on” (Hg⁺ and Cd²⁺) systems were obtained. Probe 1 was explored to mimic XOR and OR logic operations for the simultaneous detection of Hg⁺–Cu²⁺ and Hg⁺–Zn²⁺ pairs, respectively. DFT calculations were also performed to gain insight into the lowest-energy gas-phase conformation of free receptor 1 as well as the atomistic details of the coordination modes of the various metal ions.     

Eco‐friendly Sensors Developed by Herbal Based Silver Nanoparticles for Electrochemical Detection of Mercury (II) Ion

In our study, the single‐use & eco‐friendly electrochemical sensor platform based on herbal silver nanoparticles (AgNPs) was developed for detection of mercury (II) ion (Hg²⁺). For this purpose, the surface of pencil graphite electrode (PGE) was modified with AgNPs and folic acid (FA), respectively. The concentrations of AgNPs and FA were firstly optimized by differential pulse voltammetry (DPV) to obtain an effective surface modification of PGE. Each step at the surface modification process was characterized by using cyclic voltammetry (CV) and electrochemical impedence spectroscopy (EIS). The limit of detection (LOD) for Hg²⁺ was estimated and found to be 8.43 μM by CV technique. The sensor presented an excellent selectivity for Hg²⁺ against to other heavy metal ions such as Ca²⁺, Cd²⁺, Cr³⁺, Cu²⁺, Mg²⁺, Ni²⁺, Pb²⁺, Zn²⁺, Co²⁺ and Mn²⁺. Moreover, a rapid, selective and sensitive detection of Hg²⁺ was successfully performed in the samples of tap water within 1 min.     

Preparation of Silver Nanoparticles Reduced by Formamidinesulfinic Acid and Its Application in Colorimetric Sensor

A rapid one-step preparation approach of silver nanoparticles (AgNPs) was reported by employing formamidinesulfinic acid as reducing agent and soluble starch as stabilizing agent. The formation of AgNPs was further confirmed by using UV–Vis absorption spectroscopy, X-ray diffraction spectroscopy and transmission electron microscopy techniques. The resultant AgNPs could be directly used for the colorimetric reaction with metal ions. The results showed that Al³⁺, Cr³⁺, Fe³⁺ and Hg²⁺ ions could induce the color change of AgNPs from yellow to pink (Al³⁺), orange (Cr³⁺) and colorless (Fe³⁺ and Hg²⁺), respectively, which can be observed by the naked eye. Based on these, a sensitive colorimetric sensor for Al³⁺, Fe³⁺, Cr³⁺ and Hg²⁺ ions detection was developed.     

A colorimetric and surface-enhanced Raman scattering dual-signal sensor for Hg based on Bismuthiol II-capped gold nanoparticles

The addition of Bismuthiol II to the gold nanoparticles (AuNPs) solution led to the aggregation of AuNPs with a color change from red to blue. As a result, hot spots were formed and strong surface-enhanced Raman scattering (SERS) signal of Bismuthiol II was observed. However, the Bismuthiol II-induced aggregation of AuNPs could be reversed by Hg²⁺ in the system, accompanied by a remarkable color change from blue to red. As evidenced by UV–vis and SERS spectroscopy, the variation in absorption band and SERS intensity was strongly dependent on the concentration of Hg²⁺, suggesting a colorimetric and SERS dual-signal sensor for Hg²⁺. The sensor had a high sensitivity, low detection limits of 2 nM and 30 nM could be achieved by UV–vis spectroscopy and by SERS spectroscopy, respectively. Other environmentally relevant metal ions did not interfere with the detection of Hg²⁺. The method was successfully applied to detect Hg²⁺ in water samples. It was simple, rapid and cost-effective without any modifying or labeling procedure.     

Fluorescein Hydrazide-Appended Metal–Organic Framework as a Chromogenic and Fluorogenic Chemosensor for Mercury Ions

In this work, we prepared a fluorescein hydrazide-appended Ni(MOF) (Metal–Organic Framework) [Ni₃(BTC)₂(H₂O)₃]·(DMF)₃(H₂O)₃ composite, FH@Ni(MOF). This composite was well-characterized by PXRD (powder X-ray diffraction), FT-IR (Fourier transform infrared spectroscopy), N₂ adsorption isotherm, TGA (thermogravimetric analysis), XPS (X-ray photoelectron spectroscopy), and FESEM (field emission scanning electron microscopy). This composite was then tested with different heavy metals and was found to act as a highly selective and sensitive optical sensor for the Hg²⁺ ion. It was found that the aqueous emulsion of this composite produces a new peak in absorption at 583 nm, with a chromogenic change to a pink color visible to the naked eye upon binding with Hg²⁺ ions. In emission, it enhances fluorescence with a fluorogenic change to green fluorescence upon complexation with the Hg²⁺ ion. The binding constant was found to be 9.4 × 10⁵ M⁻¹, with a detection limit of 0.02 μM or 5 ppb. This sensor was also found to be reversible and could be used for seven consecutive cycles. It was also tested for Hg²⁺ ion detection in practical water samples from ground water, tap water, and drinking water.     

Fluorescence detection of mercury(II) and lead(II) ions using aptamer/reporter conjugates

We have developed a fluorescence technique for the detection of Hg²⁺ and Pb²⁺ ions using polythymine (T₃₃)/benzothiazolium-4-quinolinium dimer derivative (TOTO-3) and polyguanine (G₃₃)/terbium ions (Tb³⁺) conjugates, respectively. Hg²⁺ ions induce T₃₃ to form folded structures, leading to increased fluorescence of the T₃₃/TOTO-3 conjugates. Because Pb²⁺ ions compete with Tb³⁺ ions to form complexes with G₃₃, the extent of formation of the G₃₃-Tb³⁺ complexes decreases upon increasing the Pb²⁺ concentration, leading to decreased fluorescence at 545 nm when excited at 290 nm. To minimize interference from Hg²⁺ ions during the detection of Pb²⁺ ions, we conducted two-step fluorescence measurements; prior to addition of the G₃₃/Tb³⁺ probe, we recorded the fluorescence of a mixture of the T₃₃/TOTO-3 conjugates and Hg²⁺ ions. The fluorescence signal obtained was linear with respect to the Hg²⁺ concentration over the range 25.0-500 nM (R² = 0.99); for Pb²⁺ ions, it was linear over the range 3.0-50 nM (R² = 0.98). The limits of detection (at a signal-to-noise ratio of 3) for Hg²⁺ and Pb²⁺ ions were 10.0 and 1.0 nM, respectively. Relative to other techniques for the detection of Hg²⁺ and Pb²⁺ ions in soil and water samples, our present approach is simpler, faster, and more cost-effective.     

Catalytic gold nanoparticles for fluorescent detection of mercury(II) and lead(II) ions

In this study, we developed a fluorescence assay for the highly sensitive and selective detection of Hg²⁺ and Pb²⁺ ions using a gold nanoparticle (Au NP)-based probe. The Hg–Au and Pb–Au alloys that formed on the Au NP surfaces allowed the Au NPs to exhibit peroxidase-mimicking catalytic activity in the H₂O₂-mediated oxidation of Amplex UltraRed (AUR). The fluorescence of the AUR oxidation product increased upon increasing the concentration of either Hg²⁺ or Pb²⁺ ions. By controlling the pH values of 5 mM tris–acetate buffers at 7.0 and 9.0, this H₂O₂–AUR–Au NP probe detected Hg²⁺ and Pb²⁺ ions, respectively, both with limits of detection (signal-to-noise ratio: 3) of 4.0 nM. The fluorescence intensity of the AUR oxidation product was proportional to the concentrations of Hg²⁺ and Pb²⁺ ions over ranges 0.05–1 μM (R² = 0.993) and 0.05–5 μM (R² = 0.996), respectively. The H₂O₂–AUR–Au NP probe was highly selective for Hg²⁺ (>100-fold) and Pb²⁺ (>300-fold) ions in the presence of other tested metal ions. We validated the practicality of this simple, selective, and sensitive H₂O₂–AUR–Au NP probe through determination of the concentrations of Hg²⁺ and Pb²⁺ ions in a lake water sample and of Pb²⁺ ions in a blood sample. To the best of our knowledge, this system is the first example of Au NPs being used as enzyme-mimics for the fluorescence detection of Hg²⁺ and Pb²⁺ ions.     

Biogenic synthesis of silver nanoparticles; study of the effect of physicochemical parameters and application as nanosensor in the colorimetric detection of Hg2+ in water

This research demonstrates the ability of biogenic synthesised silver nanoparticles (AgNPs) to sensitively and selectively detect the presence of mercury (Hg²⁺) in water. To achieve this, the following study investigated the synthesis of AgNPs using plant extract from basil and characterised the synthesised AgNPs using scanning electron microscopy, energy dispersive X-ray spectroscopy, UV-visible spectrophotometry, X-ray diffractometry and Fourier transform infrared spectroscopy. We studied the effect of various factors, such as broth concentration, precursor concentration, temperature, contact time and pH, on the synthesis of the nanoparticles. The synthesised AgNPs were then used in the colorimetric detection of Hg²⁺ in water. The as-prepared AgNPs showed high selectivity to detect Hg²⁺ alone compared to other cations and high sensitivity at different concentration of Hg²⁺. The limit of detection for Hg²⁺ was 6.25 × 10^–8 mol/L (12 µg/L) indicating that these biogenic synthesised AgNPs represent a highly sensitive Hg²⁺ detection tool.     

A novel electrochemical method to detect mercury (II) ions

A novel and sensitive electrochemical method for determination of mercury (II) ions (Hg²⁺) based on the formation of thymine–Hg²⁺–thymine complexes and gold nanoparticle-mediated signal amplification is reported. Two 5′ end thiolated complementary oligonucleotides containing six strategically placed thymine–thymine mistakes were introduced in this work. One of the two oligonucleotides was immobilized on a gold electrode and the other one on gold nanoparticles (AuNPs). Due to six thymine–thymine mistakes the two oligonucleotides were not able to be hybridized, so AuNPs could not be immobilized onto the electrode surface after the electrode was immersed in the DNA–AuNPs solution. However, if Hg²⁺ existed, T–Hg²⁺–T complexes could be formed and AuNPs could be immobilized onto the electrode surface. Meanwhile, large numbers of [Ru(NH₃)₆]³⁺ molecules as electrochemical species could be localized onto the electrode surface. The Hg²⁺ detection limit of this assay could be as low as 10 nM, which is the US Environmental Protection Agency (EPA) limit of Hg²⁺ for drinkable water. This method is proven to be simple, convenient, high sensitive and selective.     

Cytosine triphosphate-capped silver nanoparticles as a platform for visual and colorimetric determination of mercury(II) and chromium(III)

This work reports on a colorimetric platform for determination of chromium ions (Cr³⁺) and mercury ions (Hg²⁺) using silver nanoparticles (AgNPs) capped with cytosine triphosphate (CTP). The capped AgNPs were synthesized one-step by reduction of AgNO₃ in the presence of CTP. It was found that such AgNPs aggregate in the presence of Cr³⁺. This results in a decrease in the intensity of the surface plasmon resonance (SPR) band at 390 nm and the formation of a new red-shifted band at 510 nm, and consequently a color change from yellow to red. Different from the Cr³⁺-induced aggregation of AgNPs, exposure to Hg²⁺ causes the formation of a mercury layer around the surface of the AgNPs. This, in turn, causes the SPR absorption of the AgNPs to decrease and to undergo a slight blue shift, and this results in a fading of the yellow color. The findings are the basis of developing a new method for quantification of either Cr³⁺ or Hg²⁺, with detection limits of 6.25 μM for Cr³⁺ and of 0.125 μM for Hg²⁺, respectively. The method was applied to the determination of the two ions in spiked drinking water and lake water samples, and recoveries ranged from 94.5% to 101.3% for Cr³⁺, and from 96% to 108% for Hg²⁺, which is satisfactory for quantitative assays performed in water samples.

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Graphical abstract Cytosine triphosphate-capped silver nanoparticles (cAgNPs) are shown to represent a viable probe for visual and colorimetric detection of Hg²⁺ and Cr³⁺ via two different mechanisms: aggregation of cAgNPs in case of Cr³⁺; and amalgamation of cAgNPs in case of Hg²⁺.

     

Dimethylcyclam based fluoroionophore having Hg- and Cd-selective signaling behaviors

Diametrically disubstituted bis(anthrylmethyl) derivative of 1,8-dimethylcyclam exhibited pronounced Hg²⁺- and Cd²⁺-selective fluorogenic behaviors in aqueous acetonitrile solution. A distinctive OFF-ON type signaling was observed for Hg²⁺ and Cd²⁺ ions in aqueous acetonitrile (CH₃CN-H₂O = 90:10, v/v) solution, while a selective ON-OFF type switching behavior toward Hg²⁺ ions was observed in solution having higher water content (CH₃CN-H₂O = 50:50, v/v). The detection limit for the analysis of Hg²⁺ ions in 50% aqueous acetonitrile was found to be 3.8 × 10⁻⁶ M. The selective OR logic gate behavior of the prepared compound toward two toxic heavy metal ions of Hg²⁺ and Cd²⁺ ions in CH₃CN-H₂O (90:10, v/v) suggests the possibility as a new chemosensing device for the two important target metal ions.     

Aptameric SERS sensor for Hg~(2+) analysis using silver nanoparticles

Aptamer–silver nanoparticles (AgNPs) based surface-enhanced Raman scattering (SERS) sensor has been developed for Hg²⁺ detection by employing the structure-switching aptamer in the presence of spermine. This simple method shows excellent sensitivity and selectivity owing to the sensitive SERS detection technique and high specificity of aptamer for binding Hg²⁺.     

Effect of selenium on the Hg,Zn, Fe and Co content of yeast cells

The yeast cells, Saccharomyces cerevisiae, were exposed to Hg²⁺ ions (10^–4M) and SeO₂ (2·10^–4–10^–2M) or Se- methionine (2·10^–4M). Instrumental neutron activation analysis (INAA) was used to analyze changes in the Hg, Zn, Fe and Co levels in these cells. When the yeast was incubated in a medium containing 10^–3M and 10^–2M SeO₂, the Hg content of the yeast markedly increased. It was also found that the uptake of Se and Hg influenced the levels of Zn, Fe and Co found in the cells. While the presence of Se-methionine (Se-Met), SeO₂ or Hg²⁺ ions caused increases in the intracellular Zn levels, the combined presence of Hg²⁺ and SeO₂ and their assumed interaction, reduced the efficiency of Se for increasing the Zn content of yeast.     

Simple and rapid surface-enhanced Raman Spectroscopy assay for safranine T and its application in highly sensitive determination of mercury (Ⅱ)

A simple and sensitive surface-enhanced Raman spectroscopy (SERS) method for the detection of safranine T (ST) and Hg²⁺ using silver nanoparticles (AgNPs) as substrate was developed. ST can absorb on the surface of AgNPs through electrostatic interaction, the electromagnetic effect combined with chemical adsorption effect give a notable Raman enhancement for ST. The presence of Hg²⁺ well decreased the absorbed ST molecules on AgNPs, leading to a significant decrease of SERS signals thus enabling to detect Hg²⁺. The determination conditions for SERS, including the amount of AgNPs, the concentration of NaCl, the concentration of HCl, the concentration of ST and the reaction time, were optimised. Under the optimised experimental conditions, good linear responses were obtained for ST and Hg²⁺ in the concentration ranges of 0.01–4.0 μmol L^?1 (3.5–1403.4 ng mL^?1) and 0.01–2.0 μmol L^?1 (2.0–401.2 ng mL^?1), the limit of detection were 3.0 nmol L^?1 (1.1 ng mL^?1) and 2.0 nmol L^?1 (0.4 ng mL^?1), respectively. The present method was subsequently applied to the determination of ST in tomato sauces and Hg²⁺ in environmental waters, the recoveries of ST and Hg²⁺ in spiked samples are 95.5–107.8% and 91.4–110.8 %, respectively.     

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.     

Preconcentration of metal ions using an immobilized dialkyldithiocarbamate in a flow system

Flow injection analysis with on-line preconcentration using a minicolumn loaded with dialkyldithiocarbamate immobilized on controlled pore glass is described for the determination of Rh(III), Co²⁺, Cu²⁺, Hg²⁺, and Hg₂²⁺. The detection limits range from 0.05 ng ml⁻¹ for Cu²⁺ to 50 ng ml⁻¹ for Hg²⁺ for 5- or 10-ml samples, improvement of 2–3 orders of magnitude compared with direct injection. The operating conditions are optimized and the effects of interferents are studied. The capacity of the collector varied from 0.9 mmol g⁻¹ for Rh(III) to ca 4 mmol g⁻¹ (Co²⁺, Cu²⁺, Hg²⁺).     

Das erste Erdalkalimetall-Argentato-Mercurat(II): BaAg2Hg2O4

Summary BaAg₂Hg₂O₄ was prepared by an oxygen high-pressure technique. Single crystal X-ray investigations led to tetragonal symmetry, space group D _4h ³ – P4/nbm;a=6.793;c=7.086 Å;Z=2. Hg²⁺ and Ag⁺ show dumb-bell like coordination by oxygen whereas Ba²⁺ ions are surrounded by 8 O^2– forming distorted cubes. The BaO₈-polyhedra distortions are discussed in respect to the incorporation of Hg²⁺ ions into the BaAg₂O ₄ ^2– network.

     

Distribution studies of metal ions on arsenophosphates of Sn(IV) and Cr(III) and on amine Sn(II) hexacyanoferrates (II) using radio tracers: Separation of Sr2+−Cs+, Hg2+−Ag+ and Hg2+−Zn2+

Summary Distribution studies of some metal ions have been made on Sn(IV) and Cr(III) arsenophosphates and on some samples of Sn(II) amine hexacyanoferrates(II), using radiotracers. The K_d values of Cs⁺ and Rb⁺ have been followed at varying HNO₃ concentrations also. As a result 3 useful binary separations have been achieved on Sn(IV) and Cr(III) arsenophosphates, such as Sr²⁺–Cs⁺, Hg²⁺–Ag⁺ and Hg²⁺–Zn²⁺.     

A Terbium Metal–Organic Framework for Highly Selective and Sensitive Luminescence Sensing of Hg2+ Ions in Aqueous Solution

A series of isomorphic lanthanide metal–organic frameworks (MOFs) Ln(TATAB)?(DMF)₄(H₂O)(MeOH)_0.5 (LnTATAB, Ln=Eu, Tb, Sm, Dy, Gd; H₃TATAB=4,4′,4′′‐s‐triazine‐1,3,5‐triyltri‐p‐aminobenzoic acid) have been solvothermally synthesized and structurally characterized. Among these MOFs, TbTATAB exhibits good water stability and a high fluorescence quantum yield. Because mercury ions (Hg²⁺) have a high affinity to nitrogen atoms, and the space between multiple nitrogen atoms from triazine and imino groups is suitable for interacting with Hg²⁺ ions, TbTATAB shows highly selective and sensitive detection of Hg²⁺ in aqueous solution with a detection limit of 4.4 nm . Furthermore, it was successfully applied to detect Hg²⁺ ions in natural water samples.     

Oligonucleotides-based biosensors with high sensitivity and selectivity for mercury using electrochemical impedance spectroscopy

A novel electrochemical biosensor with high sensitivity and selectivity for mercuric ion detection, based on DNA self-assembly electrode, is designed. Thiol functionalized poly-T oligonucleotides were used as gold electrode modifier through formation of Au–S bond between DNA and gold electrode. In presence of Hg²⁺ ions, the specific coordination between Hg²⁺ and thymine bases can change parallel ss-DNA from linear to hairpin structures, which can cause the release of partial DNA molecules from the surface of the electrode. The density of DNA on the surface of electrode correlated with the concentration of mercury in the solution and can be monitored by electrochemical impedance spectroscopy. The limit of detection of this method is pM level of mercuric ions which is far below the upper limit of Hg²⁺ mandated by United States Environmental Protection Agency (EPA), 2 ppb (10 nM). In addition, this method showed excellent selectivity. A series of divalent metal ions, including Ni²⁺, Co²⁺, Mg²⁺, Zn²⁺, Ba²⁺ and Cd²⁺, have little interference with the detection of Hg²⁺.