New Azobenzene Dye Colorimetric and Ratiometric Chemosensors for Mercury(Ⅱ)Ion

A new series of azobenzene dyes, which possessed colorimetric and ratiometric recognition to Hg²⁺ based on the mechanism of internal charge transfer (ICT), was developed and characterized. The molecules involving azo and imino functional groups can coordinate with Hg²⁺ to result in a large blue shift from 453 to 363 nm corresponding to a notable color change from orange to pale yellow in aqueous methanol solution (H₂O/CH₃OH=1/4, V/V), which can be applied to naked eye detection of Hg²⁺. The sensitivity, selectivity and binding mode of the sensors to Hg²⁺ were investigated by UV‐Vis spectroscopy.     

A Fluorescent Probe for Hg2+ Based on Gold(I) Complex with An Aggregation‐Induced Emission Feature

A gold(I) complex that exhibited aggregation‐induced emission in acetonitrile‐water mixtures was designed. It showed high selectivity and sensitivity for Hg²⁺ in acetonitrile‐H₂O (1:1, V:V) solution. Dynamic light scattering measurements were conducted to verify that the addition of Hg²⁺ changed the particle size and induced fluorescence quenching.     

A novel pyrene-based “off–on” fluorescent probe with high selectivity and sensitivity for Hg2+

In this article, a novel “off–on” fluorescent probe 2-(pyren-1-ylmethylene)-1H-indene-1,3(2H)-dione ( PID ) for Hg²⁺ was designed and synthesized. The selectivity, concentration titration, pH titration, time dependence, limit of detection, and recognition mechanism of PID for Hg²⁺ in CH₃CH₂OH/H₂O solution were also investigated. The results indicated that PID exhibited high selectivity, sensitivity, and fast response to Hg²⁺, and the limit of detection was as low as 20.7 nmol/L. In addition, PID could work in a wide pH range, and the determination of Hg²⁺ in water samples showed that it could be used as a potential detection tool in practical application.     

A Coumarin-boronic Based Fluorescent “ON-OFF” Probe for Hg2+ in Aqueous Solution

In this work, we reported a simple coumarin-boronic acid ester fluorescent probe 1 , which displayed very high “ON-OFF” fluorescence response for Hg²⁺ in an aqueous environment (H₂O/CH₃CN = 1:1, v/v) or in a PBS solution (pH = 7.4). With the addition of Hg²⁺ to the solution of probe, a color change from light yellow to orange could be observed by naked eye. The detection limits were lower than the permitted level of Hg²⁺ in drinking water defined by WHO. Infrared spectroscopy, mass spectroscopy and ¹H NMR titration studies showed that probe 1 formed a 1:1 complex with Hg²⁺. In addition, the probe was non-toxic to cells and could stain specifically the membrane region surrounding the HeLa cell.     

Aptamer-modified AuRe Nanoalloy Probe for Trace Hg2+ Using Resonance Scattering as Detection Technique

The AuRe nanoalloy particles in molar ratio of 9:1 were prepared by sodium borohydride procedure, and modified by single strand DNA (ssDNA) to prepare an aptamer AuRe nanoprobe (AuRessDNA) for Hg²⁺. In the pH 7.0 Na₂HPO₄‐NaH₂PO₄ buffer solution and in the presence of NaCl, Hg²⁺ interacted with AuRessDNA to form double‐stranded T‐Hg²⁺‐T mismatched and release AuRe nanoparticles that aggregate to large AuRe nanoparticles clusters causing the resonance scattering (RS) peak red shifting and the RS intensity enhanced linearly. On those grounds, 0.067–33.3 nmol·L^?1 Hg²⁺ can be detected rapidly by the aptamer‐modified AuRe nanoparticles RS assay, with a detection limit of 0.04 nmol·L^?1 Hg²⁺. If the aggregated AuRe particles were removed by membrane filtration, the excess AuRessDNA in the filtration solution exhibits catalytic effect on the new Te particle reaction between Na₂TeO₄ and SnCl₂. As the concentration of Hg²⁺ increased, the AuRessDNA nanoparticles in the filtrate solution decreased, the RS intensity at 734 nm decreased linearly. The Hg²⁺ concentration (c) in the range of 0.00133–0.267 nmol·L^?1 was linear to the decreased RS intensity (ΔI_734nm), with a regression equation of ΔI= ?786.4c?4.4, a correlation coefficient of 0.9975, and a detection limit of 0.9 pmol·L^?1 Hg²⁺. This method was applied to the detection of Hg²⁺ in water samples, with satisfactory results.     

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.     

In vivo Visualization of the Process of Hg2+ Bioaccumulation in Water Flea Daphnia carinata by a Novel Aggregation‐Induced Emission Fluorogen

This paper employs a specially designed aggregation‐induced emission fluorogen (AIEgen) to in vivo visualize the process of Hg²⁺ bioaccumulation in a common species of freshwater zooplankton Daphnia carinata (D. carinata) by two methods, direct Hg²⁺ absorption and ingestion of Hg²⁺ contaminated food. We analysed the relevance between photoluminescence (PL, I₅₉₅/I₄₈₀) ratios and Hg²⁺ (C_Hg2+) and developed the master curve for Hg²⁺ determination based on measuring the PL intensity of the solution. Meanwhile, fluorescent image analysis showed that the major recipient organs of Hg²⁺ in D. carinata were the compound eyes and carapace, followed by the intestine and shell gland, but not the brain or heart. The response of D. carinata to Hg²⁺ via uptake from surrounding water differed distinctly from that through food intake of the algae (Euglena gracilis) contaminated by mercury. When Hg²⁺ was encapsulated by algae membrane, no fluorescence was detected, and the carapace morphology remained intact after ingesting algae for 80 min, in contrast to the rapid carapace deformation by direct Hg²⁺ absorption. The D. carinata showed higher mortality by direct Hg²⁺ immersion than via food ingestion. The reason for the high mortality after Hg²⁺ immersion was possibly due to carapace deformity after chemical reaction between chitin and mercury, but the biochemical pathway leading to morality needs further study.     

Novel Carboxylic Acid-Capped Silver Nanoparticles as Antimicrobial and Colorimetric Sensing Agents

The present work reports the synthesis, characterization, and antimicrobial activities of adipic acid-capped silver nanoparticles (AgNPs@AA) and their utilization for selective detection of Hg²⁺ ions in an aqueous solution. The AgNPs were synthesized by the reduction of Ag⁺ ions with NaBH₄ followed by capping with adipic acid. Characterization of as-synthesized AgNPs@AA was carried out by different techniques, including UV–Visible spectroscopy, Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), X-ray diffraction (XRD), Dynamic Light Scattering (DLS), and zeta potential (ZP). In the UV–Vis absorption spectrum, the characteristic absorption band for AgNPs was observed at 404 nm. The hydrodynamic size of as-synthesized AgNPs was found to be 30 ± 5.0 nm. ZP values (−35.5 ± 2.4 mV) showed that NPs possessed a negative charge due to carboxylate ions and were electrostatically stabilized. The AgNPs show potential antimicrobial activity against clinically isolated pathogens. These AgNPs were found to be selectively interacting with Hg²⁺ in an aqueous solution at various concentrations. A calibration curve was constructed by plotting concentration as abscissa and absorbance ratio (A_Control − A_Hg/A_Control) as ordinate. The linear range and limit of detection (LOD) of Hg²⁺ were 0.6–1.6 μM and 0.12 μM, respectively. A rapid response time of 4 min was found for the detection of Hg²⁺ by the nano-probe. The effect of pH and temperature on the detection of Hg²⁺ was also investigated. The nano-probe was successfully applied for the detection of Hg²⁺ from tap and river water     

Calculation of the equilibrium constants and binding cooperativity parameters of ammonia with Group II metal cations in solution

The matrix model was used to analyze the distribution diagrams and formation functions of ammonia complexes [M(NH₃) _n ]²⁺ (n = 0−4) of Group II metal ions (Mg²⁺, Ca²⁺, Zn²⁺, Cd²⁺, and Hg²⁺) in solution. Intrinsic binding constants of the ligand (K _in) and mutual influence corrections (ω) for complex formation with aqua ions in solution were calculated. The equilibrium constants were calculated by the matrix method. The coordination sphere of Mg²⁺, Ca²⁺, and Zn²⁺ by ammonia in a cooperative manner; with Cd²⁺ and Hg²⁺, both cooperative and anticooperative binding occur concurrently. Possibilities for differentiation between tetrahedral and square planar coordination polyhedra on the basis of the characteristic features of ligand binding, determined by the matrix model, are discussed.     

Thermodynamic Studies of Bi-Univalent Electrolytes. VI. Thermodynamics of Cadmium Acetate from E. M. F. and Calorimetric Measurements

E. M. F. of the Cell, Cd-Hg (2-phase)/CdAc₂(m), Hg₂Ac₂(s)/Hg was measured at 20°, 25°, 30° and 40°C. The standard e. m. f. of the cell, Cd/CdAc₃(m), Hg₂Ac₂(c)/Hg was evaluated as E°=1.1500?11.09×10^?4T+1.06×10^?8T² The thermodynamic data of the reaction, Cd(c) + Hg₂Ac₂(c)=2Hg(l)+Cd⁺⁺(aq)+2Ac^?(aq) at 25°C were estimated as ΔF°=?42,139, ΔH°=?48,698 cal mole^?1 and ΔS°=?22.0 cal deg^?1 mole^?1 at 25°C. The thermodynamic data for the formation of Hg₂Ac₂(s) were evaluated as ΔF_f°=?202.3, ΔH_f°=?154.5 Kcal mole^?1 and S°=72.9 cal deg^?1 mole^?1. From measurements of the heats of solution of CdAc₂·2H₂O in aqueous solution, the relative partial molal enthalpies of cadmium acetate in aqueous solution were estimated.     

Solid Substrate Room Temperature Phosphorimetry for the Determination of Trace Mercury Based on the Reaction between Alkaline Phosphatase and Mercury Using Triton X-100 as a Sensitizer

A new solid substrate room temperature phosphorimetry (SSRTP) for the determination of trace mercury has been established, using Triton X‐100 as a sensitizer. The regression equation of working curve was ΔI_p=11.40m(Hg²⁺)+1.569 (ag·spot^?1, n=6, ΔI_p=I_p1?I_p2, I_p1 and I_p2 referred to the phosphorescence intensity of the blank reagent and the test solution, respectively), and correlation coefficient (r) was 0.9984. The RSD valus of the determination of 0.016 and 8.0 ag·spot^?1 Hg²⁺ were 4.1% and 1.7% (n=8), respectively, indicating that the method had good repeatability. The limit of detection (LOD) calculated by 3Sb/k was 7.0 zg·spot^?1 Hg²⁺ (corresponding concentration: 1.8×10^?17 g·mL^?1, Sb=0.025, n=11). This method has high sensitivity, selectivity and precision, which was applied to determination of trace mercury in water samples with the result being agreed very well with that of dithizone extraction spectrophotometry.     

A new class of meta-pyridine-urea oligomers for selective identification of mercury(II) ions

A series of new pyridine-urea oligomers were synthesized and tested for their ability to recognize ions in PBS or Ac buffer solution by fluorescence. The results showed that the ability of oligourea urea to selectively recognize Hg²⁺ was gradually enhanced with the increase of chain, which was further proved by DFT calculation. The 1:2 stoichiometry was established for the L7-Hg²⁺ complex on the basis of Job's plot. The binding constant (K_B) and the lowest detection limit for Hg²⁺ were also determined. DFT calculations were used to optimize the structures of L2-7 and its Hg²⁺ complexes. Highly sensitive and selective probes for the recognition of Hg²⁺ based on this report are expected to be developed and used for in vivo detection.     

Hydrolytic precipitation of magnesium polyvanadates in vanadium (IV, V) solutions

The phase and chemical composition of precipitates formed in Mg(VO₃)₂-VOSO4-H₂O system at initial pH from 1 to 7 and temperature from 80 to 90°C was studied. Polyvanadates of variable composition Mg _x V _y ⁴⁺V_12-y ⁵⁺¹O_31–δ · nH₂O (0.7 ≤ x ≤ 1.3, 1.2 ≤ y ≤ 2.4, 0.7 ≤ δ = 1.4) were formed at pH from 1 to 4 and V⁴⁺/V⁵⁺ ratio from 0.43 to 9. Compounds with the general formula Mg _x V _y ⁴⁺V_6-y ⁵⁺O_16-δ · nH₂O (0.7 ≤ x ≤ 0.65, y = 1.0, 0.8 ≤ δ ≤ 0.85) were formed at pH from 6.0 to 7.0 and V⁴⁺/V⁵⁺ ratios from 0.11 to 0.25. The maximum V⁴⁺ concentration (y = 2.4) in the precipitates was achieved at the VV⁴⁺/V⁵⁺ solution ratio of 1.0 and pH = 3. The precipitates in solutions with pH 3 were formed only upon addition of VO²⁺ ions with the maximum rate at a V⁴⁺/V⁵⁺ ratio of 0.33. These processes were limited by second-order reactions on the surface of polyvanadates.     

一种近红外发射荧光探针的合成及其荧光增强识别Hg2+

汞离子(Hg~(2+))由于高毒性以及容易对环境和人体造成损害,其检测越来越受到人们的重视。本文基于4-(二乙氨基)水杨醛设计合成了一种近红外发射荧光探针L,该探针可在MeCN/HEPES(体积比2/8,pH=7.4)缓冲溶液中高选择性地荧光增强识别Hg~(2+),其具有合成简便、抗干扰能力强、适用pH范围宽等特点。进一步研究表明,探针L可用于真实水样中Hg~(2+)的检测。     

A rhodamine-based Hg2+-selective fluorescent probe in aqueous solution

A new rhodamine-based Hg²⁺-selective fluorescent probe (I) was designed and synthesized. Compound I displays excellent selective and sensitive response to Hg²⁺ over other transition metal ions in neutral aqueous solutions. I itself is a colorless, nonfluorescent compound. Upon addition of Hg²⁺ to its solution, the thiosemicarbazide moiety of I undergoes an irreversible desulfurization reaction to form the corresponding 1,3,4-oxadiazole (II), a colorful and fluorescent product, causing instantaneous development of visible color and strong fluorescence emission. Based on this mechanism, a fluorogenic probe for Hg²⁺ was developed. The fluorescence increases linearly with the Hg²⁺ concentration up to 0.8 μmol L⁻¹ with the detection limit of 9.4 nmol L⁻ (3σ).     

Four Polyoxometalate-Viologen Discoloration Materials for UV Probing,Inkless and Erasable Printing and Visual Detection of Hg2+

In this work, four POM-based compounds containing viologen ligands were synthesized, namely {Cu^II(tybipy)₂(DMF)₂[H₂(β-Mo₈O₂₆)]₂} ⋅ 4 C₂H₇N ( 1 ), (Htybipy)₂ ⋅ (β-Mo₈O₂₆) ( 2 ) (tybipy⋅Br=1-Thiophen-3-ylmethyl-[4,4’]bipyridinyl-1-ium bromide), [Cu^II(nibipy)₂(4,4’-bipy)] ⋅ (SiW₁₂O₄₀) ( 3 ), (Hnibipy)₂ ⋅ (δ-Mo₈O₂₆) ( 4 ) (nibipy⋅Cl=1-(4-Nitro-benzyl)-[4,4’]bipyridinyl-1-ium chloride, 4,4’-bipy=4,4’-bipyridine). In compounds 1 and 3 , Cu²⁺ and mixed organic ligands modify POM anions. On the other hand, 2 and 4 are supramolecular structures only containing ligands and anions. Under Xe lamp with filter (300-400 nm) irradiation, these four compounds showed good photoresponse and photochromic ability, which can be used in mixed matrix films for visible UV detectors. Compounds 1 – 4 also have photoluminescence property and show good fluorescence quenching effect. A suspension of four compounds can be evenly spread on filter paper as inkless and erasable printing materials. Compounds 1 and 2 were also used as Hg²⁺ fluorescence detectors. The fluorescence intensity of 1 decreased by ca. 90 % when the concentration of Hg²⁺ increased to 40 mM. Moreover, we also prepared composites 1 / 2 @Hg²⁺, 1 @Cu²⁺, 1 @Co²⁺ by introducing 1 / 2 and Hg²⁺, Cu²⁺ and Co²⁺ to detection paper respectively, which can act as photochromic materials with features of fast color recovery.     

A rhodamine hydrazide–4-nitroindole-3-carboxaldehyde based turn on Hg2+ chemosensor: cytoplasmic live cell imaging,logic gate and memory device applications and computational studies

A new, highly sensitive probe L² for the selective detection of Hg²⁺ in organo-aqueous (H₂O:CH₃CN, 1:1, v/v, HEPES buffer, pH 7.2) medium has been synthesized from rhodamine 6G-hydrazide and 4-nitroindole-3-carboxaldehyde. It was thoroughly characterized by physicochemical techniques including single crystal X-ray diffraction studies. The reaction of L² with Hg²⁺ gives a 1:1 stoichiometry resulting in a 146 fold fluorescence enhancement and a binding constant (K_f) of 3?×?10⁴ M^?1. The spirolactam form of the probe is non-fluorescent; however, it shows dual channel (absorbance and fluorescence) recognition of Hg²⁺ via CHEF effect through the opening of the spirolactam ring. The quantum yields of L² (0.00045) and L²-Hg²⁺ (0.29) show the higher stability of complex in the excited state over the free ligand. The 44.5?nM LOD value demonstrates the detection of Hg²⁺ at a very low concentration range. Cell imaging studies show the cytoplasmic recognition of Hg²⁺ by L². Experimental results are comparable with theoretical values obtained by DFT studies. The fluorescence emission of the complex was completely quenched by I^- and from the reversibility studies an advance level INHIBIT logic gate and memory device can be framed.     

Spectral Studies on the Interaction between Mercuric Ion and ApoCopC

The interaction between mercuric ion and apoCopC in the absence or presence of cupric ion was investigated through difference UV spectra in Hepes buffer （10 mmol·L^-1） at pH 7.4. The results suggest that mercuric ion can bind to C- and N-terminal binding sites of apoCopC, and the conditional binding constants were calculated to be kN=（6.79± 1.12）× 10^6 mol^-1·L and kc=（3.06±0.05）× 10^5 mol^-1·L. Using urea as a chemical agent, the conformational stabilities of apoCopC and HgN^2＋ -CopC-Hgc^2＋ were monitored by fluorescence spectrum in Hepes buffer （50 mmol·L^-1） at pH 7.4. The free energy of stabilization is （14.69±0.85） and （16.66±0.55） kJ.mol^-1, respectively. HgN^2＋ -CopC-Hgc^2＋ is more stable than apoCopC.     

Fluorescent chemosensor for mercury(II) cations in an aqueous solution based on 4-acetylamino-1, 8-naphthalimide derivative containing the N-phenylazadithia-15-crown-5-ether receptor

The 4-acetylamino-1,8-naphthalimide derivative containing the N-phenylazadithia-15-crown-5-ether fragment in the N-aryl substituent at the imide nitrogen atom of the naphthalimide core was synthesized, and its cation-dependent spectral properties were studied. The resulting compound in the photoexcited state exhibits low-intensity fluorescence due to the process of electron transfer from the N-aryl group to the naphthalimide residue, which is confirmed by the data of quantum chemical calculations performed using the PM6 method. The binding of Hg²⁺ in an aqueous acetate buffer solution at pH 6.0 is accompanied by the formation of a 1: 1 metal—ligand complex in which the electron transfer is suppressed leading to fluorescence enhancement. The observed spectral changes were used for the determination of the stability constant K of the complex (logK = 6.51±0.03). The found limit of Hg²⁺ detection using the synthesized sensor (28 nmol L^?1) is fairly close the maximum permissible concentration for mercury in drinking water. The study of the selectivity of complexation showed that the presence of Cu²⁺, Zn²⁺, Ni²⁺, Pb²⁺ Cd²⁺, Ca²⁺, Mg²⁺, and Fe²⁺ cations did not impede the determination of Hg²⁺. The presented results indicate that the synthesized chemosensor is promising as a selective and highly sensitive fluorescent reagent for Hg²⁺ ions in an aqueous solution.

     

Highly sensitive and selective determination of Hg2+ by using 3-((2-(1H-benzo[d]imidazol-2-yl)phenylimino)methyl)benzene-1,2-diol as fluorescent chemosensor and its application in real water sample

A new receptor 3-((2-(1H-benzo[d]imidazol-2-yl)phenylimino)methyl)benzene-1,2-diol (1) was synthesised and developed as a highly selective fluorescent chemosensor for the detection of Hg²⁺ in semi-aqueous media. The fluorescence of receptor 1 was dramatically and selectively quenched on complexation with Hg²⁺ ion with the detection limit down to 0.20 μM. The developed sensor was successfully applied for the determination of Hg²⁺ content in water samples. Density Functional Theory (DFT) calculations were performed to study the mechanistic behaviour behind the binding of Hg²⁺ with receptor 1.