Hg Salts Research Articles

Multifunctional Biomass-Based Ionic Liquids/CuCl-Catalyzed CO2-Promoted Hydration of Propargylic Alcohols: A Green Synthesis of α-Hydroxy Ketones.

α-Hydroxy ketones are a class of vital organic skeletons that generally exist in a variety of natural products and high-value chemicals. However, the traditional synthetic route for their production involves toxic Hg salts and corrosive H2SO4 as catalysts, resulting in harsh conditions and the undesired side reaction of Meyer-Schuster rearrangement. In this study, CO2-promoted hydration of propargylic alcohols was achieved for the synthesis of various α-hydroxy ketones. Notably, this process was catalyzed using an environmentally friendly and cost-effective biomass-based ionic liquids/CuCl system, which effectively eliminated the side reaction. The ionic liquids utilized in this system are derived from natural biomass materials, which exhibited recyclability and catalytic activity under 1 bar of CO2 pressure without volatile organic solvents or additives. Evaluation of the green metrics revealed the superiority of this CuCl/ionic liquid system in terms of environmental sustainability. Further mechanistic investigation attributed the excellent performance to the ionic liquid component, which exhibited multifunctionality in activating substrates, CO2 and the Cu component.

Detection of Azo Dyes Using Carbon Dots from Olive Mill Wastes

Azo dyes are widely spread in our day life, being heavily used in cosmetics, healthcare products, textile industries, and as artificial food colorants. This intense industrial activity, which inherently includes their own production, inexorably leads to uncontrolled release of dyes into the environment. As emerging pollutants, their detection, particularly in water systems, is a priority. Herein, a fluorescence-based method was employed for the sensitive and selective detection of anionic and neutral azo dyes. Carbon dots (CDs) synthesized from wet pomace (WP), an abundant semi-solid waste of olive mills, were used as probes. An outstanding capability for detection of azo dyes methyl orange (MO) and methyl red (MR) in aqueous solutions was disclosed, which reached a limit of detection (LOD) of 151 ppb for MO. The selectivity of WP-CDs for the anionic azo dye (MO) was established through competitive experiments with other dyes, either anionic (indigo carmine) or cationic (fuchsin, methylene blue, and rhodamine 6G); perchlorate salts of transition metal cations (Cu(II), Co(II), Fe(II), Fe(III), Hg(II), and Pb(II)); and sodium salts of common anions (NO3−, CO32−, Cl−, and SO42−). Evidence has been collected that supports static quenching as the main transduction event underlying the observed quenching of the probe’s fluorescence, combined with a dynamic resonance energy transfer (RET) mechanism at high MO concentrations.

Thiacalixarenes with Sulfur Functionalities at Lower Rim: Heavy Metal Ion Binding in Solution and 2D-Confined Space.

Sulfur-containing groups preorganized on macrocyclic scaffolds are well suited for liquid-phase complexation of soft metal ions; however, their binding potential was not extensively studied at the air–water interface, and the effect of thioether topology on metal ion binding mechanisms under various conditions was not considered. Herein, we report the interface receptor characteristics of topologically varied thiacalixarene thioethers (linear bis-(methylthio)ethoxy derivative L2, O2S2-thiacrown-ether L3, and O2S2-bridged thiacalixtube L4). The study was conducted in bulk liquid phase and Langmuir monolayers. For all compounds, the highest liquid-phase extraction selectivity was revealed for Ag+ and Hg2+ ions vs. other soft metal ions. In thioether L2 and thiacalixtube L4, metal ion binding was evidenced by a blue shift of the band at 303 nm (for Ag+ species) and the appearance of ligand-to-metal charge transfer bands at 330–340 nm (for Hg2+ species). Theoretical calculations for thioether L2 and its Ag and Hg complexes are consistent with experimental data of UV/Vis, nuclear magnetic resonance (NMR) spectroscopy, and single-crystal X-ray diffractometry of Ag–thioether L2 complexes and Hg–thiacalixtube L4 complex for the case of coordination around the metal center involving two alkyl sulfide groups (Hg2+) or sulfur atoms on the lower rim and bridging unit (Ag+). In thiacrown L3, Ag and Hg binding by alkyl sulfide groups was suggested from changes in NMR spectra upon the addition of corresponding salts. In spite of the low ability of the thioethers to form stable Langmuir monolayers on deionized water, one might argue that the monolayers significantly expand in the presence of Hg salts in the water subphase. Hg2+ ion uptake by the Langmuir–Blodgett (LB) films of ligand L3 was proved by X-ray photoelectron spectroscopy (XPS). Together, these results demonstrate the potential of sulfide groups on the calixarene platform as receptor unit towards Hg2+ ions, which could be useful in the development of Hg2+-selective water purification systems or thin-film sensor devices.

Toxic metal–organic gels using a unique pyridine–pyrazole based ligand with Pb(ii), Cd(ii) and Hg(ii) salts: multi-stimuli responsiveness and toxic dye adsorption

The work presents herein the LMWG property of pyridine–pyrazole containing Schiff base ligand in presence of toxic heavy metals like Pb, Cd and Hg. These MOGs exhibited gel based remarkable toxic dye adsorption and multi-stimuli responsiveness.

Advances in mercury(II)-salt-mediated cyclization reactions of unsaturated bonds.

The synthesis of complex cyclic compounds is extremely challenging for organic chemists. Many transition-metal-salt-mediated cyclizations are reported in literature. Hg(II) salts have been successfully employed in cyclizations to form complex heterocyclic and carbocyclic structures that are impossible to synthesize with other transition metal salts. In this review, we have summarized cyclization reactions that are performed with Hg(II) salts. These salts are also successfully applied in stoichiometric or catalytic amounts to form complex cyclic structures and natural products.

Синтез, сорбционные и металлохромные свойства кремнийорганических производных 1-ацетилгуанидина

Increased interest in carbofunctional organosilicon monomers (silanes) and polymers (silsesquioxanes) is associated with the fact that these compounds are promising reagents and building blocks, materials for micro-electronics, agriculture and medicine, complexones, catalysts, and efficient sorbents. Thus, functional polysilsesquioxanes surpass mineral and organic sorbents in sorption properties. Moreover, they have the highest chemical and thermal stability. Along with sorption activity carbofunctional organosilicon compounds of both monomeric and polymeric structures can possess metallochromic properties. All this paves the way for the large-scale development of analytical systems for the creation of new complex test methods for the determination, concentration and separation of metals from solutions. In the present study the functional monomer N-[3-(triethoxysilyl)propyl]acetylguanidine 1 was synthesized by the condensation reaction of 1-acetylguanidine and 3-triethoxysilyl-propylamine. Poly-N-[3-silsesquioxanyl) propyl]acetylguanidine 2 was obtained by hydrolytic polycondensation of compound 1. The composition and structure of compounds 1 and 2 were confirmed by IR and 1H NMR spectroscopy, as well as by elemental analysis. Polymer 2 was studied as a sorbent for ions of heavy metals, such as Hg (II), and noble metals Ag (I), Au (III), Rh (II), Pd (II), Pt (IV) from solutions of their salts in hydrochloric or nitric acid. For polymer 2, the values of static sorption capacities have been calculated. The latter depend on the nature of the metal and have values from 78 mg/g (for platinum) to 366 mg/g for rhodium. The graphs of the degree of metal extraction depending on the sorption time and acid concentration have been plotted. A sorption mechanism is proposed, which is realized due to the chelate interaction of the metal cation (M+) with the amide groups of compounds 1 and 2. The interaction of monomer 1, in the form of indicator paper, and polymer 2, in the powder form, with salts of the studied metals is accompanied by intense specific coloration (metallochromy). Color tables of the samples after their contact with the Ag (I), Au (III), Pd (II), Pt (IV), Rh (III), Hg (II) salts are given.

Health risk assessment in urban parks soils contaminated by metals, Rio Grande city (Brazil) case study

Soils and artificial surfaces of urban parks can be contaminated by toxic substances and offer risk to the human health, especially to children. Rio Grande city, southern Brazil, is a peculiar site from the point of view of environmental contamination, since the current levels of contamination reflect an accumulation of different polluting sources started in the 18th century up to the urban and industrial sources of the present. The history of Hg contamination refers to the use of Hg salts in textile activities in the 18th century and the consequent use of contaminated sediments to land urban areas. The current contamination involves metals such as Cu, Ni, Pb and Zn is related to the high degree of urbanization in the city, as well as the petrochemical and fertilizer industry. The study aimed to achieve a human health risk assessment of urban parks soils, specifically for Cu, Hg, Ni, Pb and Zn. To carry out the risk assessment using the USEPA model, three urban parks with a history of contamination were studied, using different soil exposure pathways (oral, dermal and inhalation) in the carcinogenic (Ni and Pb) and non-carcinogenic (Cu, Hg, Ni, Pb and Zn) scenarios for children and adults. The non-carcinogenic risk of Pb was found in the three urban parks studied, for children and Hg in two urban parks. Pb and Ni showed no carcinogenic risk. Even so, the high non-carcinogenic risk of Hg and Pb showed that the contamination of the past and the present are found in the urban parks of Rio Grande city, putting the health of children who use these collective spaces at risk.

Influence of Aromatic Cations on the Structural Arrangement of Hg(II) Halides.

Understanding the structure and arrangement of hybrid metal halides and their contribution to the optoelectronic properties is, thus far, a challenging topic. In particular, new materials composed of d10 metal halides and pyridinium cations are still largely unexplored. Therefore, we report the synthesis and characterization of six Hg(II) salts built up from (Hg2Cl6)2– or (HgX4)2– anions (X = Cl, Br, I) and 2,2′-bipyridium (2,2′-Hbipy)+, 2,2′-bipyridine-1,1′-diium (2,2′-H2bipy)2+, or 1,10-phenantrolinium (1,10-Hphen)+ cations, using the same experimental conditions. All of them have been characterized by PXRD, EA, FTIR-ATR, and 1H NMR spectroscopies; single-crystal X-ray diffraction; and TG/DTA determinations. The study of their packing via Hirshfeld surface analysis and 3D deformation density mapping revealed the contributions of the intermolecular interactions to the structural arrangement, notably, the effect of the cation planarity on them. Successively, periodic DFT calculations showed that (i) the valence and conducting bands are mainly composed of the p orbitals of the halide and the organic cation, respectively, and (ii) the corresponding band gap depends mainly on the halide.

Morphological and Histological Study on Thyroid Gland Toxicity in Male Rats Exposed to Mercury

The present study investigated the effect of heavy metals (Mercury chloride) on the morphological andhistological feature of the thyroid gland. Rattus norvegicus male rats were selected for experimental use.the rats given doses of Hg salts (3mg/kg, Ip.3times weekly for 4 week) admin is tration alteredthe body weight, thyroid weight, length and width of thyroid gland. Morphologically, the thyroid glandwas consisted of two labs of reddish brown in color, the lobes were located on ventral Lateral side oftrachea connected caudally with isthmus. While the thyroid gland treated rats recorded changes in color(pale), swollen and enlarged. histologically, the architectural cellular structure gland of the thyroid glandof exposed rats recorded variations in the follicular thyroid, congested blood vessels and depletion of parafollicular cells in the rats treated to Hg in a comparison to that of the control rats. This signify that animalsexposed to Hg could at a risk of thyroid gland.

Concentration-dependent emission of nitrogen-doped carbon dots and its use in hazardous metal-ion detection

Nitrogen-doped carbon dots (CDts) with tunable fluorescence properties in aqueous media were synthesized hydrothermally. The excitation wavelength variation to obtain the maximum emission produced a blue shift in the emission peaks upon dilution in an aqueous solution. The shift can be explained by a re-absorption phenomenon in a concentrated solution. The interparticle interaction within was responsible to show dilution-dependent optical behavior. The as-synthesized solution of CDts did not show any prominent absorption peak over a wide range. However, upon dilution, two peaks became predominant. The concentration-dependent behavior was observed during the interaction with metal cations. Cationic salts of Co(II) and Hg(II) caused quenching at different dilutions of CDts. This might be explained by the exposure of different surface functional groups during dilution and metal-ion–CDts charge transfer. The quenched fluorescence of CDts was rescued using ascorbic acid. Therefore, the one-pot detection of Co(II)/Hg(II) and ascorbic acid was designed through a ‘Turn Off/On’ phenomenon.

A Review on Coordination Properties of Thiol-Containing Chelating Agents Towards Mercury, Cadmium, and Lead.

The present article reviews the clinical use of thiol-based metal chelators in intoxications and overexposure with mercury (Hg), cadmium (Cd), and lead (Pb). Currently, very few commercially available pharmaceuticals can successfully reduce or prevent the toxicity of these metals. The metal chelator meso-2,3-dimercaptosuccinic acid (DMSA) is considerably less toxic than the classical agent British anti-Lewisite (BAL, 2,3-dimercaptopropanol) and is the recommended agent in poisonings with Pb and organic Hg. Its toxicity is also lower than that of DMPS (dimercaptopropane sulfonate), although DMPS is the recommended agent in acute poisonings with Hg salts. It is suggested that intracellular Cd deposits and cerebral deposits of inorganic Hg, to some extent, can be mobilized by a combination of antidotes, but clinical experience with such combinations are lacking. Alpha-lipoic acid (α-LA) has been suggested for toxic metal detoxification but is not considered a drug of choice in clinical practice. The molecular mechanisms and chemical equilibria of complex formation of the chelators with the metal ions Hg2+, Cd2+, and Pb2+ are reviewed since insight into these reactions can provide a basis for further development of therapeutics.

Syntheses, Crystal Structures, Luminescent Properties, and Electrochemical Synthesis of Group 12 Element Coordination Polymers with 4-Substituted 1,2,4-Triazole Ligands

The self-assembly of Zn(II), Cd(II), or Hg(II) salts with long flexible 1,2,4-triazole-based ligands resulted in coordination polymers and mononuclear complexes of diverse topology. Indeed, the 1D chain [ZnCl2(btpm)] (1) (P1), the 2D square grid [Zn(btpm)2(H2O)](BF4)2·2btpm·8H2O (2) (P21212), and the 1D chain [Cd3Cl6(btpm)2]·8H2O (3) (P1) with btpm = bis(4-(1,2,4-triazol-4-yl)phenyl)methane were crystallized. In addition, the mononuclear complexes [ZnCl2(ppt)2] (4) (I2) and [HgBr2(ppt)2] (5) (C2) were obtained along with the 1D polymer [Cd2Cl2(ppt)4](CdCl4)·4DMF (6) (P1) with ppt = (4-phenoxyphenyl)-1,2,4-triazole. 1D chains of the formula [ZnCl2(tpca)] (7) (P21/c) and [HgBr2(tpca)] (8) (P21/c) along with the 2D net [Cd(tpca)2(H2O)2]·2H2O (C2/c) (9) with tpca = N-(1,2,4-triazol-4-yl)pyridine-3-carboxamide were obtained. In addition, the X-ray structures of tpca and ppt are described. All compounds display solid-state blue luminescence, which has been investigated in detail. Electrochemical synthesis of ...

NEW COLORIMETRIC AND FLUORESCENT CHEMOSENSORS BASED ON DIPYRROMETHENE DYES

Synthetic bis(dipyrromethene)s (H2L) is very promising compounds to create sensory systems due to a combination of spectral-luminescent and chelating properties which sensitive to structural and solvation effects. Reactions of H2L·2HBr salts with amines are accompanied by changes in the color of the solution and a clear show a transformations of H4L2+ salt spectrum in the H2L spectrum with a large (about 40 nm) difference between maxima of their intense bands which allows the use of 3,3'-bis(dipyrromethene) salts as colorimetric chemosensors of amines with sensitivity of detection upto 1·10–8 mol/l. The basis for the development of applied directions of using 3,3-bis(dipyrromethene)s as a fluorescent chemosensors of Zn2+, Cd2+ and Hg2+ ions is the bright coloristic effects, accompanying reactions of H2L with Zn(II), Cd(II) and Hg(II) salts, and significant differences in quantitative characteristics of the spectra of the complexes [M2L2] and ligands. Reactions of Zn(II), Cd(II) and Hg(II) salts with a weakly fluorescent bis(dipyrromethene) sensors are accompanied by the buildup (in 25–550 times) of fluorescence. The high sensitivity of fluorescence of d10-metal [M2L2] helikates to the properties of the environment became the basis for the development of the direction of creating fluorescent temperature sensors. The observed effect of the temperature dependence of fluorescence quantum yield of ethanol solutions of [Zn2L2] complexes is interest for the control of temperature (300–80 K). This is important in the development of cryostats or determining temperature of biomaterials cooled in them.

Intramolecular Formation of Zwitterionic Intermediates in 1,3-Diaza-Claisen Rearrangements.

Isothioureas tethered to bridged-bicyclic tertiary allylic amines can be converted to carbodiimides through reaction with Hg(II) salts. Intramolecular cyclization of the tethered tertiary allylic amines to the carbodiimides afford zwitterionic intermediates that undergo 1,3-diaza-Claisen rearrangements, affording highly substituted tricyclic guanidines.

Low doses of mercuric chloride cause the main features of anti-nucleolar autoimmunity in female outbred CFW mice.

The growth of the influence of anthropogenic factors aimed on the improvement of human life has its side effect, for example, living organisms receive increasing exposure to toxic mercuric compounds. Experimental data show that mercury (Hg) salts are able to induce systemic autoimmunity in rodents. This Hg-induced autoimmune process (HgIA) is characterized by T cell-dependent polyclonal activation of B lymphocytes, increased level of serum immunoglobulin G1 (IgG1) and immunoglobulin E (IgE), production of antinucleolar autoantibodies (ANoA), and immune complex deposition in multiple organs. HgIA in mice is used as a model of human systemic autoimmune disorders. However, the dose of mercuric chloride (HgCl2) usually used in laboratory mice to induce HgIA is above the allowable limit for everyday levels of Hg exposure in humans. So, we decided to determine the lowest dose of HgCl2 that is able to trigger autoimmunity in outbred Carworth Farms Swiss Webster (CFW) mice not genetically prone to HgIA development. The lowest dose (50 µg/kg body weight (b.w.)/week) was chosen to match the World Health Organization provisional weekly tolerable intake of total Hg for humans. We also tested HgCl2 at 500 and 1500 µg/kg b.w./week (6.5- and 2-fold less than usually used for induction of HgIA in mice). We found that even the lowest dose of Hg resulted in a statistically significant increase in serum level of IgG1 after 8 weeks of treatment. HgCl2 in doses 500 and 1500 µg/kg b.w./week resulted in a significant increase in serum level of IgG1 after 4 weeks of treatment, followed by ANoA production. Sera of HgCl2-treated mice stained the regions in which the major autoantigen in HgIA, fibrillarin, was revealed. These results suggest that low doses of Hg are able to induce the main features of HgIA in genetically heterozygous mice, and that humans chronically exposed to low doses of Hg may be at risk of autoimmunity induction regardless of their genetic background.

Hg(II) Coordination Polymers Based on N,N'-bis(pyridine-4-yl)formamidine.

Reactions of N,N’-bis(pyridine-4-yl)formamidine (4-Hpyf) with HgX2 (X = Cl, Br, and I) afforded the formamidinate complex {[Hg(4-pyf)2]·(THF)}n, 1, and the formamidine complexes {[HgX2(4-Hpyf)]·(MeCN)}n (X = Br, 2; I, 3), which have been structurally characterized by X-ray crystallography. Complex 1 is a 2D layer with the {44·62}-sql topology and complexes 2 and 3 are helical chains. While the helical chains of 2 are linked through N–H···Br hydrogen bonds, those of 3 are linked through self-complementary double N–H···N hydrogen bonds, resulting in 2D supramolecular structures. The 4-pyf- ligands of 1 coordinate to the Hg(II) ions through one pyridyl and one adjacent amine nitrogen atoms and the 4-Hpyf ligands of 2 and 3 coordinate to the Hg(II) ions through two pyridyl nitrogen atoms, resulting in new bidentate binding modes. Complexes 1–3 provide a unique opportunity to envisage the effect of the halide anions of the starting Hg(II) salts on folding and unfolding the Hg(II) coordination polymers. Density function theory (DFT) calculation indicates that the emission of 1 is due to intraligand π→π * charge transfer between two different 4-pyf- ligands, whereas those of 2 and 3 can be ascribed to the charge transfer from non-bonding p-type orbitals of the halide anions to π * orbitals of the 4-pyf- ligands (n→π *). The gas sorption properties of the desolvated product of 1 are compared with the Cu analogues to show that the nature of the counteranion and the solvent-accessible volume are important in determining their adsorption capability.

Luminescent (N^C^C) Gold(III) Complexes: Stabilized Gold(III) Fluorides

AbstractWe report the design, synthesis, and application of a (N^C^C)‐ligand framework able to stabilize highly electron‐deprived gold(III) species. This novel platform enabled the preparation of C(sp2)‐gold(III) fluorides for the first time in monomeric, easy‐to‐handle, bench‐stable form by a Cl/F ligand‐exchange reaction. Devoid of oxidative conditions or stoichiometric use of toxic Hg salts, this method was applied to the preparation of multiple [C(sp2)‐AuIII‐F] complexes, which were used as mechanistic probes for the study of the unique properties and intrinsic reactivity of AuF bonds. The improved photophysical properties of [(N^C^C)AuIII] complexes compared to classical pincer (C^N^C)‐Au systems paves the way for the design of new late‐transition‐metal‐based OLEDs.

Luminescent (N^C^C) Gold(III) Complexes: Stabilized Gold(III) Fluorides.

We report the design, synthesis, and application of a (N^C^C)-ligand framework able to stabilize highly electron-deprived gold(III) species. This novel platform enabled the preparation of C(sp(2))-gold(III) fluorides for the first time in monomeric, easy-to-handle, bench-stable form by a Cl/F ligand-exchange reaction. Devoid of oxidative conditions or stoichiometric use of toxic Hg salts, this method was applied to the preparation of multiple [C(sp(2))-Au(III)-F] complexes, which were used as mechanistic probes for the study of the unique properties and intrinsic reactivity of Au-F bonds. The improved photophysical properties of [(N^C^C)Au(III)] complexes compared to classical pincer (C^N^C)-Au systems paves the way for the design of new late-transition-metal-based OLEDs.

Selenium as an antidote in the treatment of mercury intoxication.

Selenium (Se) is an essential trace element for humans. It is found in the enzyme glutathione peroxidase. This enzyme protects the organism against certain types of damage. Some data suggest that Se plays a role in the body's metabolism of mercury (Hg). Selenium has in some studies been found to reduce the toxicity of Hg salts. Selenium and Hg bind in the body to each other. It is not totally clear what impact the amount of Se has in the human body on the metabolism and toxicity of prolonged Hg exposure.

Synthesis and structural characterization of dinuclear Cd2+, Hg2+ and Fe2+ complexes with neutral bi and tetradentate flexible pyrazole-based ligands

Four new complexes of [Hg2Cl4(bpp)]n (1), [Hg2Cl4(tdmpp)] (2), [Cd2I4(tdmpp)] (3) and [Fe2Cl4(tdmpp)] (4) were prepared by using the neutral N-donor ligands 1,3-bis(3,5-dimethyl-1-pyrazolyl)propane (bpp) and 1,1,3,3-tetrakis(3,5-dimethyl-1-pyrazolyl)propane (tdmpp) with different flexibility and appropriate metal salts of Cd(II), Hg(II) and Fe(II) ions. These compounds were characterized by the infrared spectroscopy, elemental analysis and X-ray crystallography. Flexible ligands and non-covalent CH⋯Cl hydrogen bonds play a major role in the crystal packing of compounds 1, 2 and 4. In the two-dimensional non-covalent structure of 1, there are two distinctly different coordination modes for the mercury atoms. One mercury atom has pseudo-trigonal bipyramidal geometry and the other adopts a distorted tetrahedral environment. In the dinuclear structures of 2 and 4 the neutral molecules are linked together by the CH⋯Cl hydrogen bonds, forming an infinite one-dimensional zigzag chain structure. Compounds 2–4 are isostructural with each other.