Metal Ions, Metal Chelators and Metal Chelating Assay as Antioxidant Method

Heavy metals are essential for a wide range of biological processes, including the growth and reproduction of cells, synthesis of biomolecules, many enzymatic reactions, and the body’s immunity, but their excessive intake is harmful. Specifically, they cause oxidative stress (OS) and generate free radicals and reactive oxygen species (ROS) in metabolism. In addition, the accumulation of heavy metals in humans can cause serious damage to different organs, especially respiratory, nervous and reproductive and digestive systems. Biologically, metal chelation therapy is often used to treat metal toxicity. This process occurs through the interaction between the ligand and a central metal atom, forming a complex ring-like structure. After metals are chelated with appropriate chelating agents, their damage in metabolism can be prevented and efficiently removed from the body. On the other hand, heavy metals, including Zn, Fe and Cu, are necessary for the suitable functioning of different proteins including enzymes in metabolism. However, when the same metals accumulate at levels higher than the optimum level, they can easily become toxic and have harmful effects toward biomolecules. In this case, it induces the formation of ROS and nitrogen species (RNS) resulting in peroxidation of biological molecules such as lipids in the plasma membrane. Antioxidants have an increasing interest in many fields due to their protective effects, especially in food and pharmaceutical products. Screening of antioxidant properties of compounds needs appropriate methods including metal chelating assay. In this study, a general approach to the bonding and chelating properties of metals is described. For this purpose, the basic principles and chemical principles of metal chelation methods, both in vivo and in vitro, are outlined and discussed. Hence, in the main sections of this review, the descriptions related to metal ions, metal chelating, antioxidants, importance of metal chelating in biological system and definitions of metal chelating assays as widely used methods to determine antioxidant ability of compounds are provided. In addition, some chemical properties, technical and critical details of the used chelation methods are given.

Meso-substituted cationic 3- and 4-N-Pyridylporphyrins and their Zn(II) derivatives for antibacterial photodynamic therapy

Photodynamic inactivation of microorganisms known as antibacterial photodynamic therapy (APDT) is one of the most promising and innovative approaches for the destruction of pathogenic microorganisms. Among the photosensitizers (PSs), compounds based on cationic porphyrins/metalloporphyrins are most successfully used to inactivate microorganisms. Series of meso-substituted cationic pyridylporphyrins and metalloporphyrins with various peripheral groups in the third and fourth positions of the pyrrole ring have been synthesized in Armenia. The aim of this work was to determine and test the most effective cationic porphyrins and metalloporphyrins with high photoactivity against Gram negative and Gram positive microorganisms. It was shown that the synthesized cationic pyridylporphyrins/metalloporphyrins exhibit a high degree of phototoxicity towards both types of bacteria, including the methicillin-resistant S. aureus strain. Zinc complexes of porphyrins are more phototoxic than metal-free porphyrin analogs. The effectiveness of these Zn–metalloporphyrins on bacteria is consistent with the level of singlet oxygen generation. It was found that the high antibacterial activity of the studied cationic porphyrins/metalloporphyrins depends on four factors: the presence in the porphyrin macrocycle of a positive charge (+4), a central metal atom (Zn[Formula: see text] and hydrophobic peripheral functional groups as well as high values of quantum yields of singlet oxygen. The results indicate that meso-substituted cationic pyridylporphyrins/metalloporphyrins can find wider application in photoinactivation of bacteria than anionic or neutral PSs usually used in APDT.

Tetraammonium μ-ethylenediaminetetraacetato-1κ3 O,N,O′:2κ3 O′′,N′,O′′′-bis[trioxidotungstate(VI)] tetrahydrate

The title compound, (NH4)4[W2(C10H12N2O8)O6]·4H2O, was obtained from a mixture of tungstic acid, ammonia and ethylenediaminetetraacetic acid (H4edta) in a 2:4:1 ratio. The anion of the complex contains two WO3 units and one bridging edta4− ligand. Each central metal atom is tridentately coordinated by nitrogen and two carboxylate groups of the edta4− ligand, together with the three oxido ligands, producing a distorted octahedral coordination environment around each tungsten atom. The center of the carbon–carbon bond of the ethylene bridge represents a crystallographic inversion center. The crystal structure consists of a three-dimensional supramolecular framework built up by the dinuclear cations, the ammonium counter-ions and the solvent water molecules via hydrogen bonds of the N—H...O and O—H...O type.

Interface interaction of transition metal phthalocyanines with strontium titanate (100)

We study interface properties of CoPcFx and FePcFx (x = 0 or 16) on niobium-doped SrTiO3(100) surfaces using mainly X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy. For all studied molecules, a rather complex, bidirectional charge transfer with the oxide substrate was observed, involving both the macrocycle and the central metal atom. For molecules of the first monolayer, an electron transfer to the central metal atom is concluded from transition metal 2p core level photoemission spectra. The number of interacting molecules in the first monolayer on the oxide surface depends on the central metal atom of the phthalocyanine, whereas the substrate preparation has minor influence on the interaction between CoPc and SrTiO3(100). Differences of the interaction mechanism to related TiO2 surfaces are discussed.

Tris(Butadiene) Compounds versus Butadiene Oligomerization in Second-Row Transition Metal Chemistry: Effects of Increased Ligand Fields

The geometries, energetics, and preferred spin states of the second-row transition metal tris(butadiene) complexes (C4H6)3M (M = Zr–Pd) and their isomers, including the experimentally known very stable molybdenum derivative (C4H6)3Mo, have been examined by density functional theory. Such low-energy structures are found to have low-spin singlet and doublet spin states in contrast to the corresponding derivatives of the first-row transition metals. The three butadiene ligands in the lowest-energy (C4H6)3M structures of the late second-row transition metals couple to form a C12H18 ligand that binds to the central metal atom as a hexahapto ligand for M = Pd but as an octahapto ligand for M = Rh and Ru. However, the lowest-energy (C4H6)3M structures of the early transition metals have three separate tetrahapto butadiene ligands for M = Zr, Nb, and Mo or two tetrahapto butadiene ligands and one dihapto butadiene ligand for M = Tc. The low energy of the experimentally known singlet (C4H6)3Mo structure contrasts with the very high energy of its experimentally unknown singlet chromium (C4H6)3Cr analog relative to quintet (C12H18)Cr isomers with an open-chain C12H18 ligand.

Synthesis, Spectral Characterization and Biological Evaluation of Metal Complexes of 2-Thioxoquinoline Aminophenol

A series of novel 2-thioxoquinoline aminophenol Schiff base based Co(II), Ni(II), Cu(II) and Zn(II) metal complexes [M(L)2], (M = Co2+, Ni2+, Cu2+ & Zn2+; L = 2-thioxoquinoline aminophenol) were synthesized and characterized by elemental analysis and spectral studies (FT-IR, UV-Vis, 1H NMR, ESR and ESI-Mass). All experimental results showed that in these metal complexes, the central metal atom was coordinated by oxygen, nitrogen and sulfur donor atoms of deprotonated Schiff base. Further, the ligand and its metal(II) complexes were screened against Gram-positive (Staphylococcus aureus), Gram-negative (Escherichia coli) bacteria and fungus (Candida albicans) strains. in vitro Anticancer activity of ligand and its metal(II) complexes were also screened against HeLa cells (Human cervical cancer cells).

Removal of Heavy Metal Ions from Water and Wastewaters by Sulfur-Containing Precipitation Agents

Restrictive requirements for maximum concentrations of metals introduced into the environment lead to search for effective methods of their removal. Chemical precipitation using hydroxides or sulfides is one of the most commonly used methods for removing metals from water and wastewater. The process is simple and inexpensive. However, during metal hydroxide precipitation, large amounts of solids are formed. As a result, metal hydroxide is getting amphoteric and it can go back into the solution. On the other hand, use of sulfides is characterized by lower solubility compared with that of metal hydroxides, so a higher degree of metal reduction can be achieved in a shorter time. Disadvantages of that process are very low solubility of metal sulfides, highly sensitive process to the dosing of the precipitation agent, and the risks of emission of toxic hydrogen sulfide. All these restrictions forced to search for new and effective precipitants. Potassium/sodium thiocarbonate (STC) and 2,4,6-trimercaptotiazine (TMT) are widely used. Dithiocarbamate (DTC) compounds are also used, e.g., sodium dimethyldithiocarbamate (SDTC), and ligands for permanent metal binding, e.g., 1,3-benzenediamidoethanethiol (BDETH2), 2,6-pyridinediamidoethanethiol (PyDET), a pyridine-based thiol ligand (DTPY) or ligands with open chains containing many sulfur atoms, using of a tetrahedral bonding arrangement around a central metal atom. The possibility of improving the efficiency of metal precipitation is obtained by using a higher dose of precipitating agent. However, toxic byproducts are often produced. It is required that the precipitation agents not only effectively remove metal ions from the solution but also effectively bind with dyes or metal complexes.

Cu (II) Complex of 1- Naphthaldehyde Semicarbazone: Synthesis, Characterization, Thermal Analysis and Antibacterial Activity

The ligand, L is the Schiff base formed by condensation of 1- naphthaldehyde with semicarbazide and its Cu(II) complex have been synthesized and characterized by elemental and thermogravimetric analysis and molar conductivity, magnetic and spectroscopic measurements. Elemental analysis of the chelate suggests the stoichiometry is 1:1 (metal-ligand). Infrared spectra of the complex agree with the coordination to the central metal atom through the nitrogen of the azomethine (-HC=N-) group and the carbonyl oxygen atom. Magnetic susceptibility data suggest a tetrahedral geometry for the complex. ESI-MS data also supports the proposed structure of the synthesized compounds. The ligand and its copper complex have been screened for their antibacterial activity against Enterobacter aerogenes and Bacillus cereus. The metal complex were shown to possess more antibacterial activity than the uncomplexed ligand.

The Application of Reversible Intramolecular Sulfonamide Ligation to Modulate Reactivity in Organometallic Ruthenium(II) Diamine Complexes

Metallation of biomacromolecular species forms the basis for the anticancer activity of many metallodrugs. A major limitation of these compounds is that their reactivity is indiscriminate and can, in principle, occur in healthy tissue as well as cancerous tissue, potentially leading to side effects in vivo. Here we present pH-dependent intramolecular coordination of an arene-tethered sulfonamide functionality in organometallic ruthenium(II) ethylenediamine complexes as a route to controlling the coordination environment about the central metal atom. Through variation of the sulfonamide R group and the length of the tether linking it to the arene ligand the acidity of the sulfonamide NH group, and hence the pH-region over which regulation of metal coordination occurs, can be modulated. Intramolecular sulfonamide ligation controlled the reactivity of complex 4 within the physiologically relevant pH-region, rendering it more reactive towards 5ʹ-GMP in mildly acidic pH-conditions typical of tumour tissue compared to the mildly alkaline pH-conditions typical of healthy tissue. However, the activation of 4 by ring-opening of the chelate was found to be a slow process relative to the timescale of typical cell culture assays and members of this series of complexes were found not to be cytotoxic towards the HT-29 cell line. These complexes provide the basis for the development of analogues of increased potency where intramolecular sulfonamide ligation regulates reactivity and therefore cytotoxicity in a pH-dependent, and potentially, tissue-dependent manner.