Study of the stability of violurate complexes of some d- and f-metals

The stability constants of 1: 1 and 1: 2 acidic copper(II) violurate complexes and the CuL complex, where L is the anion of violuric acid (H₂L), were determined by pH-metry at ionic strength I = 0.1 at 20°C. The stability of the violurate complexes of triply charged cations [ML]⁺ and quadruply charged thorium [ThL]²⁺ increases in the sequence La³⁺, Gd³⁺, Y³⁺, Sc³⁺, Th⁴⁺, Fe³⁺. It was shown that violuric acid behaves as either mono- or dibasic, depending on the conditions, with respect to all of these cations.     

Configuration mixing in the s-hole states of metal ions

Configuration interaction calculation have been carried out on the s-hole states of Mn²⁺ Fe²⁺ (both high- and low-spin configurations). Co²⁺, Ca²⁺, K⁺ and Na⁺ including configurations involving virtual orbitals. The results show good agreement with the multiplet structures found in X-ray photoelectron spectra of these ions.     

Characterization of a Novel Laccase LAC-Yang1 from White-Rot Fungus Pleurotus ostreatus Strain Yang1 with a Strong Ability to Degrade and Detoxify Chlorophenols

In this study, a laccase LAC-Yang1 was successfully purified from a white-rot fungus strain Pleurotus ostreatus strain yang1 with high laccase activity. The enzymatic properties of LAC-Yang1 and its ability to degrade and detoxify chlorophenols such as 2,6-dichlorophenol and 2,3,6-trichlorophenol were systematically studied. LAC-Yang1 showed a strong tolerance to extremely acidic conditions and strong stability under strong alkaline conditions (pH 9–12). LAC-Yang1 also exhibited a strong tolerance to different inhibitors (EDTA, SDS), metal ions (Mn²⁺, Cu²⁺, Mg²⁺, Na⁺, K⁺, Zn²⁺, Al³⁺, Co²⁺, and metal ion mixtures), and organic solvents (glycerol, propylene glycol). LAC-Yang1 showed good stability in the presence of Mg²⁺, Mn²⁺, glycerol, and ethylene glycol. Our results reveal the strong degradation ability of this laccase for high concentrations of chlorophenols (especially 2,6-dichlorophenol) and chlorophenol mixtures (2,6-dichlorophenol + 2,3,6-trichlorophenol). LAC-Yang1 displayed a strong tolerance toward a variety of metal ions (Na²⁺, Zn²⁺, Mn²⁺, Mg²⁺, K⁺ and metal ion mixtures) and organic solvents (glycerol, ethylene glycol) in its degradation of 2,6-dichlorophenol and 2,3,6-trichlorophenol. The phytotoxicity of 2,6-dichlorophenol treated by LAC-Yang1 was significantly reduced or eliminated. LAC-Yang1 demonstrated a good detoxification effect on 2,6-dichlorophenol while degrading this compound. In conclusion, LAC-Yang1 purified from Pleurotus ostreatus has great application value and potential in environmental biotechnology, especially the efficient degradation and detoxification of chlorophenols.     

Luminescence and optical absorption of fluorozirconate glass doped with K2MnF6

Fluorozirconate glass doped with K₂MnF₆ was produced to obtain a red-emitting phosphor, and K₂MnF₆ was synthesized according to a specially developed procedure using xenon difluoride. The luminescence spectrum exhibited a band at 550 nm attributed to Mn²⁺, and the absorption spectra belonged to Mn²⁺ and Mn³⁺ ions, which were formed due to the reduction of Mn⁴⁺ ions.     

New generation of functionalized bipyrazolic tripods: synthesis and study of their coordination properties towards metal cations

A simple and easily synthesis of new generation of N-donor bipyrazolic tripods by coupling of functionalized pyrazole derivatives and an appropriate primary amine derivative via condensation or nucleophilic substitution reaction is presented. The complexation capacity of these compounds towards bivalent metal ions (Hg²⁺, Cu²⁺, Pb²⁺, Cd²⁺) and alkaline metal ions (Li⁺, Na⁺, K⁺) were investigated using the liquid–liquid extraction process. The percentage limits of extraction were determined by atomic absorption measurements.     

Synthesis of new benzimidazolium salts with tunable emission intensities and their application as fluorescent probes for Fe in pure aqueous media

A series of novel, water-soluble benzimidazolium salts with common ‘fluorophore–spacer–receptor’ PET design has been synthesized. Despite the common PET scaffold these benzimidazolium salts displayed diverse emission intensities in pure aqueous solutions. The observed emission intensities were found to be influenced by the functionalized alkyl side arms present on the benzimidazolium ring. These benzimidazolium salts were also found to act as selective sensors for Fe³⁺ ions over other metal ions like Na⁺, K⁺, Ca²⁺, Mg²⁺, Ba²⁺, Al³⁺, Cr³⁺, Co²⁺, Ni²⁺, Mn²⁺, Zn²⁺, Pb²⁺, Ag⁺, Cu²⁺ and Hg²⁺ in pure aqueous media.     

Kinetics and Determination of Some Transition Metals with Peri-Dihydroxynaphthindenone

Abstract

A simple sensitive and selective spectrophotometric method has been developed for determination of some transition metal ions. It is based on the reaction of the metal ions with excess peri-dihydroxynaphthindenone in 80% v/v ethyl alcohol-water mixture at 30°C. The colored products obtained display maximum absorption band at 560–590 nm depending upon the type of transition metal ion used, and E_{1 cm} ^1% in the range 70–480. Under the optimum conditions results with an average recovery of 96%, (mean standard deviation ±3% are obtained for 6 different transition metal ions without any significant interference from Li⁺, Na⁺, K⁺, Cs⁺, Rb⁺, Ba²⁺, Sr²⁺, Ni²⁺, Bi³⁺, Co²⁺, Mn⁺², Cd⁺² and Al⁺³. Kinetic data reveal that the reaction proceeds via a second order route (first order with respect to either the metal cation or ligand). The activation parameters and a suggested mechanism have been presented, and the nature of bonding in the solid chelate products has been verified.     

An acyclic,dansyl based colorimetric and fluorescent chemosensor for Hg(II) via twisted intramolecular charge transfer (TICT)

An efficient fluorescent chemosensor for Hg²⁺ ion, based on 5-(dimethylamino)-N-(2-mercaptophenyl)naphthalene-1-sulfonamide, has been developed. It exhibits Hg²⁺-selective on–off fluorescence quenching behavior via twisted intramolecular charge transfer (TICT) mechanism, which is rationalized by time dependent density functional theory (TD-DFT) calculations. The system exhibits visible color change from colorless to gray upon Hg²⁺ binding with very high selectivity and sensitivity (as low as 5.0 × 10⁻¹⁰ mol L⁻¹) over other metal ions such as K⁺, Na⁺, Ag⁺, Mn²⁺, Ca²⁺, Ba²⁺, Fe²⁺, Zn²⁺, Pb²⁺, Cu²⁺, Sn²⁺, Cd²⁺, Ni²⁺ and Co²⁺. The present sensing system is also successfully applied for the detection of Hg²⁺ ion in real samples.     

Optical absorption and EPR spectroscopic studies of (30 − x)Li2O–xK2O–10CdO–59B2O3–1Fe2O3: An evidence for mixed alkali effect

Optical absorption and EPR spectroscopic studies were carried on (30 ? x)Li₂O–xK₂O–10CdO–59B₂O₃–1Fe₂O₃ (x = 0–30) glass system to understand the effect of progressive doping of Li⁺ ion with K⁺ ion. Optical absorption results show typical spectra of Fe³⁺ ions and the various optical parameters such as, optical band gap, Urbach energy, oxide ion polarizability, optical basicity and interaction parameter were evaluated from the experimental data. The observed optical band gap and Urbach energy values show large deviation from the linearity where as the other parameters show small deviation from the linearity with the progressive substitution of Li⁺ ions with K⁺ ions. The observed EPR spectra are representative of Fe³⁺ ion in octahedral and axial fields in the glass network. The number of paramagnetic centers and paramagnetic susceptibility values were evaluated at different resonance lines for all the specimens and these parameters show non-additive nature with the progressive substitution of Li⁺ ions with K⁺ ions in the glass network. This is first ever observation of mixed alkali effect (MAE) in EPR and optical parameters of mixed alkali borate glasses.     

An EPR study of manganese(II) complexes in potassium chromate single crystal

Electron paramagnetic resonance study of Mn²⁺-doped K₂CrO₄ single crystals at room temperature and liquid nitrogen temperature revealed the presence of two pairs of inequivalent Mn²⁺ complexes. It is concluded that Mn²⁺ ions are incorporated in the host substitutionally at potassium sites, and an equal number of K⁺ vacancies are created for charge compensation. The spin—Hamiltonian parameters are evaluated. The principal directions of the crystalline field experienced by the manganese (II) ion are determined and they are found to be consistent with the electrostatic considerations. The hyperfine parameters indicate the significant extent of covalent bonding of ligands with the metal ion.     

Die gravimetrische Halbmikro-Bestimmung des Palladiums mit Violursäure

Zusammenfassung Die Fällung des Palladiums als Violurat eignet sich zur Bestimmung des als Chlorid vorliegenden Metalls neben Pt⁴⁺, Co²⁺, Ni²⁺, Fe³⁺, Cu²⁺, Mn²⁺, Zn²⁺, Ca²⁺, den Alkalien und neben größeren Mengen von Pb²⁺-Ionen.

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Summary The precipitation of palladium as violurate is suitable for the determination of the metal present as chloride even in the presence of: Pt⁴⁺, Co²⁺, Ni²⁺, Fe³⁺, Cu²⁺, Mn²⁺, Zn²⁺, Ca²⁺, the alkalis and also considerable amounts of Pb²⁺ ions.

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Résumé Le précipité de violurate de palladium convient pour le dosage de cet élément préexistant sous forme de chlorure, en présence de Pt⁴⁺, Co²⁺, Ni²⁺, Fe³⁺, Cu²⁺, Mn²⁺, Zn²⁺, Ca²⁺, des métaux alcalins et de grandes quantités d'ions Pb²⁺.

     

EPR spectroscopic studies in (30 − x) Li2O-xK2O-10CdO-59B2O3-1MnO2 multi-component glass system

EPR studies were carried out in (30 - x) Li₂O-xK₂O-10CdO-59B₂O₃-1MnO₂ multi-component glass system to understand the effect of the variation in the alkali ratios on the EPR parameters. The observed EPR spectra of Mn²⁺ ion exhibits resonances at g = 2.0, 3.3 and 4.3. The resonance at g = 2.0 is due to Mn²⁺ ions in an environment close to the octahedral symmetry, where as the resonances at g = 3.3 & 4.3 are due to the rhombic surroundings of Mn²⁺ ions. Hyperfine splitting constant values at g = 2.0 and number of paramagnetic centers & paramagnetic susceptibility at different observed resonances were evaluated. These parameters show non linear variation with progressive substitution of Li⁺ ion with K⁺ ions may be due to the changes in cation field strengths and local structural variation due to the variation in mixed alkali ion ratios.     

DDB liver drug as a novel ionophore for potentiometric barium (II) membrane sensor

Dimethyl-4,4-dimethoxy-5,6,5′,6′-dimethylene dioxy biphenyl-2,2-dicarboxylate (DDB) liver drug is used as a novel ionophore in plasticized poly (vinyl chloride) (PVC) matrix membrane sensors for barium ions. Optimum performance characteristics are displayed by membrane sensor incorporating DDB ionophore, potassium tetrakis(4-chlorophenyl)borate as lipophilic salt, and o-nitrophenyloctyl ether as plasticizer. The sensor exhibits a linear response over the concentration range 10⁻¹-10⁻⁵ mol l⁻¹ BaCl₂ with a Nernstian slope of 30 mV per decade and high selectivity towards Ba²⁺ with respect to Li⁺, Na⁺, K⁺, Rb⁺, NH₄⁺, Mg²⁺, Ca²⁺, Sr²⁺, Mn²⁺, Co²⁺, Ni²⁺, Cd²⁺, Al³⁺, La³⁺, and Ce³⁺ ions. The sensor response is stable over a wide pH range (4-9) and the lifetime is about 2 months. The proposed sensor is successfully applied to the determination of Ba²⁺contents of some rocks.     

A Highly Selective and Sensitive Fluorescent Chemosensor for Detection of Al3+ in Totally Aqueous Media

A fluorescent chemosensor ( 1 ) based on 2‐hydroxy‐1‐naphthaldehyde Schiff‐base was developed for the detection of Al³⁺ in 100% aqueous solution. Upon addition of Al³⁺, a significant fluorescence enhancement was observed, which was not affected by other metal ions including Na⁺, K⁺, Ca²⁺, Mg²⁺, Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Cr³⁺, Ag⁺, Pb²⁺, Zn²⁺, Cd²⁺, Hg²⁺, Fe²⁺ and Fe³⁺ under weak acid conditions. Moreover, the specific response to Al³⁺ was visible under natural light. The binding mode between 1 and Al³⁺ was clarified by ESI‐MS and ¹H NMR.     

Preparation and electrochemical properties of nano-sized cryptomelane particles for the formation of potentiometric potassium ion sensors

The potentiometric response of 100-nm spherical K_1.3Mn₈O₁₆ particles versus K⁺ ions has been studied in aqueous media using a polymeric technology. The stoichiometry of this material evolves in potassium nitrate solution towards K_1.08Mn₈O₁₆. A stable and reversible response has been obtained with a sensitivity of 47 mV dec^?1 in the range from 8?×?10^?5 to 1 mol·L^?1, and a rather good selectivity towards Li⁺, Na⁺, Mg²⁺ and Ca²⁺ $\left( {{\text{log K}}_{{{{\text{K}}^{\text{ + }} } \mathord{\left/ {\vphantom {{{\text{K}}^{\text{ + }} } {{\text{X}}^{n + } }}} \right. \kern-0em} {{\text{X}}^{n + } }}} \approx - {\text{3}}} \right)$ . We assume that this potentiometric response is the result of the ability of K_1.08Mn₈O₁₆ to specifically adsorb K⁺ ions.     

Probing the interaction of alkali and transition metal ions with bradykinin and its des-arginine derivatives via matrix-assisted laser desorption/ionization and postsource decay mass spectrometry

The complexes of the peptides (Pep) bradykinin (RPPGFSPFR), des-Arg¹-bradykinin, and des-Arg⁹-bradykinin with the metal (M) ions Na⁺, K⁺, Cs⁺, Cu⁺, Ag⁺, Co²⁺, Ni²⁺, and Zn²⁺ are generated in the gas phase by matrix-assisted laser desorption/ionization and the structures of the corresponding [Pep + M⁺]⁺ or [Pep − H⁺ + M²⁺]⁺ cations are probed by postsource decay (PSD) mass spectrometry. The PSD spectra depend significantly on the metal ion attached; moreover, the various metal ions respond differently to the presence or absence of a basic arginine residue. The Na⁺ and K⁺ adducts of all three peptides mainly produce N-terminal sequence ions upon PSD; the fragments observed point out that these metal ions are anchored by the PPGF segment and not the arginine residue(s). In contrast, the adducts of Cu⁺ and Ag⁺ show a strong dependence on the position of Arg; complexes of des-Arg¹-Pep (which contains a C-terminal Arg) produce primarily y_n ions whereas those of des-Arg⁹-Pep generate exclusively a_n and b_n ions. These trends are consistent with Cu⁺ ligation by Arg’s guanidine group. The [Pep + Cs⁺]⁺ ions mainly yield Cs⁺; a second significant fragmentation occurs only if a C-terminal arginine is present and involves elimination of this arginine’s side chain plus water. This reaction is rationalized through a salt bridge mechanism. The most prominent PSD products from [Pep − H⁺ + Co²⁺]⁺ and [Pep − H⁺ + Ni²⁺]⁺ contain at least one phenylalanine residue, revealing a marked preference for these divalent metal ions to bind to aromatic rings; the fragmentation patterns of the complexes further suggest that Co²⁺ and Ni²⁺ bind to deprotonated amide nitrogens. The coordination chemistry of Zn²⁺ combines features found with the divalent Co²⁺/Ni²⁺ as well as the monovalent Cu⁺/Ag⁺ transition metal ions. Generally, the structure and fragmentation behavior of each complex reflects the intrinsic coordination preferences of the corresponding metal ion.     

Tridentate benzimidazole ligand and its metal complexes: Synthesis,characterization, photo physical and sensor properties

A tridentate bisbenzimidazole-pyridine ligand (L-C⁵) with two pentyl side-units and its metal complexes with Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺ metal ions were synthesized and characterized. The structures of the ligand (L-C⁵) and its five coordinate [Mn(L-C⁵)Cl₂] were elucidated by single crystal X-ray diffraction studies. The absorption and photoluminescence properties of the compounds were studied in solution media. The ligand is highly fluorescent, and binding of the metal ions to the ligand has caused significant changes in the emission band (shift or quenching). Moreover, the effect of aggregation on UV–Vis. absorption and emission properties was examined in MeOH-water mixtures. The ligand was found to show aggregation-induced quenching in the MeOH-water mixture. The ligand was also screened for its colorimetric and fluorometric sensing ability of several metal ions [Na⁺, K⁺, Mg²⁺, Al³⁺, Ca²⁺, Mn²⁺, Fe²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Hg²⁺, Pb²⁺]. The ligand showed selective sensing ability towards Zn²⁺, and the limit of detection was calculated as 3.09 × 10⁻⁷ m . The ligand also showed a distinguishable color change in the presence of Fe²⁺ under daylight.     

Evaluation of Metal Ions and Surfactants Effect on Cell Growth and Exopolysaccharide Production in Two-Stage Submerged Culture of Cordyceps militaris

During the two-stage submerged fermentation of medicinal mushroom Cordyceps militaris, it was found that K⁺, Ca²⁺, Mg²⁺, and Mn²⁺ were favorable to the mycelial growth. The EPS production reached the highest levels in the media containing Mg²⁺ and Mn²⁺. However, Ca²⁺ and K⁺ almost failed to increase significantly exopolysaccharides (EPS) production. Sodium dodecyl sulfate (SDS) significantly enhanced EPS production compared with that of without adding SDS when SDS was added on static culture stage of two-stage cultivation process. The presence of Tween 80 in the medium not only simulated mycelial growth but also increased EPS production. By response surface methods (RSM), EPS production reached its peak value of 3.28?g/L under optimal combination of 27.6?mM Mg²⁺, 11.1?mM Mn²⁺, and 0.05?mM SDS, which was 3.76-fold compared with that of without metal ion and surfactant. The results obtained were useful in better understanding the regulation for efficient production of EPS of C. militaris in the two-stage submerged culture.     

Fluorescent chemosensor based-on naphthol-quinoline for selective detection of aluminum ions

In this study, an assay to quantify the presence of aluminum ions with a receptor containing naphthol and quinoline moieties was developed using a turn-on fluorescence enhancement approach. Upon treatment with aluminum ions, the fluorescence of the receptor was enhanced at 510 nm due to the formation of a complex between the ligand and aluminum ions at room temperature. As the concentration of Al³⁺ was increased, the fluorescence gradually increased. Other metal ions, such as K⁺, Ag⁺, Ca²⁺, Mg²⁺, Zn²⁺, Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Cd²⁺, Cr³⁺, Fe³⁺, In³⁺, had no significant effect on the fluorescence.