Metal chelates of ampicillin versus amoxicillin: synthesis,structural investigation,and biological studies

Solid chelates derived from some alkaline earth and transition metal complexes with ampicillin (Hamp, a) and amoxicillin (Hamox, b) were synthesized and characterized using elemental analysis, molar conductivity, IR, magnetic susceptibility, and thermogravimetric studies. Both drugs behave as tetradentate ligands coordinating to metal through amino, imino, and carboxylate as well as through β-lactamic carbonyl. All chelates have octahedral geometry except Cu(II) complexes which have square planar structure and uranium has pentagonal bipyramidal coordination. ¹H- and ¹³C-NMR of the Zn(II) and UO₂(VI) chelates are compared with the free ligands. The antimicrobial activity of the prepared chelates was determined.     

COMPLEXES OF GALLIUM(III) WITH HYDROXYAROMATIC LIGANDS

Abstract

The equilibria between gallium(III) ion and selected hydroxyaromatic and dihydroxyaromatic ligands at 25°C, μ=0.100 M (KNO₃) have been determined. Potentiometric measurements on 1:1, 2:1, and 3:1 molar ratios of ligand to Ga(III) have been made as a function of degree of neutralization over the entire accessible ?log [H⁺] scale. Calculations were carried out so as to take account of competing hydrolytic reactions, and formation constants of gallium(III) with chromotropic acid, 8-hydroxyquinoline-5-sulfonic acid, 5-sulfosalicylic acid, and 1,2-dihydroxy-benzene-3,5-disulfonic acid were obtained. Stable hydroxo chelates do not form under the reaction conditions employed. The protonation constants of the ligands and the formation constants of the gallium chelates are discussed and compared with previously published work on these gallium chelates and on chelates of “analogous” metal ions such as those of Fe(III) and A1(III).     

High-performance liquid chromatographic determination of nickel,copper and zinc as their tetraphenylporphine chelates

Nickel(II), copper(II) and zinc(II) ions are extracted from an aqueous solution into carbon tetrachloride as their diethyldithiocarbamate (DDC) chelates. The extract, after removal of the solvent, is treated with meso-tetraphenylporphine (TPP) in benzyl alcohol at 140°C for 60 min. Quantitative conversion of the DDC chelate to the TPP chelate is obtained over the range 0.25–4.5 μg of each metal by use of 3 μgmol of TPP. The reaction mixture is analysed by reversed-phase high-performance liquid chromatography with spectrophotometric detection at 412 nm. Simultaneous determination of Cu and Zn in NBS bovine liver is possible by this procedure.     

Distribution of metal chelates between aqueous and surfactant phases separated from a micellar solution of a nonionic surfactant

A dilute micellar solution of poly(oxyethylene) 4-nonylphenyl ether with oxyethylene units 7.5 (PONPE-7.5) was separated into two phases (aqueous and surfactant phases) at room temperature. The partition constants of several chelating reagents and their metal chelates between the two phases were determined at 293 K and ionic strength 0.1 (NaClO₄). The partition constants of the neutral metal chelates depend on the kind of metal ions and were considerably smaller than those expected from the regular solution theory. These facts suggested that the chelates were incorporated into a hydrocarbon environment in the surfactant phase, whereas the chelating reagents were distributed in the poly(oxyethylene) part of PONPE-7.5. A brief review was also presented on the analytical applications to the extraction of metal ions and organic compounds.     

The High Pressure Liquid Chromatogrpaphy of Metal Chelates of Diethyldithiocarbmic Acid and Dithizone

Abstract

The HPLC behavior of Ni(II), Co(III), Cu(II), Zn(II), Cd(II), Hg(II) and Pb(II) chelates of diethyldithiocarbamic acid, H(DDTC), and dithizone, H(D_z), was studied on silica gel columns with toluene as the mobile phase. Calibration plots gave linear results for plots of peak area vs. amount of metal injected over the low nanogram to milligramrange. Calibration plots for the above cations were determined on the basis of 3 to 5 replicate determinations for 8 to 10 different concentration levels over the above range with a relative standard deviation less than 5.0% for all metals studied. A variable wavelength photometric detector was used and the detection limits at 270 nm were in the range of 5 to 200 ng depending on the metal species. The best separations were obtained on a1/4″ × 35 cm stainless-steel packed with 10 micron μ-Porasil.     

Polymer-Metal Complexes: Synthesis and Characterization of Poly-(2-Hydroxy-4-acryloxyacetophenone-semicarbazone) Metal Complexes

Abstract

2-Hydroxy-4-acryloxyacetophenone (HAAP) was synthesized and polymerized in 2-butanone using benzoyl peroxide as initiator at 65 °CC. Poly(2-hydroxy-4-acryloxyacetophenone-semicarbazone) (HAAPS) was prepared from poly(HAAP) and semicarbazide hydrochloride and was characterized by IR and NMR spectral studies. The molecular weights of the polymer was determined by gel permeation chromatography. Cu(II) and Ni(II) chelates of poly(HAAPS) were synthesized. Thermogravimetric analysis of the polychelates have been carried out. Elemental analysis of the poly chelates suggest a metal to ligand ratio as 1:2. The polychelates were also characterized by infrared, electronic spectral studies, magnetic, and conductivity measurements.     

Thin-Layer Chromatographic Separation of Copper and Mercury Chelates

Abstract

Thin-layer chromatographic separation of metal ions has become immensely popular in analytical chemistry in view of its speed, selectivity and applicability at tracer level. Quinoline-2-aldehyde thiosemicarbazone^1,2 was found to form yellow coloured chelates with metal ions such as copper, nickel, zinc, mercury, iron and lead at pH 7.5 and extract into chloroform. This, however reduces the sensitivity of the reagent as a chromogenic agent but the chromatographic run of the chelates on a thin layer of silica gel coated on glass plate increases the specificity and selectivity of the reagent. In this article we propose a method for separation of copper and mercury chelates from binary mixtures containing chelates of zinc, lead, iron and nickel. The method is applicable for analysis of synthetic mixtures and standard samples.     

Water and Organic Solvent Adducts on Metal Chelates

Abstract

The number of water and organic solvent molecule adducts surrounding several ligands and metal chelates were determined in both the aqueous and organic phases. Data is presented to show that these adducts change in number during an extraction.     

Spectrophotometric Studies of Nickel(II) and Copper(II) Chelates of p-(2-Hydroxy-1-Naphthylazo)-Benzenesulphonate

The ionization constant of p-(2-hydroxy-1-naphthylazo)benzene-sulphonate (Orange II) and the formation constants of the metal chelates of this reagent with Ni(II) and Cu(II) have been determined spectrophotometrically in aqueous solution at 25° and at an ionic strength of 0.10M. The ionization constant of orange II was found to be pK_a=10.95. Formation of orange II chelates with Ni(II) and Cu(II) was pH dependent, and the optimum pH range of the Ni(II) Chelate was at pH 9.2-9.4, and Cu(II) chelate at 9.5-9.7, respectively. The mole ratio of orange II to both of metal ions was found to be 2 to 1 stoichiometry. The formation constants (logK) of the Ni(II) and Cu(II) chelates were 12.50 and 16.11, respectively. The molar extinction coefficients and the photometric sensitivities of these chelates were determined.     

Novel Synthesis of Aza-phthalimidine Hydroxylactams

A novel and convenient synthetic route for preparing aza-phthalimidine hydroxylactams (5a–j) by N-bromosuccinimide (NBS) was developed. This method involved the substitution reactions of substrates (3a–j) with NBS via unstable intermediate bromides (4a–j) rapidly hydrolyzed into hydroxyl products in the course of the workup process.     

Perchlorate Ion-Selective Electrodes with the Liquid Membranes of the O-Phenanthroline Chelate or its Related Compounds

Abstract

The metal chelates of o-phenanthroline, a, a′-dipyridyl or bathophenanthroline were used as the ion exchanger in the liquid membrane of the perchlorate ion-selective electrode. The electrode with a nitrobenzene membrane containing tris(bathophenanthroline)ferrous perchlorate is the highest sensitive one and gives a linear Nernstian response up to about 1 × 10 ^?5 M perchlorate. The membrane electrode having the ferrous ion-chelate of o-phenanthroline as an ion exchanger shows an excellent selectivity for perchlorate ion over nitrate or iodide Ion. The effects of the chelate concentration in the membrane and the central metal species of the chelate are examined on the electrode performance.     

Synthesis,DNA-binding,and cytotoxic studies on three copper(II) complexes of unsymmetrical synthetic analogues of curcumin

Copper(II) chelates of three unsymmetrical synthetic analogs of curcumin, namely (2E)-2-(4-hydroxy-3-methoxybenzylidene)-5-((E)-3-(4-hydroxy-3-methoxyphenyl)acryloyl)cyclopentanone(1), (2E)-2-(3,4-dihydroxybenzylidene)-5-((E)-3-(3,4-dihydroxyphenyl)acryloyl)cyclopentanone(2), and (2E)-2-(3,4-dimethoxybenzylidene)-5-((E)-3-(3,4-dimethoxyphenyl)acryloyl)cyclopeantanone(3) have been synthesized and characterized by physicochemical and spectroscopic methods. The ligands were in their enolic form and metal complexes have 1 : 2 metal:ligand stoichiometry. The DNA-binding properties of the ligands and their metal complexes were studied by absorption titrations, fluorescence quenching experiments, and viscosity measurements with calf-thymus DNA. The interactions of copper(II) complexes were higher than that of free ligands. The observed intrinsic binding constants reveal moderate interaction of copper(II) complexes with calf-thymus DNA. The binding involves intercalative mode through non-covalent interactions and produced conformational changes in the structure of DNA. The compounds were investigated for their possible cytotoxic and antitumor activities. All the compounds were cytotoxic towards Dalton’s lymphoma ascites cells. It was found that copper chelates are remarkably active compared to free curcumin analogs. Concentrations needed for 50% cell death were 10–22 μg mL^?1 for copper complexes and 27–52 μg mL^?1 for curcumin analogs. Copper complex of 2 with two hydroxyl groups in the phenyl ring was most active towards Dalton’s lymphoma ascites cells (increase in life span 77.91%). Copper(II) complex of 3, which possesses methoxy groups in the phenyl ring system, showed the lowest activity towards increase in lifespan of tumor-bearing mice (increase in lifespan 60.14%). Copper chelates of all curcuminoid analogs showed a significant reduction in solid tumor volume in mice.     

Incorporation of transition metals into Mg-Al layered double hydroxides: Coprecipitation of cations vs. their pre-complexation with an anionic chelator

A comparative study on two different methods for preparing Mg-Al layered double hydroxides (LDH) containing various divalent transition metals M (M=Co, Ni, Cu) has been carried out. The first (conventional) method involved coprecipitation of divalent metals M(II) with Mg(II) and Al(III) cations using carbonate under basic conditions. The second approach was based on the ability of transition metals to form stable anionic chelates with edta⁴⁻ (edta⁴⁻=ethylenediaminetetraacetate) that were synthesized and further introduced into LDH by coprecipitation with Mg and Al. The synthesized LDHs were characterized by X-ray diffraction (XRD) and X-ray fluorescence (XRF) methods, thermogravimetry with mass-selective detection of decomposition products (TG-MSD), Fourier transform infrared (FTIR) and Raman spectroscopy techniques. The results obtained were discussed in terms of efficiency of transition metal incorporation into the LDH structure, thermal stability of materials and the ability of metal chelates to intercalate the interlayer space of Mg-Al LDH. Vibrational spectroscopy studies confirmed that the integrity of the metal chelates was preserved upon incorporation into the LDH.     

Chalcogen-containing metal chelates as single-source precursors of nanostructured materials: recent advances and future development

Abstract

The analysis of the use of chalcogenide metal chelates as single-source precursors of nanostructured materials has been carried out. The influence of the nature of the ligand, temperature, capping agents, thermolysis time, and solvent on the kinetic laws of thermolysis and the properties of the resulting nanomaterials is considered. Particular attention is paid to thermolysis of polynuclear chalcogenide metal chelates. The basic data on the synthesis of metal-polymer nanocomposites by thermolysis of chalcogenide metal chelates in the presence of polymers are summarized. The problems and future prospects of obtaining nanostructured materials by thermolysis of chalcogenide metal chelates are outlined. The bibliography includes articles published during the last 5 years.     

Gel Chromatography of Metal Acetylacetonates in Organic Solvents

Abstract

Tris (acetylacetonato)cobalt(III) and tris(acetylacetonato)-chromium(III) have been eluted by gel chromatography through styrene-divinylbenzene copolymer gel using an organic solvent as an eluent. Elution counts of these chelates in these solvents reflect some mutual interactions between metal chelate, gel and solvent. When benzene or chloroform was used as an eluent, sieving effect seems to be dominant for the separation of these chelates. Discussions were done in relation to solubility parameters of the solvent, the complex and the gel.     

Preparation and reactivity of metal-containing monomers

The stability of chelates of several bivalent metals with poly(methacryloylacetone) was determined by pH titration. Two models in which the fragment of a polymeric molecule in the coordination sphere of a metal was approximated by either a mono- or a bidentate ligand were considered. Different mechanisms of complex formnation were realized depending on the nature of M(II).For part 29 seeIzv. Akad. Nauk, Ser. Khim., 1993, 975 [Russ. Chem. Bull., 1993,42, 937 (Eng.Transl.)].Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1063–1066, June, 1993.     

Studies in heavy ion activation analysis

A procedure for measuring trace amounts of Li and Be in different types of samples has been studied using a 12.5 MeV¹⁴N beam. At this energy the principal nuclear reactions are⁶Li(¹⁴N, d)¹⁸F,⁷Li(¹⁴N, t)¹⁸F, and⁹Be(¹⁴N, αn)¹⁸F. Detection limit for destructive analysis for either beryllium or lithium has been calculated at 300 ppb with a determination limit of 5 ppm for an irradiation with a beam of 1 μA·h/cm². Destructive analysis was performed on CANMET SY-2 and USGS BCR-1 (rock samples 1–10 ppm Be). Non-destructive analysis for beryllium and lithium was performed on NBS SRM 610 (500 ppm trace element glass), NBS 612 (50 ppm trace element glass), and NBS SRM 181 (Spodumene ore, 6.4% Li₂O). Detection limit of 2 ppm has been calculated for nondestructive analysis of either lithium or beryllium.     

Equilibrium analysis of reactions of metal-pyridylazoresorcinolato chelates with quaternary ammonium ion, nonionic surfactant and polyethylene glycol in aqueous solution by capillary zone electrophoresis.

The resolutions of metal-4-(2-pyridylazo)resorcinol chelates by capillary zone electrophoresis (CZE) were investigated in the presence of some interacting reagents; also, equilibrium reactions between the chelates and the interacting reagents were analyzed in an aqueous solution. Among nine metal chelates formed in aqueous solution, the chelates of VV, FeII, CoIII, NiII, and CuII were resolved and detected by CZE, while other chelates were decomposed during electrophoretic migration. The electrophoretic mobility of the chelates of FeII, NiII, and CuII increased with increasing pH of the migrating solution; also, the acid-dissociation constants of these three chelates were determined by analyzing the mobility change. The ion-association constants of the five anionic chelates and pyridylazoresorcinolate ion with quaternary ammonium ions were also determined by analyzing the mobility change. The binding behavior of the ligand and its chelates with nonionic surfactant micelle, as well as with polyethylene glycol, were investigated, and their binding constants were determined through the mobility change. When Brij 35 was used as a nonionic surfactant interacting with the anionic chelates, the FeII chelate decomposed at Brij 35 concentrations over 6.67 mM. The equilibrium constants and the reactivity were compared with each other.     

Crystal Structures of DOTMA Chelates from Ce3+ to Yb3+: Evidence for a Continuum of Metal Ion Hydration States

The crystal structures of chelates formed between each stable paramagnetic lanthanide ion and the octadentate polyamino carboxylate ligand DOTMA are described. A total of 23 individual chelates structures were obtained; in each chelate the coordination geometry around the metal ion is best described as a twisted square antiprism (torsion angle −25.0°–−31.4°). Despite the uniformity of the general coordination geometry provided by the DOTMA ligand, there is a considerable variation in the hydration state of each chelate. The early Ln³⁺ chelates are associated with a single inner sphere water molecule; the Ln-OH₂ interaction is remarkable for being very long. After a clear break at gadolinium, the number of chelates in the unit cell that have a water molecule interacting with the Ln³⁺ decreases linearly until at Tm³⁺ no water is found to interact with the metal ion. The Ln-OH₂ distance observed in the chelates of the later Ln³⁺ ions are also extremely long and increase as the ions contract (2.550–2.732 Å). No clear break between hydrated and dehydrated chelates is observed; rather this series of chelates appear to represent a continuum of hydration states in which the ligand gradually closes around the metal ion as its ionic radius decreases (with decreased hydration) and the metal drops down into the coordination cage.     

Novel mono-and binuclear complexes of Cu(II) with hydrazones of salicylaldehyde derivatives

A series of new mono-and binuclear metal chelates of Cu(II) with ligands, which are the products of condensation of 3,5-di(tert-butyl)salicylaldehyde with hetarylhydrazines or 4-phenylsemi(thiosemi)carbazide, were synthesized. Their compositions and structures were determined by the elemental analysis, IR and ¹H NMR spectroscopies, magnetochemistry, and conductometry measurements. It was shown for the first time that in the case of hetarylhydrazones, only mononuclear complexes were formed due to steric effect of tert-butyl fragments, whereas arylhydrazones gave binuclear complexes with two Cu atoms bonded by the spin-spin interaction. The exchange parameters 2J were calculated for binuclear metal chelates.