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1.
Abstract

The formation constants of ternary complexes of title systems have been determined pH-metrically in biologically relevant conditions at an ionic strength of 0.16 mol dm-3 and 303 K. The overall stability constants have been evaluated using MINIQUAD75 computer program. The complexation equilibria have been derived on the basis of species distribution diagram. In the present study L-Dopa and 1, 10-phenanthroline are found to be compatible ligands, proving greater stability of ternary complexes as compared to binary ones. The trend in variation of stability constants with change in dielectric constant of medium is explained on the basis of electrostatic and non-electrostatic forces. Distributions of the species with pH at different compositions of propanediol-water mixtures are also presented. The factors responsible for the compatibility of both the ligands have also been discussed.  相似文献   

2.
3.
The effects of free mercury(II), cadmium(II) and lead(II) ions and their metalloporphyrin-derivatives on Trypanosoma brucei brucei growth in culture were studied. All experiments were conducted in the dark. IC(50) values on growth obtained in 24-h time-course experiments were 1.5 x 10(-7), 2.4 x 10(-6), 4.4 x 10(-6) and 2.6 x 10(-5) M for mercury(II) porphyrin, cadmium(II) porphyrin, lead(II) porphyrin and free base porphyrin, respectively. While the IC50 values for Hg2+, Cd2+ and Pb2+ were 3.6 x 10(-6), 1.5 x 10(-5) and 1.6 x 10(-5) M, respectively. These results clearly indicate that the toxicity of the metalloporphyrin complexes of mercury(II), cadmium(II) and lead(II) to T. b. brucei parasites was much higher compared to their free metal ions and free base porphyrin at low concentrations. It was also observed after 8 h incubation that the metalloporphyrins were effective in inhibiting the division of the parasites at concentrations >1.25 x 10(-7) M for mercury(II) porphyrin, concentrations >1.2 x 10(-6) M for cadmium(II) and lead(II) porphyrins and at concentrations >3.6 x 10(-6) M for Hg2+ ion. These observations were not detected in samples treated with the free metal ions and the free base porphyrin at the same concentrations. Interestingly, trypanosomes treated with metalloporphyrin complexes displayed different morphological features from those cells treated with free base porphyrin or metal ions. The chemotherapeutic potential of the metalloporphyrins of H2TMPyP for treatment of African trypanosomiasis is discussed.  相似文献   

4.
The toxicity of soft metals is of broad interest to microbiologists, both because such metals influence the community structures in natural environments and because several metals are used as antimicrobial agents. Their potency roughly parallels their thiophilicity, suggesting that their primary biological targets are likely to be enzymes that contain key sulfhydryl moieties. A recent study determined that copper poisons Escherichia coli in part by attacking the exposed [4Fe-4S] clusters of dehydratases. The present investigation sought to test whether other soft metals also target these enzymes. In vitro experiments revealed that low-micromolar concentrations of Ag(I) and Hg(II) directly inactivated purified fumarase A, a member of the dehydratase family. The enzyme was also poisoned by higher levels of Cd(II) and Zn(II), but it was unaffected by even millimolar concentrations of Mn(II), Co(II), Ni(II), and Pb(II). Electron paramagnetic resonance analysis and measurements of released iron confirmed that damage was associated with destruction of the [4Fe-4S] cluster, and indeed, the reconstruction of the cluster fully restored activity. Growth studies were then performed to test whether dehydratase damage might underlie toxicity in vivo. Barely toxic doses of Ag(I), Hg(II), Cd(II), and Zn(II) inactivated all tested members of the [4Fe-4S] dehydratase family. Again, activity was recovered when the clusters were rebuilt. The metals did not diminish the activities of other sampled enzymes, including NADH dehydrogenase I, an iron-sulfur protein whose clusters are shielded by polypeptide. Thus, the data indicate that dehydratases are damaged by the concentrations of metals that initiate bacteriostasis.  相似文献   

5.
Complexes of the type [M(bssdh)]Cl and [M(dspdh)]Cl, where M = Co(II), Ni(II), Cu(II), Zn(II) and Cd(II); Hbssdh = benzil salicylaldehyde succinic acid dihydrazone, Hdspdh = diacetyl salicylaldehyde phthalic acid dihydrazone have been synthesized and characterized with the help of elemental analyses, electrical conductance, magnetic susceptibility measurements, electronic, ESR and IR spectra and X–ray diffraction studies. Magnetic moment values and electronic spectral transitions indicate a spin free octahedral structure for Co(II), Ni(II) and Cu(II) complexes. IR spectral studies suggest that both the ligands behave as monobasic hexadentate ligands coordinating through three > C = O, two > C = N– and a phenolate group to the metal. ESR spectra of Cu(II) complexes are axial type and suggest as the ground state. X–ray powder diffraction parameters for [Co(bssdh)]Cl and [Co(dspdh)]Cl complexes correspond to an orthorhombic crystal lattice. The ligands as well as their metal complexes show a significant antifungal and antibacterial activity against various fungi and bacteria. The metal complexes are more active than the parent ligands.  相似文献   

6.
Complexes of the type [M(bssdh)]Cl and [M(dspdh)]Cl, where M = Co(II), Ni(II), Cu(II), Zn(II) and Cd(II); Hbssdh = benzil salicylaldehyde succinic acid dihydrazone, Hdspdh = diacetyl salicylaldehyde phthalic acid dihydrazone have been synthesized and characterized with the help of elemental analyses, electrical conductance, magnetic susceptibility measurements, electronic, ESR and IR spectra and X-ray diffraction studies. Magnetic moment values and electronic spectral transitions indicate a spin free octahedral structure for Co(II), Ni(II) and Cu(II) complexes. IR spectral studies suggest that both the ligands behave as monobasic hexadentate ligands coordinating through three > C = O, two > C = N- and a phenolate group to the metal. ESR spectra of Cu(II) complexes are axial type and suggest d(x(2)-y(2)) as the ground state. X-ray powder diffraction parameters for [Co(bssdh)]Cl and [Co(dspdh)]Cl complexes correspond to an orthorhombic crystal lattice. The ligands as well as their metal complexes show a significant antifungal and antibacterial activity against various fungi and bacteria. The metal complexes are more active than the parent ligands.  相似文献   

7.
The chelating behavior of 2,6-diacetylpyridine bis(2-aminobenzoylhydrazone) (H2dapa) towards manganese(II), cadmium(II) and oxovanadium(IV) ions has been studied by elemental analyses, conductance measurements, magnetic properties and spectral (IR, 1H NMR, UV-Vis and EPR) studies. The IR spectral studies suggest the pentadentate nature of the ligand with pyridine nitrogen, two azomethine nitrogens and two carbonyl oxygen atoms as the ligating sites. Six coordinate structure for [VO(H2dapa)]SO4 · H2O and seven coordinate structures for [Mn(H2dapa)(Cl)(H2O)]Cl · 2H2O and [Cd(H2dapa)Cl2] · H2O complexes have been proposed. Pentagonal bipyramidal geometry for [Mn(H2dapa)(Cl)(H2O)]Cl · 2H2O and [Cd(H2dapa)(Cl2)] · H2O complexes was confirmed by single crystal analysis. The X-band EPR spectra of the oxovanadium(IV) and manganese(II) complexes in the polycrystalline state at room (300 K) and also at liquid nitrogen temperature (77 K) were recorded and their salient features are reported.  相似文献   

8.
Seven cadmium complexes: [CdX2(Hapro)(H2O)n] (X: Cl(1), Br(2)), [CdX2(Hgaba)] (X: Cl(3), Br(4)), [Cd(Hahex)2(H2O)2][CdCl4] (5), and [CdX2(Haze-3)](H2O)n (X: Cl(6), Br(7)) have been prepared and investigated by means of IR and FT Raman spectra. The crystal and molecular structures of 2, 3, 5 and 7 were determined by a single-crystal X-ray diffraction method. In complex 2, the cadmium atom is in a distorted octahedral geometry, ligated by two carboxyl oxygen atoms of Hapro, a water molecule, and three bromine atoms; one is terminal and each of the other two is bridging two cadmium atoms to make a polymer. The structure of 3 consists of one-dimensional polymers bridged by two chlorine atoms and a carboxyl group. The carboxyl oxygen atoms of Hgaba coordinate forkedly to two cadmium atoms. The cadmium atom of [Cd(Hahex)2(H2O)2]2+ in complex 5 is in a distorted octahedral geometry, ligated by four carboxyl oxygen atoms of two molecules of Hahex and by two water molecules. [Cd(Hahex)2(H2O)2]2+ exists between two layers which are formed of infinite [CdCl4]2- chains. The carboxyl oxygen atoms of Hahex coordinate to the same cadmium atom. In complex 7, the cadmium atom is ligated by two carboxyl oxygen atoms and four bridging bromine atoms to make a polymer.  相似文献   

9.
Reactions of the 1:2 condensate (L) of benzil dihydrazone and 2-acetylpyridine with Hg(ClO4)2 · xH2O and HgI2 yield yellow [HgL2](ClO4)2 (1) and HgLI2 (2), respectively. Homoleptic 1 is a 8-coordinate double helical complex with a Hg(II)N8 core crystallising in the space group Pbca with cell dimensions: a = 16.2250(3), b = 20.9563(7), c = 31.9886(11) Å. Complex 2 is a 4-coordinate single helical complex having a Hg(II)N2I2 core crystallising in the space group P21/n with cell dimensions a = 9.8011(3), b = 17.6736(6), c = 16.7123(6) Å and β = 95.760(3)o. In complex 1, the N-donor ligand L uses all of its binding sites to act as tetradentate. On the other hand, it acts as a bidentate N-donor ligand in 2 giving rise to a dangling part. From variable temperature 1H NMR studies both the complexes are found to be stereochemically non-rigid in solution. In the case of 2, the solution process involves wrapping up of the dangling part of L around the metal.  相似文献   

10.
Vitamin K3-thiosemicarbazone (C12H11N3NaO4S2 x 5H2O, abbreviated as VT), a new Schiff base derivative, has been synthesized. Its crystal structure, determined by X-ray diffraction, is triclinic, space group P1. We have also prepared five novel complexes of VT with transition metals: [M(VT)(2)2H2O] x nH2O, (n = 1 and 2 for M = Cu(II) and Zn(II), respectively) and [M'(HVT)2Cl2] x mH2O, (m = 4, 5, and 7 for M' = Co(II), Mn(II), and Ni(II), respectively). These compounds were characterized by IR and UV-Vis spectroscopy, molar conductivity, thermal analyses, complexometric titration, and elemental analysis. In all the complexes, the VT ligand coordinates through sulfur and oxygen atoms, and the geometry around metal atom is best described as octahedral. In vitro tests of antibacterial activity showed that VT and its complexes with Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) all had strong inhibitory actions against G(+) Staphylococcus aureus, G(+) Hay bacillus, and G(-) Escherichia coli.  相似文献   

11.
As a part of our study on iron reduction-mobilization in biological systems, in particular at root-soil interface, the effect of the addition of different metal ions to the iron(III)-D-galacturonic acid system has been investigated. The ions which are found to form particularly stable complexes with the galacturonate ligand strongly increase the yield of the reduction of iron(III) to iron(II). These findings are in agreement with the capability of some metal ions to form stable complexes through interaction both with the carboxylate group and with the ring oxygen atom of the sugar molecule, inducing opening of the ring and formation of a free aldehydic group. The importance of these processes in availability of iron to plant roots is emphasized.  相似文献   

12.
Hemocyanins are oligomeric metalloproteins containing binuclear copper centers that reversibly combine with oxygen molecules. The structural stability and functional properties of these proteins are modified by divalent cations. Equilibrium dialysis was used to study the reversible interaction of Callinectes sapidus and Limulus polyphemus hemocyanins with the divalent cations calcium, cadmium, zinc, copper, and mercury. The number of binding sites and association constants for each cation were obtained from an analysis of the binding data by a nonlinear least-squares minimization procedure. Spectral analysis showed Limulus hemocyanin to possess two mercury-reactive sulfhydryl groups per subunit (Kassoc = 2.02 X 10(45) M-1). Callinectes hemocyanin contains only one such group (Kassoc = 2.29 X 10(34) M-1). Cadmium and zinc are shown to substitute for calcium ions. Oxygen binding studies with Limulus hemocyanin showed that all five divalent metal ions increase its oxygen affinity. Calcium ions increase cooperativity of oxygen binding, while heavy-metal ions have an opposite effect. Binding of two mercuric ions per Limulus hemocyanin subunit irreversibly fixes the 48 subunit aggregate in a high-affinity noncooperative conformational state. These results offer a striking contrast to the functional consequences of heavy-metal ion interactions with Callinectes hemocyanin [Brouwer, M., Bonaventura, C., & Bonaventura, J. (1982) Biochemistry 21, 2529-2538]. The functional alterations associated with metal ion interactions are discussed within the context of an extension of the two-state model for allosteric transitions of Monod et al. [Monod, J., Wyman, J., & Changeux, J.P. (1965) J. Mol. Biol. 12, 88-118]. Incubation of Limulus oxy- or deoxyhemocyanin with mercuric chloride results in the conversion of 60% of the binuclear copper sites to stable half-apo sites. The remaining active sites are stable with respect to mercury-induced copper displacement when oxygen is bridging both coppers. In the absence of oxygen these sites will eventually lose both copper atoms. Under the same conditions 50% of the binuclear copper sites of Callinectes deoxyhemocyanin are converted to half-apo sites. In this case oxygen completely protects against copper displacement [Brouwer, M., Bonaventura, C., & Bonaventura, J. (1982) Biochemistry 21, 2529-2538]. The binuclear copper center of Busycon carica is not affected at all, demonstrating profound differences between the active sites of hemocyanins of a chelicerate arthropod (Limulus), a crustacean arthropod (Callinectes), and a gastropod mollusc (Busycon).  相似文献   

13.
Vitamin D3 (LH) complexes with manganese(II), iron(II), iron(III) and zinc(II) were identified in water-ethanol medium (30/70). Their stability constants were determined at 298 K and at a constant ionic strength of 0.100 M using potentiometric methods. The computerisation of the experimental data showed the presence of ML (M = metal, L = deprotonated vitamin D3) and ML2 species in all cases; in addition, the ML3 iron(III) complex was detected. The calculated overall stability constants beta for MnIIL, FeIIL, FeIIIL and ZnIIL are, respectively, in logarithms, 12.4, 16.5, 28.5 and 16.5. Under the experimental conditions, the only protonated species MLH detected was with iron(III).  相似文献   

14.
The potentiometric and spectroscopic methods were applied to describe the equilibria for the Cu(II), Ni(II), and Co(II), D-galactosamine solutions. The stability constants, the spectral data, and the results obtained earlier precisely defined the binding ability of the aminosugars.  相似文献   

15.
Biosorption is potentially an attractive technology for treatment of wastewater for retaining heavy metals from dilute solutions. This study investigated the feasibility of anaerobic granules as a novel type of biosorbent, for lead, copper, cadmium, and nickel removal from aqueous solutions. Anaerobic sludge supplied from a wastewater treatment plant in the province of Quebec was used. Anaerobic granules are microbial aggregates with a strong, compact and porous structure and excellent settling ability. After treatment of the biomass with Ca ions, the cation exchange capacity of the biomass was approximately 111 meq/100 g of biomass dry weight which is comparable to the metal binding capacities of commercial ion exchange resins. This work investigated the equilibrium, batch dynamics for the biosorption process. Binding capacity experiments using viable biomass revealed a higher value than those for nonviable biomass. Binding capacity experiments using non-viable biomass treated with Ca revealed a high value of metals uptake. The solution initial pH value affected metal sorption. Over the pH range of 4.0-5.5, pH-related effects were not significant. Meanwhile, at lower pH values the uptake capacity decreased. Time dependency experiments for the metal ions uptake showed that adsorption equilibrium was reached almost 30 min after metal addition. It was found that the q(max) for Pb2+, Cd2+, Cu2+, and Ni2+ ions, were 255, 60, 55, and 26 mg/g respectively (1.23, 0.53, 0.87, and 0.44 mmol/g respectively). The data pertaining to the sorption dependence upon metal ion concentration could be fitted to a Langmiur isotherm model. Based on the results, the anaerobic granules treated with Ca appear to be a promising biosorbent for removal of heavy metals from wastewater due to its optimal uptake of heavy metals, its particulate shape, compact porous structure, excellent settling ability, and its high mechanical strength.  相似文献   

16.
An 1H NMR (nuclear magnetic resonance) spectroscopic structural analysis of Cd2+ complexes formed with the pentapeptide phytochelatin, (NH3)+−(ψ-Glu-Cys)2−Gly−COO−(PC2), at a pH of 7.5 showed that the two thiol groups of the Cys residues and either the carbonyl or amide group of the peptide bond between Glu1 and Cys1 act as possible donor groups in the complexes at Cd2+/PC2 ratios up to 0.4. As the ratio increases, the carboxylate group of Glu2 and either the carbonyl or amide group of the peptide bond between Cys1 and Glu2 comes to serve as a donor group. The manner in which Cd2+ forms complexes with PC2 is distinctly different from Zn2+ and might account for the role of phytochelatin in Cd2+ detoxification. Electron absorption spectrometry demonstrated that the Cd2+ complexes are coordinated in a tetrahedral fashion by four thiol groups and that several sulfur atoms might bridge Cd2+ ions, resulting in the formation of polynuclear complexes. This contrasts with Zn2+ complex formation, which consists exclusively of a 1:1 complex.  相似文献   

17.
N-(2-Pyridyl)acetamide (aapH) complexes of palladium(II), cobalt(II), nickel(II), and copper(II) have been studied by means of magnetic susceptibilities, and infrared, electronic, and PMR spectra. In the octahedral complexes M(aapH)2X2(M = Co, Ni, Cu; X = Cl, Br, NCS, NO3), bidentate aapH is chelated through the pyridine-N and amid-O atomes, whereas in the square-planar Pd(aapH)2X2 (X = Cl, Br) unidentate aapH is coordinated through the pyridine-N atom alone. Under alkaline conditions aapH is deprotonated in the presence of palladium(II) to form Pd(aap)2·4H2O, aap being an anionic bidentate ligand and chelating through the pyridine-N and amide-O atoms.  相似文献   

18.
Putterill  Brandon  Rono  Charles  Makhubela  Banothile  Meyer  Debra  Gama  Ntombenhle 《Biometals》2022,35(4):771-784
BioMetals - Infection by the human immunodeficiency virus, which gives rise to acquired immunodeficiency syndrome, is still a major global health challenge, with millions of people being affected....  相似文献   

19.
The acid-base properties and Cu(II), Ni(II), Ag(I) and Hg(II) binding abilities of PAMAM dendrimer, L, and of the simple model compounds, the tetraamides of EDTA and PDTA, L1, were studied in solution by pH-metric methods and by 1H NMR and UV-Vis spectroscopy. PAMAM is hexabasic and six pKa values have been determined and assigned. PAMAM forms five identifiable complexes with copper(II), [CuLH4]6+, [CuLH2]4+, [CuLH]3+, [CuL]2+ and [CuLH-1]+ in the pH range 2-11 and three with nickel(II), [NiLH]3+, [NiL]2+ and [NiLH-1]+ in the pH range 7-11. The complex [CuLH4]6+, which contains two tertiary nitrogen and three amide oxygen atoms coordinated to the metal ion, is less stable than the analogous EDTA and PDTA tetraamide complexes [CuL1]2+, which contain two tertiary nitrogen and four amide oxygen atoms, due to ring size and charge effects. With increasing pH, [CuLH4]6+ undergoes deprotonation of two coordinated amide groups to give [CuLH2]4+ with a concomitant change from O-amide to N-amidate coordination. Surprisingly and in contrast to the tetraamide complexes [CuL1]2+, these two deprotonation steps could not be separated. As expected the nickel(II) complexes are less stable than their copper(II) analogues. The tetra-N-methylamides of EDTA, L1(b), and PDTA form mononuclear and binuclear complexes with Hg(II). In the case of L1(b) these have stoichiometries HgL1(b)Cl2, [HgL1(b)H−2Cl2]2−, [Hg2L1(b)Cl2]2+, Hg2L1(b)H−2Cl2 and [Hg2L1(b)H−5Cl2]3−. Based on 1H NMR and pH-metric data the proposed structure for HgL1(b)Cl2, the main tetraamide ligand containing species in the pH range <3-6.5, contains L1(b) coordinated to the metal ion through the two tertiary nitrogens and two amide oxygens while the structure of [HgL1(b)H−2Cl2]2−, the main tetraamide ligand species at pH 7.5-9.0, contains the ligand similarly coordinated but through two amidate nitrogen atoms instead of amide oxygens. The proposed structure of [Hg2L1(b)Cl2]2+, a minor species at pH 3-6.5, also based on 1H NMR and pH-metric data, contains each Hg(II) coordinated to a tertiary amino nitrogen, two amide oxygens and a chloride ligand while that of [Hg2L1(b)H−5Cl2]3−, contains each Hg(II) coordinated to a tertiary amino nitrogen, two amidate nitrogens, a chloride and a hydroxo ligand in the case of one of the Hg(II) ions. The parent EDTA and PDTA amides only form mononuclear complexes. PAMAM also forms dinuclear as well as mononuclear complexes with mercury(II) and silver(I). In the pH range 3-11 six complexes with Hg(II) i.e. [HgLH4Cl2]4+, [HgLH3Cl2]3+, [Hg2LCl2]2+, [Hg2LH−1Cl2]+, [HgLH−1Cl2] and [HgLH−2Cl2]2− were identified and only two with Ag(I), [AgLH3]4+ and [Ag2L]2+. Based on stoichiometries, stability constant comparisons and 1H NMR data, structures are proposed for these species. Hence [HgLH4Cl2]4+ is proposed to have a similar structure to [CuLH4]6+ while [Hg2LCl2]2+has a similar structure to [Hg2L1(b)H−5Cl2]3−.  相似文献   

20.
The reaction of Zn(ClO4)2 · 6H2O and Cu(ClO4)2 · 6H2O with H3Sas (H3Sas = N-(2-hydroxybenzyl)-L-aspartic acid in water afforded the complexes [Zn6(Sas)4(H2O)8]·5H2O (1) and [Cu(HSas)(H2O)] (2), respectively, which were characterized by infrared spectroscopy, elemental analysis, thermogravimetry and single-crystal X-ray crystallography. In 1, the pentanuclear clusters formed by four H3Sas ligands and five Zn(II) metal ions are bridged by the “[Zn(H2O)4]2+” cations to form 1D polymeric chains. While in 2, the mononuclear [Cu(HSas)(H2O)] repeating units form a 1D zigzag chain and further extended by strong intermolecular hydrogen bonds to form a 2D sheet. The different coordination geometries of Cu(II) and Zn(II) show significant influence on the polymeric structures.  相似文献   

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