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Metal Ions (metal + ion)
Kinds of Metal Ions Terms modified by Metal Ions Selected AbstractsDesign of Neutral Metallomesogens from 5,5-Dimethyldipyrromethane: Metal Ion Mediated Control of Folding and Hairpin StructuresEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 32 2008Kelly A. Ames Abstract New ligands derived from 5,5-dimethyldipyrromethane and their corresponding neutral complexes with ZnII and PdII are described. The ligands incorporate either a hexacatenar [H2(1n), n = 1, 10, 12, 14 and 16], tetracatenar [H2(2n), n = 1 and 16] or an extended dicatenar structure [H2(3n), n = 1and 16]. Single-crystal X-ray structure determinations of [Zn2(11)2] and [Zn2(31)2] confirm a distorted tetrahedral geometry at ZnII to afford double-stranded helical structures, while the PdII species [Pd(31)] shows a distorted square-planar geometry with the ligand adopting an alternative hairpin conformation. The metal-free hexacatenar ligands H2(1n) (n = 10, 12, 14, 16) and the corresponding complexes [Zn2(116)2] and [Pd(1n)] (n = 12, 14, 16) are not mesomorphic. However, the tetracatenar complex [Zn2(216)2] generates a smectic mesophase, as confirmed by X-ray diffraction, while [Pd(216)] and the metal-free ligand H2(216) show no mesomorphic behaviour. Two of the extended dicatenar compounds, H2(316) and [Zn2(316)2] are non-mesomorphic, while [Pd(316)] displays a smectic A phase.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Stabilization of Long Cationic EMACs by Reduction or Loss of One Metal IonEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 27 2008Rayyat H. Ismayilov Abstract The new pyrimidyl- and naphthyridyl-modulated pentapyridyltetramine ligand (H3N9 -2pm) and its linear nona- and octanickel chain complexes were successfully synthesized. The nonanickel complex [Ni9(,9 -N9 -2pm)4Cl2](PF6)2 (1) contains two fully delocalized, mixed-valence [Ni2(napy)4]3+ units. Magnetic measurements performed on the defective octanuclear complex [Ni8(,8 -N9 -2pm)4Cl2](PF6)2 (2) demonstrate that the metal chain provides a pathway of magnetic superexchange coupling over the extended metal atom chain (EMAC). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Palladium-Catalyzed meso-Amination and Amidation of Porphyrins: Marked Acceleration with the Ni(II) Central Metal Ion.CHEMINFORM, Issue 1 2004Toshikatsu Takanami Abstract For Abstract see ChemInform Abstract in Full Text. [source] Peculiarities of Electrochemical Bismuth Film Formation in the Presence of Bromide and Heavy Metal IonsELECTROANALYSIS, Issue 15 2009Giedr, Grincien Abstract Bi films were deposited on glassy carbon electrode from solutions with and without KBr. The morphology of both types of the films was characterized by scanning electron microscopy (SEM), and their electrochemical behavior was studied by square wave (SWV) and cyclic voltammetry (CV). Bi films were also co-deposited with common analyte-heavy-metals in the presence of KBr and these films also were characterized by SEM, SWV and CV in order to understand the formation of the mixed metal films. All films studied had a different morphology. Bromide addition made the Bi films more compact and uniform, whereas Pb catalyzed Bi film deposition. [source] Facilitated Transfer of Alkali Metal Ions by a Tetraester Derivative of Thiacalix[4]arene at the Liquid,Liquid InterfaceELECTROANALYSIS, Issue 12 2008Akgemci, Emine Guler Abstract The facilitated transfer of alkali metal ions (Na+, K+, Rb+, and Cs+) by 25,26,27,28-tetraethoxycarbonylmethoxy-thiacalix[4]arene across the water/1,2-dichloroethane interface was investigated by cyclic voltammetry. The dependence of the half-wave transfer potential on the metal and ligand concentrations was used to formulate the stoichiometric ratio and to evaluate the association constants of the complexes formed between ionophore and metal ions. While the facilitated transfer of Li+ ion was not observed across the water/1,2-dichloroethane interface, the facilitated transfers were observed by formation of 1,:,1 (metal:ionophore) complex for Na+, K+, and Rb+ ions except for Cs+ ion. In the case of Cs+ a 1,:,2 (metal:ionophore) complex was obtained from its special electrochemical response to the variation of ligand concentrations in the organic phase. The logarithms of the complex association constants, for facilitated transfer of Na+, K+, Rb+, and Cs+, were estimated as 6.52, 7.75, 7.91 (log ,1°), and 8.36 (log ,2°), respectively. [source] Electrochemical Investigation of Binding of Heavy Metal Ions to Turkish LignitesELECTROANALYSIS, Issue 16 2004Erol Pehlivan Abstract Adsorption and desorption of Cu2+, Pb2+, Cd2+, Ni2+ and Zn2+ ions on samples of lignites (young brown coal) from three areas in the vicinity of Konya (Anatolia, Turkey) were followed using the polarographic method of analysis. This method enables the determination of free metal ions in suspensions containing both small and colloidal particles of lignite. Effects of pH, nature of the metal ion, and origin of the lignite on its adsorption capacity were followed. Binding is only between 5 and 30% reversible, indicating that ion exchange is not the predominant factor. The role of the size and shape of cavities inside pulverized lignite and of the functional groups inside these cavities was considered. [source] Selective Electrochemical Analysis of Various Metal Ions at an EDTA Bonded Conducting Polymer Modified ElectrodeELECTROANALYSIS, Issue 16 2004Aminur Rahman Abstract An EDTA-bonded conducting polymer modified electrode was prepared and characterized by FT-IR. The modified electrode was used for the selective electrochemical analysis of various trace metal ions such as, Cu(II), Hg(II), Pb(II), Co(II), Ni(II), Fe(II), Cd(II), and Zn(II) at the different pHs by linear sweep and square wave voltammetry. Dynamic ranges were obtained using square wave voltammetry from 0.1,,M to 10.0,,M for Co(II), Ni(II), Cd(II), Fe(II), and Zn(II) and 0.5,nM to 20,nM for Cu(II), Hg(II), and Pb(II) after 10,min of preconcentration. The detection limits were determined to be 0.1,nM, 0.3,nM, 0.4,nM, 50.0,nM, 60.0,nM, 65.0,nM, 80.0,nM, and 90.0,nM for Cu(II), Hg(II), Pb(II), Co(II), Ni(II), Cd(II), Fe(II), and Zn(II), respectively. The technique offers an excellent way for the selective trace determination of various heavy metal ions in a solution. [source] Synthesis and Structural Characterisation of Copper(II) 15-Metallacrown-5 Complexes with PbII, HgII, AgI, NaI and YIII Central Metal IonsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 19 2007Sabry Hamed Seda Abstract The new copper(II) 15-metallacrown-5 complexes with the central metal ions PbII, HgII, AgI, NaI and YIII, with the formula [MCu5L5]Xn {H2L is 2-picolinehydroxamic acid or (S)-phenylalaninehydroxamic acid and X, is NO3, or Cl,}, have been synthesised and characterised by NMR and UV/Vis spectroscopy, electrospray mass spectrometry and elemental analysis. The PbII - and HgII 15-metallacrown-5 complexes were obtained in the crystalline form as pyridine adducts [PbCu5(picha)5(py)6](NO3)2·3(py) and [HgCu5(picha)5(py)7](NO3)2·2(py) and their X-ray crystal structures were determined. In both complexes, each peripheral CuII ion of the metallacrown is coordinated by one pyridine molecule bonded in the axial position. In the case of the PbII derivative, one additional axial pyridine molecule is bound to the central metal ion, while in the case of the HgII derivative, two axial pyridine ligands are bound to the central HgII ion. The relative stability of the copper(II) 15-metallacrown-5 complexes with various central metal ions was determined on the basis of competition reactions. The relative preference of the 15-metallacrown-5 system for the central metal ion follows the series NaI, AgI < lanthanide(III), HgII < PbII.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] A Cyclic Fc,Histidine Conjugate: Synthesis and Properties , Interactions with Alkali Metal IonsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 5 2006Somenath Chowdhury Abstract The synthesis of the novel N,N, -(ferrocenophane-1,1,-diyldicarbonyl)-bridged histidine methyl ester 1 and of the acyclicbis(histidine methyl ester) derivative 3 are reported. The structure of 1 was studied in the solid state and in solution. The single-crystal structure of 1 shows that both proximal ferrocenyl (Fc) carbonyl groups are syn with respect to each other, which is a new structural motif for Fc,amino acid conjugates. This new syn conformation allows effective binding to alkali metal cations. Binding is evaluated by cyclic voltammetry monitoring the halfwave potential of the Fc group. Cation binding causes a shift to lower potential (Na+ > Li+ > K+, Cs+). Upon binding, compound 1 shows selectivity towards Na+ ions. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] A New Carrier for Selective Removal of Heavy Metal Ions from Aqueous Solutions through Bulk Liquid MembranesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 18 2004Nicoletta Spreti Abstract The carrier-mediated transport of heavy metal ions through bulk liquid membranes has been examined: toxic Hg2+, Cd2+ and Pb2+ ions were studied, along with Cu2+ ions for comparative purposes. The ability of a new carrier, 2,2,-bis(p -octyloxybenzyl)diethylenetriamine (bis- pODET), to complex and transport all the selected metal ions is reported. Differing affinities of the carrier for the different metal ions and the different experimental conditions required for their release into the receiving phase allowed the selective separation of equimolar binary mixtures. For Hg2+/Cd2+ and Hg2+/Pb2+ mixtures, two different separation methods were performed, while the inefficacy of the separation of Cd2+/Pb2+ and Hg2+/Cu2+ mixtures was for two different reasons: (i) the carrier is able to extract the metal ions with similar levels of ability, and (ii) the carrier metal ion complexes require the same acidity of the receiving phase to release the metal ions. The capability of the carrier to transport Hg2+ efficiently in consecutive cycles is also reported: over 90% of the metal ions were transferred into the receiving phase for three consecutive processes. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Carrier-Mediated Transport of Toxic Heavy Metal Ions in Bulk Liquid MembranesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 6 2004Lucia Brinchi Abstract Transport through a dichloromethane liquid membrane has been studied to investigate the ability of 1,1,7,7-tetraethyl-4-tetradecyldiethylenetriamine (TE14DT), previously tested for the transport of copper, to act as a carrier for toxic heavy metal ions such as Cd2+, Pb2+ and Hg2+. The carrier displayed a remarkable capability to extract all the metal ions from the source to the organic phases but only cadmium was efficiently transported across the membrane. The experimental conditions optimised for the transport of copper are inadequate for lead and mercury. In fact, the inefficacy of their transport could be due, as regards lead, to the slow diffusion of the complex through the membrane, while mercury remained in the organic phase because of the high stability of the mercury-carrier complex. Selectivity tests using binary mixtures of the metal ions showed TE14DT's capability to transport copper or cadmium also in the presence of lead in the source phase. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Structural Studies on Hydrogen-Bonding Receptors for Barbiturate Guests That Use Metal Ions as Allosteric InhibitorsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 1 2004Mohammad H. Al-Sayah Abstract Receptor 1 was designed to bind barbiturate substrates through a six-point hydrogen-bonding motif only in the absence of metal allosteric cofactors. It was predicted that the binding of metal ions by bipyridine ligands in 1 would result in a geometric change in the receptor to inhibit substrate recognition. However, receptor 1 showed minimal affinity for the barbiturate guests even in the absence of the metal. Binding studies on model compounds 2, 3, 5, and 6 revealed that the inactivity of 1 is due to an intramolecular hydrogen bond between the N,H donor groups and the nitrogen atoms on the first heterocycle of the bipyridine ligands. This intramolecular hydrogen-bonding was eliminated by altering the position of the tether between the bipyridine ligands and the active site to produce receptor 7. Consequently, the high affinity exhibited by 7 for the barbiturate substrate (Ka = 2.8±0.7 × 103M,1 in 9:1 CD2Cl2/CD3CN) was significantly reduced by the addition of ZnII ions as a negative allosteric co-factor. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Modulation of the Lifetime of Water Bound to Lanthanide Metal Ions in Complexes with Ligands Derived from 1,4,7,10-Tetraazacyclododecane Tetraacetate (DOTA)HELVETICA CHIMICA ACTA, Issue 5 2005Shanrong Zhang A series of di- and tetraamide derivatives of DOTA were synthesized, and their lanthanide(III) complexes were examined by multinuclear 1H-, 13C-, and 17O-NMR spectroscopy, and compared with literature data of similar, known complexes (Table). All ligands formed structures similar to the parent [LnIII(DOTA)], complexes, with four N-atoms and four O-atoms from DOTA and one O-atom from the inner-sphere water molecules. Interestingly, the lifetimes ,M of the inner-sphere, metal-bound water molecules vary widely, ranging from nano- to milliseconds, depending on the identity of the pendent amide side chains. In general, positively charged [LnIII(DOTA-tetraamide)]3+ complexes display the longest residence times (high ,M values), while complexes with additional charged functional groups on the extended amides display much smaller ,M values, even when the side groups are not directly coordinated to the central Ln3+ ions. The design of novel [LnIII(DOTA-tetraamide)]3+ complexes with a wide, tunable range of ,M values is of prime importance for the application of fast-responding, paramagnetic chemical-exchange-saturation-transfer (PARACEST) imaging agents used for the study of physiological and metabolic processes. [source] Combinatorial Fabrication of Fluorescent Patterns with Metal Ions Using Soft Lithography,ADVANCED MATERIALS, Issue 8 2006L. Basabe-Desmonts A new combinatorial methodology for the fabrication and direct visualization of fluorescent and metal-ion micrometer patterns is presented. Microcontact printing is used to transfer different metal salts onto a variety of fluorescent monolayers on glass (see figure). [source] Kinetics of Urea Decomposition in the Presence of Transition Metal Ions: Ni2+JOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 2 2006Bora Mavis The literature on kinetics of the urea decomposition reaction was reviewed for the 333,373 K range of temperature. Possible reactions in the pH range of 5,9 were identified. Kinetic simulations indicated significant accumulation of the cyanate intermediate in the pH-time,temperature range that was studied. The effects of Ni2+ hydrolysis and complexation with the urea decomposition products were incorporated into the simulations. The kinetic simulation of the rate of Ni2+ removal from the solutions was compared against the experimental data. The experimental results indicated an agglomerative growth mechanism for the precipitation process. Chemical analyses showed that the composition of the precipitate varies with digestion time, in agreement with the predictions of the kinetic simulation. [source] Metal-Chelating Amino Acids as Building Blocks for Synthetic Receptors Sensing Metal Ions and Histidine-Tagged Proteins.CHEMINFORM, Issue 9 2004Silke Hutschenreiter No abstract is available for this article. [source] ChemInform Abstract: Task-Specific Ionic Liquids for the Extraction of Metal Ions from Aqueous SolutionsCHEMINFORM, Issue 17 2001Ann E. Visser Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] ChemInform Abstract: Light-Emitting meso-Structured Sulfides with Hexagonal Symmetry: Supramolecular Assembly of [Ge4S10]4- Clusters with Trivalent Metal Ions and Cetylpyridinium Surfactant.CHEMINFORM, Issue 4 2001K. Kasthuri Rangan Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Can Electrophilicity Act as a Measure of the Redox Potential of First-Row Transition Metal Ions?CHEMISTRY - A EUROPEAN JOURNAL, Issue 33 2007Jan Moens Abstract Previous contributions concerning the computational approach to redox chemistry have made use of thermodynamic cycles and Car,Parrinello molecular dynamics simulations to obtain accurate redox potential values, whereas this article adopts a conceptual density functional theory (DFT) approach. Conceptual DFT descriptors have found widespread use in the study of thermodynamic and kinetic aspects of a variety of organic and inorganic reactions. However, redox reactions have not received much attention until now. In this contribution, we prove the usefulness of global and local electrophilicity descriptors for the prediction of the redox characteristics of first row transition metal ions (from Sc3+|Sc2+ to Cu3+|Cu2+) and introduce a scaled definition of the electrophilicity based on the number of electrons an electrophile ideally accepts. This scaled electrophilicity concept acts as a good quantitative estimate of the redox potential. We also identify the first solvation sphere together with the metal ion as the primary active region during the electron uptake process, whereas the second solvation sphere functions as a non-reactive continuum region. [source] Programming Heteropolymetallic Lanthanide Helicates: Thermodynamic Recognition of Different Metal Ions Along the StrandsCHEMISTRY - A EUROPEAN JOURNAL, Issue 5 2004Sébastien Floquet Dr. Abstract Under stoichiometric conditions, the segmental tris-tridentate ligand L9 assembles with two different lanthanide metal ions Ln1 and Ln2 (Ln1, Ln2=La, Nd, Sm, Eu, Yb, Lu, Y) to give mixtures of the heterotrimetallic triple-stranded helicates [(Ln1)x(Ln2)3,x(L9)3]9+ (x=0,3) in acetonitrile. The combination of qualitative (ESI-MS) and quantitative (1H NMR) speciations provides a set of thermodynamic data that were analysed with various statistical chemical models. A satisfying description requires the consideration of different affinities for the terminal N6O3 sites (k) and for the central N9 site (k) for each specific lanthanide. The nontrivial dependence of these parameters on the ionic radius provides size-discriminating effects that favour the formation of heterotrimetallic helicates in which the central site is occupied by the larger metal of the pair. Combining the latter enthalpic driving forces with entropic contributions due to specific stoichiometric conditions allows partial selection (i.e., programming) of a specific heterotrimetallic species in solution, which can be isolated by crystallisation, as demonstrated for [Eu2.04La0.96(L9)3](CF3SO3)9(CH3NO2)9 (1, Eu2.04La0.96C207H222N48O51S9F27, monoclinic, P21/c, Z=4) in which the cation [EuLaEu(L9)3]9+ is the major component in the crystal. The scope and limitation of this approach is discussed together with the conditions for explicitly considering intermetallic interaction parameters uLn1Ln2 in more sophisticated chemical models. [source] Self-Assembly of [B -SbW9O33]9, Subunit with Transition Metal Ions (Mn2+, Cu2+, Co2+) in Aqueous Solution: Syntheses, Structures and Magnetic Properties of Sandwich Type Polyoxometalates with Subvalent SbIII HeteroatomCHEMISTRY - AN ASIAN JOURNAL, Issue 5 2008Jing-Ping Wang Prof. Abstract Rational self-assembly of Sb2O3 and Na2WO4, or (NH4)18[NaSb9W21O86] with transition-metal ions (Mn2+, Cu2+, Co2+), in aqueous solution under controlled conditions yield a series of sandwich type complexes, namely, Na2H2[Mn2.5W1.5(H2O)8(B -,-SbW9O33)2],32,H2O (1), Na4H7[Na3(H2O)6Mn3(,-OAc)2(B -,-SbW9O33)2],20,H2O (OAc=acetate anion) (2), NaH8[Na2Cu4Cl(B -,-SbW9O33)2],21,H2O (3), Na8K[Na2K(H2O)2{Co(H2O)}3(B -,-SbW9O33)2], 10,H2O (4), and Na5H[{Co(H2O)2}3W(H2O)2(B -,-SbW9O33)2],11.5,H2O (5). These structures are determined by using the X-ray diffraction technique and further characterized by obtaining IR spectra and performing elemental analysis. Structure analysis reveals that polyoxoanions in 1 and 5 comprise of two [B -,-SbW9O33]9, building units, whereas 2, 3, and 4 consist of two isomerous [B -,-SbW9O33]9, building blocks, which are all linked by different transition-metal ions (Mn2+, Cu2+, or Co2+) with different quantitative nuclearity. It should be noted that compound 2 represents the first one-dimensional sinusoidal chain based on sandwich like tungstoantimonate building blocks through the carboxylate-bridging ligands. Additionally, 3 is constructed from sandwiched anions [Na2Cu4Cl(B -,-SbW9O33)2]9, linked to each other to form an infinitely extended 2D network, whereas 5 shows an interesting 3D framework built up from offset sandwich type polyoxoanion [{Co(H2O)2}3W(H2O)2(B -,-SbW9O33)2]6, linked by Co2+ and Na+ ions. EPR studies performed at 110,K and room temperature reveal that the metal cations (Mn2+, Cu2+, Co2+) reside in a square-pyramidal geometry in 2, 3, and 4. The magnetic behavior of 1,4 suggests the presence of weak antiferromagnetic coupling interactions between magnetic metal centers with the exchange integral J=,0.552,cm,1 in 2. [source] High Sensibility of Quantum Dots to Metal Ions Inspired by Hydroxyapatite MicrobeadsCHINESE JOURNAL OF CHEMISTRY, Issue 6 2010Xiang Wang Abstract An approach for the sensitive and selective determination of Ag+, Cu2+ and Hg2+ ions was developed based on the fluorescence quenching of mercaptopropionic acid (MPA) capped CdTe quantum dots in the existence of hydroxyapatite (HAP) nanoribbon spherulites. Among various metal ions investigated, it was found that the fluorescence of CdTe QDs was only sensitive to Ag+, Cu2+ and Hg2+ ions. The addition of HAP into the CdTe system could bring forward a sensitivity improvement of about 1 to 2 orders of magnitude in the detection of Ag+ and Cu2+ compared with the plain CdTe system without the existence of HAP; while there was no sensitization effect for Hg2+. Under optimal conditions, the detection limits for Ag+, Cu2+ and Hg2+ were 20, 56 and 3.0 nmol·L,1, respectively, and the linear ranges were 0.02,50, 0.056,54 and 0.003,2.4 µmol·L,1, respectively. Mechanisms of both QDs fluorescence quenching by metal ions and the sensitization effect by HAP were also discussed. [source] Activation Function of Chloroperoxidase in the Presence of Metal Ions at Elevated Temperature from 25 to 55°CCHINESE JOURNAL OF CHEMISTRY, Issue 7 2009Qiang GAO Abstract The investigation and comparison of chlorination activity of chloroperoxidase (CPO) from Caldariomyces fumago in metal ion solutions to those in pure buffer indicated that CPO could be effectively activated by some alkaline-earth metals and transition metals. The obtained maximum relative activity of CPO was 1.33 time at 75 µmol·L,1 Ca2+, 1.37 time at 90 µmol·L,1 Mg2+, 1.34 time at 90 µmol·L,1 Ni2+, and 1.27 time at 105 µmol·L,1 Co2+ at 25°C. Moreover, the CPO stability against temperature was improved in the presence of the above metal ions. At 55°C, CPO could retain only about 40% of activity whereas 75% and 81% of activity were maintained in Mg2+ and Ca2+ media, respectively. It was suggested that the metal ions bind to the acid-base catalytic groups Glu183, His105 and Asp106 around the active site of CPO, and activate CPO by both an enrichment of substrate concentration and the conformational change of CPO, which are favorable to the substrate access. The analysis of kinetic parameters indicated that the activation was mainly due to an increase in kcat values. The affinity and specificity of CPO to substrates were also improved in these metal ion media. The results in this work are promising in view of industrial applications of this versatile biological catalyst. [source] Biological significance of metals partitioned to subcellular fractions within earthworms (Aporrectodea caliginosa),ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 3 2006Martina G. Vijver Abstract Metal ions in excess of metabolic requirements are potentially toxic and must be removed from the vicinity of important biological molecules to protect organisms from adverse effects. Correspondingly, metals are sequestrated in various forms, defining the accumulation pattern and the magnitude of steady-state levels reached. To investigate the subcellular fractions over which Ca, Mg, Fe, Cu, Zn, Cd, Pb, Ni, and As are distributed, earthworms (Aporrectodea caliginosa) collected from the field were analyzed by isolating metal-rich granules and tissue fragments from intracellular microsomal and cytosolic fractions (i.e., heat-stable proteins and heat-denatured proteins). The fractions showed metal-specific binding capacity. Cadmium was mainly retrieved from the protein fractions. Copper was equally distributed over the protein fraction and the fraction comprising tissue fragments, cell membranes, and intact cells. Zinc, Ca, Mg, and As were mainly found in this fraction as well. Lead, Fe, and Ni were mainly isolated from the granular fraction. To study accumulation kinetics in the different fractions, three experiments were conducted in which earthworms were exposed to metal-spiked soil and a soil contaminated by anthropogenic inputs and, indigenous earthworms were exposed to field soils. Although kinetics showed variation, linear uptake and steady-state types of accumulation patterns could be understood according to subcellular compartmentalization. For risk assessment purposes, subcellular distribution of metals might allow for a more precise estimate of effects than total body burden. Identification of subcellular partitioning appears useful in determining the biological significance of steady-state levels reached in animals. [source] Effects of metals and pH on in vitro growth of Armillaria ostoyae and other root and butt rot fungi of red spruceFOREST PATHOLOGY, Issue 1 2001P. M. Wargo Armillaria ostoyae, Perenniporia subacida, Resinicium bicolor and Scytinostroma galactinum, root and butt rot fungi found on red spruce, Picea rubens, were tested, in vitro, for their sensitivity to metals typically found in high elevation forest soils where red spruce grows. Rhizomorph production by A. ostoyae from woody inocula in soils from red spruce stands at three elevations at each of five mountainous sites in the eastern United States was inhibited completely in the mineral soil from all elevations at all sites, and was also reduced significantly in the organic horizon from the upper two elevations at three of the sites. Inhibition was correlated with concentrations of metal ions in the soil. Growth of rhizomorphs into an agar medium containing lead and other heavy metals was inhibited for isolates of A. ostoyae from red spruce, but not for an isolate of Armillaria gallica from sugar maple; aluminium inhibited rhizomorph growth of isolates of both species. Mycelial growth of all four root and butt rot fungi was inhibited by lead, aluminium and other heavy metals depending on the solubility and concentration of metal and pH of the medium; growth inhibition was usually greater at an initial pH of 3.5 than at pH 4.5. Metal ions inhibited radial growth of Armillaria species more than that of the other three fungi. Rhizomorph growth of Armillaria was inhibited more than radial growth. Because local spread of A. ostoyae occurs frequently by means of rhizomorph growth between near roots, increases in lead, aluminium and other metals in the forest floor may contribute to this fungus' scarcity in high elevation soils and reduced incidence of infection at these sites in the eastern United States. [source] Thermo-Switchable Charge Transport and Electrocatalysis Using Metal-Ion-Modified pNIPAM-Functionalized ElectrodesADVANCED FUNCTIONAL MATERIALS, Issue 15 2009Michael Riskin Abstract Metal ions (Ag+, Cu2+, Hg2+) are incorporated into an electropolymerized, poly(N -isopropyl acrylamide), pNIPAM, thermosensitive polymer associated with an electrode using the "breathing-in" method. The ion-functionalized pNIPAM matrices reveal ion-dependent gel-to-solid phase-transition temperatures (28,±,1,°C, 25,±,1,°C, 40,±,1,°C for the Ag+, Cu2+, and Hg2+ -modified pNIPAM, respectively). Furthermore, the ion-functionalized polymers exhibit quasi-reversible redox properties, and the ions are reduced to the respective Ag0, Cu0, and Hg0 nanocluster-modified polymers. The metal-nanocluster-functionalized pNIPAM matrices enhance the electron transfer (they exhibit lower electron-transfer resistances) in the compacted states. The electron-transfer resistances of the metal-nanocluster-modified pNIPAM can be cycled between low and high values by temperature-induced switching of the polymer between its contracted solid and expanded gel states, respectively. The enhanced electron-transfer properties of the metal nanocluster-functionalized polymer are attributed to the contacting of the metal nanoclusters in the contracted state of the polymers. This temperature-switchable electron transfer across a Ag0 -modified pNIPAM was implemented to design a thermo-switchable electrocatalytic process (the temperature-switchable electrocatalyzed reduction of H2O2 by Ag0 -pNIPAM). [source] Application of a carbon sorbent for the removal of cadmium and other heavy metal ions from aqueous solutionJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 4 2002I El-Shafey Abstract Treatment of flax shive with sulfuric acid produces a carbonaceous material that has been used to remove metal ions from aqueous solution. Metal ions including Cd(II), Cu(II), Cr(III), Co(II), Ni(II), Zn(II) and Pb(II) have been investigated for kinetic behaviour and sorption capacities. These metal ions show fast sorption kinetics following a first order rate equation. Cadmium was chosen as representative of these metal ions and a detailed study was carried out. The effect of pH on sorption was studied and it was found that maximum uptake occurred above pH 3,7, sorption was accompanied by release of protons into the solution and a ratio of [H+] released to [Cd2+] sorbed of approximately 2 was found. The sorption capacity showed no significant increase with increase of temperature. The presence of other metal ions such as K+, Na+, Mg2+ and Ca2+ decreases the Cd(II) capacity, indicating competition for the ion exchange sites. Successive sorption of Cd(II) shows that the capacity exceeds the monolayer capacity calculated from the Langmuir equation. Column studies showed good performance over a total of seven cycles of loading/stripping. These studies indicate that the sorption mechanism for these metal ions is related to a reversible ion exchange process on the carbon surface. © 2002 Society of Chemical Industry [source] Effects on the removal of Pb2+ from aqueous solution by crab shellJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 11 2001Dong Seog Kim Abstract The effects of temperature, pH, chitin and chitosan on Pb2+ removal by crab shell were investigated. Pb2+ removal by crab shell was greater than that of chitin and chitosan, indicating that chitin did not contribute to Pb2+ removal by crab shell. The quantity and rate of Pb2+ removal increased as the pH value increased. The rate of Pb2+ removal increased with increased temperature, but the maximum amount of Pb2+ removal was constant irrespective of temperature. Metal ions (K+, Na+, Mg2+, Ca2+) were released from crab shell concomitant with Pb2+ removal by ion exchange. The amount of Ca2+ released was greater than any for other metal ions in both Pb2+ and Pb2+ -free solutions. The amount of Ca2+ released in Pb2+ solution was greater than that in Pb2+ -free solution, whereas CO32, release in Pb2+ solution was less than in Pb2+ -free solution. Pb2+ removal was mainly a consequence of dissolution of CaCO3(s) with consequence precipitation of Pb3(CO3)2(OH)2(s) and PbCO3(s). Pb2+ accelerated the dissolution of CaCO3(s) by ion exchange and the precipitation occurred both at the surface and in the inner part of the crab shell. © 2001 Society of Chemical Industry [source] l -leucine aminopeptidase production by filamentous Aspergillus fungiLETTERS IN APPLIED MICROBIOLOGY, Issue 6 2005K.M. Nampoothiri Abstract Aims:, To screen various filamentous fungi belonging to Aspergillus spp. producing leucine and methionine aminopeptidases. Methods and Results:, Twenty-eight Aspergillus strains representing 14 species within the genus were screened for l -leucine aminopeptidase (LAP) production in two media in shake flask fermentation. Two Aspergillus sojae (NRRL 1988 and NRRL 6271) and one Aspergillus oryzae (NRRL 6270) strains were selected as the best producers for further studies. The peak LAP activities were 2·61, 2·59 and 1·30 IU ml,1 for the three fungi on days 2, 5 and 4 respectively. In addition to LAP, l -methionine aminopeptidase (MAP) activity was also detected. Apart from submerged fermentation, the highest LAP yields by solid-state fermentation were 11·39, 17·40 and 13·02 IU g,1 dry matter for the above fungi. The temperature and pH optimum of the enzyme was found to be in the range of 65,75°C at pH 8·0,9·0 for all three fungi. Metal ions, Co2+ and Fe2+ in 2 mmol l,1 concentration apparently enhanced the relative enzyme activity and heat stability. Conclusions:, Two A. sojae (NRRL 1988 and NRRL 6271) and one A. oryzae (NRRL 6270) strains were found to be the best producers of LAP and MAP. The preliminary characterization studies revealed that the enzyme is considerably thermostable and belongs to the class metalloenzymes. Significance and Impact of the Study:, A good number of aspergilli were screened and the ability of the fungal aminopeptidase to release a particular N-terminal amino acid along with its high thermal stability, makes them interesting for controlling the degree of hydrolysis and flavour development for a wide range of substrate. [source] Cofactor effects on the protein folding reaction: Acceleration of ,-lactalbumin refolding by metal ionsPROTEIN SCIENCE, Issue 4 2006Natalia A. Bushmarina Abstract About 30% of proteins require cofactors for their proper folding. The effects of cofactors on the folding reaction have been investigated with ,-lactalbumin as a model protein and metal ions as cofactors. Metal ions accelerate the refolding of ,-lactalbumin by lessening the energy barrier between the molten globule state and the transition state, mainly by decreasing the difference of entropy between the two states. These effects are linked to metal ion binding to the protein in the native state. Hence, relationships between the metal affinities for the intermediate states and those for the native state are observed. Some residual specificity for the calcium ion is still observed in the molten globule state, this specificity getting closer in the transition state to that of the native state. The comparison between kinetic and steady-state data in association with the , value method indicates the binding of the metal ions on the unfolded state of ,-lactalbumin. Altogether, these results provide insight into cofactor effects on protein folding. They also suggest new possibilities to investigate the presence of residual native structures in the unfolded state of protein and the effects of such structures on the protein folding reaction and on protein stability. [source] | |||||||||||||||||||||||||||||||||||||||||||||||||||||||