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Metal Species (metal + species)
Selected AbstractsChromosomal antioxidant genes have metal ion-specific roles as determinants of bacterial metal toleranceENVIRONMENTAL MICROBIOLOGY, Issue 10 2009Joe J. Harrison Summary Microbiological metal toxicity involves redox reactions between metal species and cellular molecules, and therefore, we hypothesized that antioxidant systems might be chromosomal determinants affecting the susceptibility of bacteria to metal toxicity. Here, survival was quantified in metal ion-exposed planktonic cultures of several Escherichia coli strains, each bearing a mutation in a gene important for redox homeostasis. This characterized ,250 gene,metal combinations and identified that sodA, sodB, gor, trxA, gshA, grxA and marR have distinct roles in safeguarding or sensitizing cells to different toxic metal ions (Cr2O72,, Co2+, Cu2+, Ag+, Zn2+, AsO2,, SeO32, or TeO32,). To shed light on these observations, fluorescent sensors for reactive oxygen species (ROS) and reduced thiol (RSH) quantification were used to ascertain that different metal ions exert oxidative toxicity through disparate modes-of-action. These oxidative mechanisms of metal toxicity were categorized as involving ROS and thiol-disulfide chemistry together (AsO2,, SeO32,), ROS predominantly (Cu2+, Cr2O72,) or thiol-disulfide chemistry predominantly (Ag+, Co2+, Zn2+, TeO32,). Corresponding to this, promoter- luxCDABE fusions showed that toxic doses of different metal ions up- or downregulate the transcription of gene sets marking distinct pathways of cellular oxidative stress. Altogether, our findings suggest that different metal ions are lethal to cells through discrete pathways of oxidative biochemistry, and moreover, indicate that chromosomally encoded antioxidant systems may have metal ion-specific physiological roles as determinants of bacterial metal tolerance. [source] Pseudomonas fluorescens' view of the periodic tableENVIRONMENTAL MICROBIOLOGY, Issue 1 2008Matthew L. Workentine Summary Growth in a biofilm modulates microbial metal susceptibility, sometimes increasing the ability of microorganisms to withstand toxic metal species by several orders of magnitude. In this study, a high-throughput metal toxicity screen was initiated with the aim of correlating biological toxicity data in planktonic and biofilm cells to the physiochemical properties of metal ions. To this end, Pseudomonas fluorescens ATCC 13525 was grown in the Calgary Biofilm Device (CBD) and biofilms and planktonic cells of this microorganism were exposed to gradient arrays of different metal ions. These arrays included 44 different metals with representative compounds that spanned every group of the periodic table (except for the halogens and noble gases). The minimum inhibitory concentration (MIC), minimum bactericidal concentration (MBC) and minimum biofilm eradication concentration (MBEC) values were obtained after exposing the biofilms to metal ions for 4 h. Using these values, metal ion toxicity was correlated to the following ion-specific physicochemical parameters: standard reduction-oxidation potential, electronegativity, the solubility product of the corresponding metal,sulfide complex, the Pearson softness index, electron density and the covalent index. When the ions were grouped according to outer shell electron structure, we found that heavy metal ions gave the strongest correlations to these parameters and were more toxic on average than the other classes of the ions. Correlations were different for biofilms than for planktonic cells, indicating that chemical mechanisms of metal ion toxicity differ between the two modes of growth. We suggest that biofilms can specifically counter the toxic effects of certain physicochemical parameters, which may contribute to the increased ability of biofilms to withstand metal toxicity. [source] Dynamic coupled metal transport-speciation model: Application to assess a zinc-contaminated lakeENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 10 2004Satyendra P. Bhavsar Abstract A coupled metal transport and speciation/complexation model (TRANSPEC) has been developed to estimate the speciation and fate of multiple interconverting species in surface aquatic systems. Dynamic-TRANSPEC loosely, sequentially couples the speciation/complexation and fate modules that, for the unsteady state formulation, run alternatively at every time step. The speciation module first estimates species abundance using, in this version, MINEQL+ considering time-dependent changes in water and pore-water chemistry. The fate module is based on the quantitative water air sediment interaction (QWASI) model and fugacity/aquivalence formulation, with the option of using a pseudo-steady state solution to account for past discharges. Similarly to the QWASI model for organic contaminants, TRANSPEC assumes the instantaneous equilibrium distribution of metal species among dissolved, colloidal, and particulate phases based on ambient chemistry parameters that can be collected through conventional field methods. The model is illustrated with its application to Ross Lake (Manitoba, Canada) that has elevated Zn concentrations due to discharges over 70 years from a mining operation. Using measurements from field studies, the model reproduces year-round variations in Zn water concentrations. A 10-year projection for current conditions suggests decreasing Zn remobilization and export from the lake. Decreasing Zn loadings increases sediment-to-water transport but decreases water concentrations, and vice versa. Species distribution is affected by pH such that a decrease in pH increases metal export from the lake and vice versa. [source] Organic Ligands Made Porous: Magnetic and Catalytic Properties of Transition Metals Coordinated to the Surfaces of Mesoporous OrganosilicaADVANCED FUNCTIONAL MATERIALS, Issue 7 2010Andreas Kuschel Abstract Inorganic solids with porosity on the mesoscale possess a high internal surface area and a well-accessible pore system. Therefore, it is a relevant task to equip the surfaces of such materials with a maximum density of various organic functional groups. Among these functions it is the capability of coordinating to metal species as a ligand that is of extraordinary importance in many areas, for example, in catalysis. This paper describes how prominent ligands containing donor functions such as carboxylic, thio, chelating, or amine groups can be obtained in the form of nanoporous organosilica materials. The coordination of metal centers such as CoII, MnII, VIV, or PtIV is studied in detail. The magnetic properties of the corresponding materials and some applications in catalysis are reported. A quantitative determination of the surface density of donor atoms by distance measurements using EPR spectroscopy is shown. [source] Metal-Containing Carbon Nitride Compounds: A New Functional Organic,Metal Hybrid MaterialADVANCED MATERIALS, Issue 16 2009Xinchen Wang The electronic and optical functions of polymeric C3N4 can be easily modified by the inclusion of metal species such as Fe in its structure. The metal species lowers the bandgap and expands the light absorption of the material further into the visible region of the electromagnetic spectrum, while keeping a sufficient overpotential for carrying out oxidation reactions. [source] Poly(trimethylene carbonate) from Biometals-Based Initiators/Catalysts: Highly Efficient Immortal Ring-Opening Polymerization ProcessesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 9 2009Marion Helou Abstract The ring-opening polymerization (ROP) of trimethylene carbonate (TMC) was evaluated in bulk at 60,110,°C using various catalyst systems based on bio-friendly metals, including the metal bis(trimethylsilylamides) Mg[N(SiMe3)2]2, Ca[N(SiMe3)2]2(THF)2, Y[N(SiMe3)2]3, (BDI)Fe[N(SiMe3)2] [BDI=CH(CMeNC6H3 -2,6- i- Pr2)2], Fe[N(SiMe3)2]2, Fe[N(SiMe3)2]3, Zn[N(SiMe3)2]2, (BDI)Zn[N(SiMe3)2] and ZnEt2, associated with an alcohol such as isopropyl or benzyl alcohol. The actual metal alkoxide initiating species has been formed in situ prior to the addition of TMC. Introduction of the alcohol component in excess leads to the "immortal" ring-opening polymerization (ROP) of TMC. According to such an "immortal" ROP process of TMC, whichever the metal species, as many as 200 polycarbonate chains could be successfully grown from a unique metal center in a well controlled ROP process. The best performances were obtained using the discrete (BDI)Zn[N(SiMe3)2] precursor. Under optimized conditions, as many as 50,000 equivalents of TMC could be fully converted from as little as 20,ppm of this metallic precursor, allowing the preparation of a polytrimethylene carbonate (PTMC) with a molar mass as high as 185,200,g,mol,1 with a relatively narrow molar mass distribution (Mw/Mn=1.68). A double monomer feed experiment carried out with the (BDI)Zn[N(SiMe3)2]/BnOH initiating system proved the "living" character of the polymerization. Characterization of the PTMCs by NMR and size exclusion chromatography (SEC) showed well-defined ,-hydroxy-,-alkoxycarbonate telechelic polymers, highlighting the controlled character of this "living and immortal" ROP process. Using the (BDI)Zn[N(SiMe3)2] precursor, varying the alcohol (ROH) to 2-butanol, 3-buten-2-ol or 4-(trifluoromethyl)benzyl alcohol, revealed the versatility of this approach, allowing the preparation of accordingly end-functionalized HO-PTMC-OR polymers. The very low initial loading of metal catalyst considerably limits the potential toxicity and thus allows such polycarbonates to be used in the biomedical field. [source] Palladium and platinum sorption on a thiocarbamoyl-derivative of chitosanJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2010A. Butewicz Abstract Immobilizing thiourea onto chitosan allowed using the polymer for the recovery of platinum groups metals (PGMs) in acidic solutions (up to 1,2M HCl concentrations). At low HCl concentration protonated amine groups may sorb chloroanionic metal species (electrostatic attraction mechanism); however, most of sorption proceeds through chelation on sulfur containing groups (less sensitive to acidic conditions). The bi-site Langmuir equation was used for fitting sorption isotherms. The sorption of PGMs was weakly affected by the composition of the solution (presence of high concentration of anions and base metals). Maximum sorption capacities for Pd(II) and Pt(IV) ranged between 274 and 330 mg g,1 in 0.25M HCl solutions and decreased to 150,198 mg g,1 in 2M HCl solutions: Pd(II) sorption was systematically higher than Pt(IV) sorption. The pseudo-second rate equation was used for modeling the uptake kinetics. Agitation speed hardly affected uptake kinetics indicating that external diffusion resistance is not the rate controlling step. Desorption yield higher than 85% were obtained using thiourea in 0.1M HCl solution. The adsorbents could be reused for at least three cycles. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] Inhibitory effects of Cu, Zn, Ni and Co on nitrification and relevance of speciationJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 4 2010Ferhan Çeçen Abstract BACKGROUND: The speciation of metals is often overlooked in understanding their observed inhibitory effect in biological systems, in particular in nitrification systems. This study examines the effects of Cu, Zn, Ni and Co on a nitrifying sludge, where the aim is to relate inhibition to speciation. RESULTS: Nitrification inhibition was monitored by O2 and CO2 measurements, an approach rarely followed to date. The IC50 value of each metal was expressed in terms of total, free and labile metal. Zn and Cu formed similar species, but had different free and labile fractions. Although free and labile fractions of Cu were much lower than the others, it was the most inhibitory metal. Ni and Co exhibited quite different inhibitory effects on nitrification despite the formation of similar metal species. Co was the least inhibitory metal and exhibited its effect very slowly. CONCLUSION: The study is among the few which examine inhibition and speciation of several metals in a comparative way. In the same nitrification medium each metal formed different species, which is a factor to be considered in interpretation of inhibition. The results may be projected to nitrifying systems to clarify the underlying factors in inhibition. Copyright © 2009 Society of Chemical Industry [source] Hybrid metal,polymer composites from functional block copolymersJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 19 2005Robert B. Grubbs Abstract The combination of metals and polymers in hybrid materials is a research area of great current interest. A number of methods for controlling the positioning of metallic species within polymer matrices on the nanometer scale have been developed. This highlight focuses on the use of functional block copolymers for the localization of metal species, especially nanoparticles, on the nanometer scale through block copolymer phase segregation. Research from the author's group on the use of alkyne-functional block copolymers for the preparation of cobalt-containing materials is discussed in this context. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4323,4336, 2005 [source] Gettering in silicon photovoltaics: current state and future perspectivesPHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 4 2006M. Seibt Abstract This paper summarizes current understanding and predictive simulations of gettering processes predominantly applied in silicon photovoltaics. Special emphasis is put on various processes limiting gettering efficiency and kinetics, i.e. the mobility of interstitially dissolved metal species, the formation of the gettering layer, and the effect of immobile metal species. The latter are substitutional metal species, precipitates, complexes with defects related to non-metallic impurities, and finally the interaction with extended defects, in particular dislocations. Finally, alternative annealing schemes involving high-temperature rapid thermal processing are explored by simulations. It is shown that a processing window exists for a two-step process efficient for the removal of precipitates even under the constraints of a fixed thermal budget for phosphorus diffusion. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Selective organic synthesis through generation and reactivity control of hyper-coordinate metal speciesTHE CHEMICAL RECORD, Issue 6 2008Tamejiro Hiyama Abstract This paper is a review of my 40 years of research at Kyoto, Sagamihara, and Yokohama, all based on the generation of hyper-coordinate metal species such as ate complexes and pentacoordinate silicates. The topics are: (i) carbenoid reagents for carbon,carbon bond-forming reactions, (ii) nucleophilic substitution at acetal carbons using aluminate reagents, (iii) preparation of magnesium enolates and its reaction with nitriles, (iv) Cr(II) reagents for reduction of organic halides and highly selective carbon,carbon bond formation, (v) organic synthesis with organosilion reagents/fluoride ions, (vi) cross-coupling reaction of organosilicon compounds, and (vii) silicon-based conjugate addition to ,,,-unsaturated carbonyl acceptors. © 2008 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 8: 337,350; 2008: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.20162 [source] Cobalt- and Nickel-Catalyzed Regio- and Stereoselective Reductive Coupling of Alkynes, Allenes, and Alkenes with AlkenesCHEMISTRY - A EUROPEAN JOURNAL, Issue 35 2008Masilamani Jeganmohan Dr. Abstract Transition-metal-catalyzed coupling of two different CC , components through a metallacycle intermediate is a highly atom economical method to construct CC bonds in organic synthesis. The metal-catalyzed coupling of an alkene and alkyne generally gives an Alder-ene or reductive coupling product. In this article, we focus on the cobalt- and nickel-catalyzed reductive coupling of alkynes, allenes, and alkenes with alkenes. These reductive coupling reactions provide convenient methods for the synthesis of various alkenes, dienes, functionalized alkanes, lactones, lactams, and cyclic alcohols in a highly regio- and stereoselective manner. A chemselective formation of metallacyclopentene intermediate from the two different CC , components and a low-valence metal species plays a key role for the high regio- and stereoselectivity of the catalytic reaction. [source] | ||||||||||||||||